CN105366722A - Normal temperature extraction method for producing high-purity vanadium pentoxide - Google Patents
Normal temperature extraction method for producing high-purity vanadium pentoxide Download PDFInfo
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- CN105366722A CN105366722A CN201510871635.3A CN201510871635A CN105366722A CN 105366722 A CN105366722 A CN 105366722A CN 201510871635 A CN201510871635 A CN 201510871635A CN 105366722 A CN105366722 A CN 105366722A
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- high purity
- solid
- normal temperature
- vanadic anhydride
- vanadium pentoxide
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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 126
- 238000000605 extraction Methods 0.000 title claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000001704 evaporation Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 26
- 239000012498 ultrapure water Substances 0.000 claims description 26
- 238000003828 vacuum filtration Methods 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- -1 NH4NO3 Chemical compound 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 239000012809 cooling fluid Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 230000002000 scavenging effect Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006200 vaporizer Substances 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing high-purity vanadium pentoxide by normal temperature extraction. The method disclosed by the invention solves the problem that according to a preparation method in the prior art, the unit consumption of an intermediate raw material is increased, a process flow is tedious and the product quality is not high. The method disclosed by the invention comprises the steps of: (1) slowly adding industrial ammonium metavanadate and/or industrial vanadium pentoxide into an extracting agent and selectively dissolving ammonium metavanadate and/or vanadium pentoxide to form a vanadium-containing solution; adding a precipitator into the vanadium-containing solution to precipitate impurities; (2) obtaining a filtrate after a filter operation; (3) heating and evaporating the filtrate, adjusting the pH of the evaporated liquid to 1-6, and then obtaining a solid-liquid mixed liquid by cooling crystallization; (4) performing solid-liquid separation on the solid-liquid mixed liquid, and cleaning and filtering the solid by a cleaning agent; and (5) baking the filtered solid at a temperature of 400-600 DEG C, then cooling the solid and preparing a finished product. The method disclosed by the invention has advantages of being simple in process and low in cost, and good in the product quality and the like.
Description
Technical field
The present invention relates to the preparation method of high purity vanadic anhydride, what be specifically related to is the method that high purity vanadic anhydride is produced in normal temperature extraction.
Background technology
Extract from navajoite stone in the technique of Vanadium Pentoxide in FLAKES, after roasting ion-exchange gained desorbed solution in Vanadium Pentoxide in FLAKES product in containing Fe
+ 2, Pb
+ 4, Cu
+ 2, Cr
+ 3, Cd
+ 2, S
1-2, As
-2, K
+ 1, Na
+ 1etc. plurality of impurities, need purify and just can obtain highly purified Vanadium Pentoxide in FLAKES product.High purity vanadic anhydride is widely used in the field such as aerospace, vanadium cell, has wide market outlook.
In prior art, the method for purification of high purity vanadic anhydride is carried out mostly under neutrality or weak basic condition, and preparation process is under this condition too tediously long, although through twice crystallization, its purity only reaches 99.0%.Present method effectively can obtain high purity vanadic anhydride under normal temperature condition, and its purity can reach more than 99.9%, very high purity, and adopt the method for the acid extractive crystallization of normal temperature, its operation is easier, and the additional substance consumed in technological process is less, and cost is cheaper.
The patent of publication number CN101456587A provides " a kind of production method of high purity vanadic anhydride ", it is characterized in that with NaOH, Na
2cO
3as precipitation agent, make a large amount of positively charged ions generate precipitation, then use KClO
3as oxygenant, at about 90 DEG C temperature, the Low Valent Vanadium in solution is oxidized to Vanadium Pentoxide in FLAKES, finally with dilute sulphuric acid adjustment solution pH value, after filtration, calcining obtains the higher Vanadium Pentoxide in FLAKES product of purity in an oxidizing environment.This method rotation calcining link is high to equipment requirements, investment is large, and oxidation operation energy consumption of heating is higher, and the positively charged ion adding precipitation agent and oxygenant is difficult in later stage removing, and generally, quality product is difficult to control refining effect.
Summary of the invention
The intermediate raw material unit consumption that the object of the invention is to overcome preparation method in prior art increases, technical process is tediously long, and the problem that quality product is not high; A kind of normal temperature extraction solved the problem is provided to produce the method for high purity vanadic anhydride.
For achieving the above object, technical scheme of the present invention is as follows:
The method of high purity vanadic anhydride is produced in normal temperature extraction, comprising:
(1) by industrial ammonium meta-vanadate or/and industrial Vanadium Pentoxide in FLAKES adds in extraction agent under agitation slowly, optionally dissolve ammonium meta-vanadate or/and Vanadium Pentoxide in FLAKES, formed containing vanadium solution; Contamination precipitation is made containing adding precipitation agent in vanadium solution;
(2) after filter operation, filtrate is obtained;
(3) filtrate heating evaporation, after evaporation by the pH regulator of liquid to 1-6, then obtain solid-liquid mixed solution by crystallisation by cooling;
(4) solid-liquid mixed solution is carried out solid-liquid separation, solid clean-out system cleaning and filtering;
(5) solid after filtering toasts at 400-600 DEG C of temperature, then after cooling, makes finished product.Solid after filtration baking time at 400-600 DEG C of temperature is 2-12 hour.
By the high purity vanadic anhydride that the present invention produces, its production cost only only has 6000-8000 yuan/ton, with low cost, Be very effective.
Described extraction agent is made up of one or more formulas in A1-A5;
A1: by mass percent concentration be 0.5-3.0% Peracetic Acid, the high purity water of 1.0-6.0% ammonia, 91.0-98.5% forms;
A2: by mass percent concentration be 0.6-6.0% hydrogen peroxide, 1.0-9.0% ammonia, 85.0-98.4% high purity water form;
A3: be that the ethamine of 0.2-6.0% and the high purity water of 94.0-99.8% form by mass percent concentration;
A4: be that the methylamine of 0.2-8.0% and the high purity water of 92.0-99.8% form by mass percent concentration;
A5: be that the quadrol of 0.2-5.0% and the high purity water of 95.0-99.8% form by mass percent concentration.
Described precipitation agent is by Na
2cO
3, (NH
4)
2cO
3(NH
4)
2one or more in S are formed; Described often liter contains Na in vanadium solution
2cO
3(NH
4)
2cO
3add-on be 0.2-6.0g, (NH
4)
2the add-on of S is 0.6-6.0g.
After extraction liquid extraction, most foreign metal ion can be removed, then by after the process of precipitation agent, the metal ion of residue trace can be become Precipitation.Principal reaction is as follows:
（1）Fe+2+S-2=FeS↓；（2）Cu+2+S-2=CuS↓；
（3）Pb+2+S-2=PbS↓；（4）Cr+2+S-2=CrS↓；
（5）Cd+2+S-2=CdS↓；（6）Ca+2+CO3-2=CaCO3↓。
Described clean-out system is made up of one or more in Na2CO3, NH4NO3, acetone and ethanol; Wherein, Na
2cO
3concentration is 10g-80g/L, NH
4nO
3concentration is 10-70g/L, acetone concentration is 10g-80g/L, and alcohol concn is 40g-120g/L.
The detailed process of described step (1) is as follows:
By industrial ammonium meta-vanadate or/and industrial Vanadium Pentoxide in FLAKES adds in extraction agent under agitation slowly, optionally dissolve ammonium meta-vanadate or/and Vanadium Pentoxide in FLAKES, formed containing vanadium solution; Stirring 10-30 minute containing adding precipitation agent in vanadium solution, then carrying out vacuum filtration realizes solid-liquid separation afterwards to leave standstill 30-60 minute, the filtering net of vacuum filtration is 800-5000 order.
In order to cost-saving better, reduce the admixture loss added, and effectively reduce the waste liquid of discharging, when the filtrate of vacuum filtration being evaporated in described step (3), after the condensation of gas of this filtrate evaporation, become ammoniacal liquor, and then recycling use.
Separate out in order to the ammonium meta-vanadate in filtrate and Vanadium Pentoxide in FLAKES can be made better, in described step (3), the steam output of filtrate is the 10-40% of filtrate cumulative volume, regulate its pH value to 1-5 by acid after evaporation, and then pass through crystallisation by cooling, till xln is separated out completely, obtain solid-liquid mixed solution.
Preferred as one, the nitric acid of the acid of described adjust ph to be mass percent concentration be 10-70%.
In order to improve the purity of product better, the detailed process of described step (4) is as follows: by vacuum filtration, solid-liquid mixed solution is carried out solid-liquid separation, clean solid 3-8 time with clean-out system, in the process of cleaning, carry out vacuum filtration, the filtering net of vacuum filtration is 800-5000 order.
Further, in described step (5), finished product is packed after levigate.
The present invention compared with prior art, has the following advantages and beneficial effect:
1, the present invention has the features such as technique is simple, cost is low, and in the present invention, the cost of finished product per ton is about 6000-8000 unit; Adopt method of the present invention, part extraction liquid also can be recycled simultaneously;
2, good product quality of the present invention, the purity of finished product of the present invention can reach more than 99.9%, and higher than in prior art, other carry out the method for purifying far away.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The method of high purity vanadic anhydride is produced in normal temperature extraction, and detailed process is as follows:
(1) 1000g industry ammonium meta-vanadate is first taken, configuration extraction liquid;
Extraction liquid contain the hydrogen peroxide of volume hundred to 2.0%, the ammonia of 1.6% and 97.4% high purity water;
Industrial ammonium meta-vanadate is added slowly in 30 liters of extraction liquids, stirring and dissolving under normal temperature condition, after industrial ammonium meta-vanadate has all dissolved, left standstill 1-6 hour and obtain containing vanadium solution;
In the present invention, this normal temperature condition is 5 ~ 35 DEG C, and in the present embodiment, this normal temperature condition is 25 DEG C.
(2) first carry out vacuum filtration with the G4 sand core filter of 1000 milliliters to containing vanadium solution, the high purity water having filtered rear 200-800ml washs 2-8 time;
Then under agitation, the solid Na of 20g is added
2cO
3be the Na of 30% with 20ml mass percent
2s, continues stirring 30 minutes, leaves standstill 24 hours, carries out vacuum filtration afterwards obtain filtrate with G4 sand core filter.
(3) after filtering, filtrate is placed in evaporation withdrawer to evaporate, after steam output is cumulative volume 30%, neutralize with the nitric acid that mass percent is 20%, filtrate pH is made to reach 2, by neutralization after liquid in water cooler with water cooling to room temperature, until ammonium meta-vanadate is all separated out, obtain solid-liquid mixed solution.Ammoniacal liquor is become, recycling use after condenses after evaporation.
(4) cooled solid-liquid mixed solution carries out vacuum filtration, and having filtered rear use 30 mass per liter per-cent is the NH of 0.1%
4nO
3scavenging solution clean under the condition of vacuum filtration.
(5) after having cleaned, high-purity ammonium meta-vanadate is placed in retort furnace, under 550 DEG C of temperature condition, carries out calcination 4 hours, after calcination is complete, be cooled to room temperature rapidly, sieve can pack with 100 order sub-sieves in the environment that drying is dustless.
Take out 1.0g sample and carry out impurity analysis, quality product reaches 99.91% after testing.
Embodiment 2
The difference of the present embodiment and embodiment 1 is, this extraction liquid in the present embodiment, precipitation agent are different with the composition of clean-out system, and precipitation agent specifically add step difference, and the condition of reaction is different, specifically arranges as follows:
(1) first take 1000g industry ammonium meta-vanadate, configuration extraction liquid: extraction liquid contain mass percent concentration be the hydrogen peroxide of 2.5%, the ammonia of 2.0% and 95.5% high purity water.Then added slowly in 25 liters of extraction liquids by industrial ammonium meta-vanadate, add precipitation agent and stir while adding extraction liquid, this precipitation agent comprises the Na of 1.5g/L
2cO
3with 0.6g/L (NH
4)
2s, after ammonium meta-vanadate dissolves completely, leaves standstill the solution obtaining after 6 hours and contain vanadium.
(2) vacuum filtration acquisition filtrate is carried out with the husky core strainer of G4 of 1000 milliliters.
(3) filtrate feeding evaporation withdrawer carries out evaporation recovery, after evaporator evaporation goes out total liquid volume 20%, stop evaporation, open vaporizer lid and add the nitric acid that a certain amount of concentration is 50% under agitation, by the price modification of liquid pH value to 6, move into cooling fluid water by liquid cooling to room temperature, leave standstill 24 hours, till ammonium meta-vanadate crystallization is all separated out, and acquisition solid-liquid mixed solution (by analyzing, V in liquid
2o
5concentration is less than 1g/ml and is considered as successfully crystallization).Ammoniacal liquor is become, recycling use after condenses after evaporation.
(4) ammonium meta-vanadate crystal and liquid mixture being sent in the husky core strainer of 2000MLG4 and filter with vacuum filtration process, after filtration, is that 5% acetone high purity water scavenging solution cleans 10 times with the mass percent concentration of about 20 liters.
(5) after having cleaned, high-purity ammonium meta-vanadate crystal is sent in square quartz crucible, quartz crucible is positioned in retort furnace, dry 8 hours at 450 DEG C of temperature.Be quickly cooled to room temperature afterwards, then sieved by the high purity vanadic anhydride powder of reddish-brown 100 object sub-sieves, can pack, analyzing and testing purity of vanadium pentoxide is 99.92%.
Embodiment 3
The difference of the present embodiment and embodiment 2 is, this extraction liquid in the present embodiment, precipitation agent are different with the composition of clean-out system, and the condition of reaction is different, and specific operation process is as follows:
(1) first take 1000g industry Vanadium Pentoxide in FLAKES, configuration extraction liquid: extraction liquid contain mass percent concentration be the Peracetic Acid of 0.6%, the ammonia of 3.6% and 95.8% high purity water.Then at room temperature slowly stir and add in 25 liters of extraction liquids by industrial Vanadium Pentoxide in FLAKES, continue stirred liq afterwards and add precipitation agent, this precipitation agent comprises 0.3g/L(NH
4)
2cO
3, 0.2g/L(NH4)
2s, after Vanadium Pentoxide in FLAKES has all dissolved, has stopped stirring, has left standstill 3 hours.
(2) vacuum filtration is carried out with the husky core strainer of 1000MLG4.
(3) after having filtered, filtrate is sent into evaporation withdrawer and carry out evaporation recovery, after liquid evaporation falls 15% of cumulative volume, stop evaporation, can be used as extraction liquid after the cold liquid that evaporation is reclaimed and recycle.Use the HNO of 25% under agitation
3evaporated liquor PH is adjusted to 2, then send chiller water to be cooled to room temperature, treat that ammonium meta-vanadate crystal is all separated out, in detection remaining liq, Vanadium Pentoxide in FLAKES concentration is less than 1g/L is qualified.
(4) sent by solidliquid mixture the husky core strainer of 2000MLG4 to carry out vacuum filtration, after having filtered, clean solidliquid mixture 6 times with containing 30g/L ethanol high purity water solution 10 liters, use 5L high purity water cleaning solid-liquid mixture 3 times afterwards again.
(5) cleaned high-purity ammonium meta-vanadate is sent in rectangle quartz crucible, dry 5 hours at 500 DEG C of temperature, be down to rapidly the high purity vanadic anhydride that room temperature obtains reddish-brown afterwards, sieve with 100 object sub-sieves and pack.
It is 99.95% that above-mentioned finished product detects the purity content obtaining Vanadium Pentoxide in FLAKES by analysis, and wherein, impurity Si content is 1ppm, Fe content is 8ppm.
Embodiment 4
The difference of the present embodiment and embodiment 1-3 be the composition of this extraction liquid, precipitation agent and clean-out system in the present embodiment close to or exceed the upper limit of the ratio range in claims, specific operation process is as follows:
(1) first take 1000g industry Vanadium Pentoxide in FLAKES, configuration extraction liquid: extraction liquid contain mass percent concentration be the hydrogen peroxide of 6.6%, the ammonia of 9% and 84.4% high purity water.Then at room temperature slowly stir and add in 15 liters of extraction liquids by industrial Vanadium Pentoxide in FLAKES, continue stirred liq afterwards and add precipitation agent, this precipitation agent comprises 9.0/L(NH
4)
2cO
3, 6.6g/L(NH4)
2s, after Vanadium Pentoxide in FLAKES has all dissolved, has stopped stirring, has left standstill 2 hours.
(2) vacuum filtration is carried out with the husky core strainer of 1000MLG4.
(3) after having filtered, filtrate is sent into evaporation withdrawer and carry out evaporation recovery, after liquid evaporation falls 35% of cumulative volume, stop evaporation, can be used as extraction liquid after the cold liquid that evaporation is reclaimed and recycle.Use the HNO of 68% under agitation
3evaporated liquor PH is adjusted to 5, then send chiller water to be cooled to room temperature, treat that ammonium meta-vanadate crystal is all separated out, in detection remaining liq, Vanadium Pentoxide in FLAKES concentration is less than 1g/L is qualified.
(4) the husky core strainer of 2000MLG4 is sent by solidliquid mixture to carry out vacuum filtration, after having filtered, with containing 70g/LNH
4nO
3high purity water solution 10 liters cleaning solidliquid mixture 6 times, cleans solid-liquid mixture 3 times with 5L high purity water afterwards again.
(5) cleaned high-purity ammonium meta-vanadate is sent in rectangle quartz crucible, dry 6 hours at 600 DEG C of temperature, be down to rapidly the high purity vanadic anhydride that room temperature obtains reddish-brown afterwards, sieve with 100 object sub-sieves and pack.
It is 99.2% that above-mentioned finished product detects the purity content obtaining Vanadium Pentoxide in FLAKES by analysis, and wherein, impurity Si content is 20ppm, Fe content is 50ppm.
Embodiment 5
The difference of the present embodiment and embodiment 1-4 is that the composition of this extraction liquid, precipitation agent and clean-out system in the present embodiment is near or below the lower limit of the ratio range in claims, and specific operation process is as follows:
(1) 1000g industry Vanadium Pentoxide in FLAKES is first taken, configuration extraction liquid: it is the ethamine of 0.3% and the high purity water of 99.7% that extraction liquid contains mass percent concentration.Then at room temperature slowly stir and add 60 liters of extraction liquids and dissolve industrial Vanadium Pentoxide in FLAKES, continue stirred liq afterwards and add precipitation agent, this precipitation agent comprises 0.1/L(NH
4)
2cO
3, 0.1g/L(NH4)
2s, after Vanadium Pentoxide in FLAKES has all dissolved, has stopped stirring, has left standstill 2 hours.
(2) vacuum filtration is carried out with the husky core strainer of 1000MLG4.
(3) after having filtered, filtrate is sent into evaporation withdrawer and carry out evaporation recovery, after liquid evaporation falls 10% of cumulative volume, stop evaporation, can be used as extraction liquid after the cold liquid that evaporation is reclaimed and recycle.Use the HNO of 12% under agitation
3evaporated liquor PH is adjusted to 5, then send chiller water to be cooled to room temperature, treat that ammonium meta-vanadate crystal is all separated out, in detection remaining liq, Vanadium Pentoxide in FLAKES concentration is less than 1g/L is qualified.
(4) sent by solidliquid mixture the husky core strainer of 2000MLG4 to carry out vacuum filtration, after having filtered, clean solidliquid mixture 6 times with containing 10g/L acetone high purity water solution 10 liters, use 5L high purity water cleaning solid-liquid mixture 3 times afterwards again.
(5) cleaned high-purity ammonium meta-vanadate is sent in rectangle quartz crucible, dry 6 hours at 400 DEG C of temperature, be down to rapidly the high purity vanadic anhydride that room temperature obtains reddish-brown afterwards, sieve with 100 object sub-sieves and pack.
It is 99.70% that above-mentioned finished product detects the purity content obtaining Vanadium Pentoxide in FLAKES by analysis, and wherein, impurity Si content is 5ppm, Fe content is 15ppm, and this embodiment supplies consumption is comparatively large, without economic benefit.
Embodiment 6
The present embodiment and the difference of embodiment 1 are that in the present embodiment, the proportioning of this extraction liquid is different, and in the present embodiment, this extraction liquid is composed as follows:
A1:0.6% Peracetic Acid, 3.2% ammonia, 97.1% high purity water;
Or the methylamine of A3:3% and the high purity water of 97%;
Or the quadrol of A5:1.5% and the high purity water of 98.5%.
Carry out analyzing and testing to the finished product adopting the extraction liquid of above-mentioned different components and proportioning to obtain, the purity content situation obtaining Vanadium Pentoxide in FLAKES is as follows:
When adopting the extraction liquid of above-mentioned A1 moiety, the purity content of this Vanadium Pentoxide in FLAKES is 99.92%, and wherein, impurity Si content is 6ppm, Fe content is 16ppm;
When adopting the extraction liquid of above-mentioned A3 moiety, the purity content of this Vanadium Pentoxide in FLAKES is 99.91%, and wherein, impurity Si content is 8ppm, Fe content is 15ppm;
When adopting the extraction liquid of above-mentioned A5 moiety, the purity content of this Vanadium Pentoxide in FLAKES is 99.89%, and wherein, impurity Si content is 9ppm, Fe content is 18ppm.
Above-described embodiment is only the preferred embodiments of the present invention, not limiting the scope of the invention, as long as adopt principle of design of the present invention, and the change carried out non-creativeness work on this basis and make, all should belong within protection scope of the present invention.
Claims (10)
1. the method for high purity vanadic anhydride is produced in normal temperature extraction, it is characterized in that, comprising:
(1) by industrial ammonium meta-vanadate or/and industrial Vanadium Pentoxide in FLAKES adds in extraction agent slowly, optionally dissolve ammonium meta-vanadate or/and Vanadium Pentoxide in FLAKES, formed containing vanadium solution; Contamination precipitation is made containing adding precipitation agent in vanadium solution;
(2) after filter operation, filtrate is obtained;
(3) filtrate heating evaporation, after evaporation by the pH regulator of liquid to 1-6, then obtain solid-liquid mixed solution by crystallisation by cooling;
(4) solid-liquid mixed solution is carried out solid-liquid separation, solid clean-out system cleaning and filtering;
(5) solid after filtering toasts at 400-600 DEG C of temperature, then after cooling, makes finished product.
2. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, and it is characterized in that, described extraction agent is made up of one or more formulas in A1-A5;
A1: by mass percent concentration be 0.5-3.0% Peracetic Acid, the high purity water of 1.0-6.0% ammonia, 91.0-98.5% forms;
A2: by mass percent concentration be 0.6-6.0% hydrogen peroxide, 1.0-9.0% ammonia, 85.0-98.4% high purity water form;
A3: be that the ethamine of 0.2-6.0% and the high purity water of 94.0-99.8% form by mass percent concentration;
A4: be that the methylamine of 0.2-8.0% and the high purity water of 92.0-99.8% form by mass percent concentration;
A5: be that the quadrol of 0.2-5.0% and the high purity water of 95.0-99.8% form by mass percent concentration.
3. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, and it is characterized in that, described precipitation agent is by Na
2cO
3, (NH
4)
2cO
3(NH
4)
2one or more in S are formed; Described often liter contains Na in vanadium solution
2cO
3(NH
4)
2cO
3add-on be 0.2-6g, (NH
4)
2the add-on of S is 0.6-6g.
4. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, and it is characterized in that, described clean-out system is by Na
2cO
3, NH
4nO
3, one or more in acetone and ethanol form; Wherein, Na
2cO
3concentration is 10g-80g/L, NH
4nO
3concentration is 10g-70g/L, acetone concentration is 10g-80g/L, and alcohol concn is 40g-120g/L.
5. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, and it is characterized in that, the detailed process of described step (1) is as follows:
By industrial ammonium meta-vanadate or/and industrial Vanadium Pentoxide in FLAKES adds in extraction agent under agitation slowly, optionally dissolve ammonium meta-vanadate or/and Vanadium Pentoxide in FLAKES, formed containing vanadium solution; Stirring 10-30 minute containing adding precipitation agent in vanadium solution, then carrying out vacuum filtration realizes solid-liquid separation afterwards to leave standstill 30-60 minute, the filtering net of vacuum filtration is 800-5000 order.
6. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, it is characterized in that, when the filtrate of filtration being evaporated in described step (3), becomes ammoniacal liquor after the condensation of gas of this filtrate evaporation, and then recycling use.
7. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, it is characterized in that, in described step (3), the steam output of filtrate is the 10-40% of filtrate cumulative volume, regulate its pH value to 1-5 by acid after evaporation, and then pass through crystallisation by cooling, till xln is separated out completely, obtain solid-liquid mixed solution.
8. the method for high purity vanadic anhydride is produced in normal temperature according to claim 7 extraction, it is characterized in that, the nitric acid of the acid of described adjust ph to be mass percent concentration be 10-70%.
9. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, it is characterized in that, the detailed process of described step (4) is as follows: by vacuum filtration, solid-liquid mixed solution is carried out solid-liquid separation, solid is cleaned 3-8 time with clean-out system, in the process of cleaning, carry out vacuum filtration, the filtering net of vacuum filtration is 800-5000 order.
10. the method for high purity vanadic anhydride is produced in normal temperature extraction according to claim 1, and it is characterized in that, in described step (5), finished product is packed after levigate.
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| 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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| 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 |
| CN106966431A (en) * | 2017-05-15 | 2017-07-21 | 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 |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849795A (en) * | 2011-07-02 | 2013-01-02 | 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5014565B2 (en) * | 2004-04-08 | 2012-08-29 | Ｊｘ日鉱日石金属株式会社 | High purity V2O5 and production method thereof |
| 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 |
| CN105060344A (en) * | 2015-07-20 | 2015-11-18 | 常州市好利莱光电科技有限公司 | Method for extracting vanadium pentoxide from waste vanadium catalyst |
| CN105366722B (en) * | 2015-12-02 | 2017-08-25 | 雅安市中甫新能源开发有限公司 | The method of normal temperature extraction production high purity vanadic anhydride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849795A (en) * | 2011-07-02 | 2013-01-02 | 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106966431A (en) * | 2017-05-15 | 2017-07-21 | 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 |
| 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 |
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| CN105366722B (en) | 2017-08-25 |
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