CN110527828A - A method of vanadic anhydride is produced by high phosphorus vanadium-containing material - Google Patents
A method of vanadic anhydride is produced by high phosphorus vanadium-containing material Download PDFInfo
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- CN110527828A CN110527828A CN201910989432.2A CN201910989432A CN110527828A CN 110527828 A CN110527828 A CN 110527828A CN 201910989432 A CN201910989432 A CN 201910989432A CN 110527828 A CN110527828 A CN 110527828A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention provides a kind of methods by high phosphorus vanadium-containing material production vanadic anhydride, which comprises carries out dissolution after mixing high phosphorus vanadium-containing material with lye and reacts, solid-liquor separation obtains the first dissolution fluid and tailings；By the first dissolution fluid crystallisation by cooling, mixed crystal and the second dissolution fluid are obtained；It is mixed after mixed crystal is dissolved with calcification agent, reaction generates solid precipitating；Solid precipitating is made after slurries and is mixed with ammonium agent, is reacted under heating condition, obtains ammonium metavanadate solution and hybrid solid；By calcination processing after ammonium metavanadate solution crystallisation by cooling, vanadic anhydride product is obtained.The present invention dissolves out high phosphorus vanadium-containing material by using alkali liquor efficient, and the dissolution rate of vanadium reaches 93% or more, then is made the transition by calcification precipitating and ammoniumization, realizes efficiently separating for vanadium and phosphorus, the purity of vanadic anhydride product obtained reaches 98.5% or more；The method is easy to operate, and mild condition has industrial operability, it can be achieved that medium recycles.
Description
Technical field
The invention belongs to metallurgical vanadium extraction technical fields, are related to a kind of side by high phosphorus vanadium-containing material production vanadic anhydride
Method.
Background technique
Vanadium is applied as a kind of important transition metal element in fields such as steel, aerospace, chemical industry, electronic technology
Extensively, as the improvement of downstream application product upgrades, to the purity of vanadium product, more stringent requirements are proposed.The content of phosphorus is to measure
One important index of vanadium-containing material, the presence of phosphorus can significantly reduce the toughness of vanadium and vanadium alloy, plasticity, strong influence vanadium
The use of product.However often phosphorus content is higher for presently used vanadium-containing material, and in addition to stone containing navajoite, some waste materials containing vanadium, such as
During the recyclings such as discarded vanadium containing catalysts, slag containing vanadium smelting, it is also desirable to separate vanadium and phosphorus, five oxygen of high-purity are made
Change two vanadium.
Vanadium-containing material is obtained firstly the need of leaching containing vanadium solution, then carries out subsequent removal of impurities, purification, traditional processing method
It generally requires and first carries out calcining process, as sodium roasting, calcification baking or empty roasting are leached to obtain clinker, then using process is leached
Clinker is to obtain containing vanadium leachate, and since calcining process energy consumption is higher, vanadium will be contained by the way of acidleach or alkali leaching at present by also having
Material directly leaches, and then using the removal of impurities of the methods of extraction, chemical precipitation or ion exchange, when wherein phosphorus content is higher, needs
Dephosphorization processing first is carried out to leachate, just can be carried out subsequent precipitation technique, and current phosphorus removing method is usually that dephosphorization agent is added,
It will cause a large amount of vanadium loss while dephosphorization.
CN 109207740A discloses a kind of extraction vanadium method of vanadium-bearing slag of high calcium and high phosphor, and vanadium-bearing slag of high calcium and high phosphor is roasted to obtain
Then clinker uses sulfuric acid leaching, obtain the first leachate and the first residue, and the first leachate accesses bodied ferric sulfate as dephosphorization
Agent obtains solution containing vanadium after separation；After first residue leaches again, leachate alkaline reagent dephosphorization again is then used as level-one
The mother liquor of leaching, solution containing vanadium carry out precipitation, solid product calcining.Vanadium can be equally taken out of during this method dephosphorization, cause vanadium
Loss, and operating procedure is complex, process is numerous, and energy consumption is higher.
CN 105800689A discloses a kind of preparation method of ultrapure vanadic anhydride, is first cleaned in advance, and it is molten will to contain vanadium
Phosphorus and silicon in liquid are transferred to solid phase removing, then carry out calcification precipitation, and the impurity such as chromium, manganese, potassium, sodium are stayed and are removed in liquid phase, then
The transferred vanadium to solid phase turns molten to liquid phase using ammonium salt, using ammonium type cation exchange system, by the micro of liquid phase remnants
Cation replacement is ammonium ion, realizes deep purifying, then calcine to obtain vanadic anhydride through cooling precipitation and deamination.This method is only
Suitable for the lower processing containing vanadium solution of phosphorus content, if solution containing vanadium cleans when higher for phosphorus content, it will cause a large amount of of vanadium
Loss, and this method is related to the removal of impurities of different kinds of ions, operating procedure is numerous.
In conclusion the processing for high phosphorus vanadium-containing material, also needs Optimal improvements processing method, vanadium and phosphorus can either be realized
Efficiently separate, obtain high-purity vanadium product, and can simplify operating procedure, reduce cost.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide one kind produces five oxygen by high phosphorus vanadium-containing material
Change the method for two vanadium, the method is turned on the basis of alkali liquor efficient dissolves out high phosphorus vanadium-containing material by calcification separation and ammoniumization
Type realizes efficiently separating for vanadium and phosphorus, and the vanadic anhydride product of high-purity is prepared, it is right to greatly reduce phosphorus content height
The influence of product quality.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of methods by high phosphorus vanadium-containing material production vanadic anhydride, and the method includes following steps
It is rapid:
(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tail
Slag；
(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and second molten again
Liquid out；
(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；
(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted, obtain under heating condition
Ammonium metavanadate solution and hybrid solid；
(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.
In the present invention, high phosphorus vanadium-containing material is dissolved out using lye first, by crystallization so that need it is to be separated at
Dividing mainly includes vanadate and phosphate, recycles the difference of the two solubility, passes through calcification precipitating and ammoniumization makes the transition and realizes vanadium
With efficiently separating for phosphorus, high purity vanadic anhydride product is further prepared；The method is easy to operate, mild condition, cost compared with
Low, separation product can recycle, no waste discharge.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the content of phosphorus pentoxide is 3 in step (1) the high phosphorus vanadium-containing material
~45wt%, such as 3wt%, 6wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%, 40wt% or 45wt%
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, step (1) described lye includes sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the concentration of step (1) described lye be 10~80wt%, such as 10wt%, 20wt%, 30wt%,
40wt%, 50wt%, 60wt%, 70wt% or 80wt% etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable.
Preferably, it is (3~8) that step (1) lye and the liquid of high phosphorus vanadium-containing material, which consolidate mass ratio: 1, such as 3:1,4:
1,5:1,6:1,7:1 or 8:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
As currently preferred technical solution, the temperature of step (1) the dissolution reaction is 80~260 DEG C, such as 80
DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 240 DEG C or 260 DEG C etc., it is not limited to cited numerical value, the number
It is equally applicable to be worth other unlisted numerical value in range.
Preferably, the time of step (1) the dissolution reaction is 0.5~6h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, step (1) the dissolution reaction pressure be 0~1.5MPa, such as 0,0.2MPa, 0.5MPa, 0.8MPa,
1.0MPa, 1.2MPa or 1.5MPa etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.Wherein, heretofore described reaction pressure refers to gauge pressure.
In the present invention, due to the difference of the type of high phosphorus vanadium-containing material, when being dissolved out with lye, the concentration of required lye,
Additional amount has difference, and by the selection of dissolution reaction temperature, pressure, improves the dissolution rate of vanadium as far as possible.
Preferably, when step (1) dissolution is reacted, it is passed through oxidizing gas.
Preferably, the oxidizing gas includes oxygen and/or air.
In the present invention, the vanadium in vanadium product and vanadium-containing material is generally pentavalent vanadium, but may also have in vanadium-containing material
The presence of Low Valent Vanadium needs to be oxidized in dissolution, therefore is passed through oxidizing gas.
As currently preferred technical solution, the temperature of step (2) described crystallisation by cooling is 10~45 DEG C, such as 10
DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C or 45 DEG C etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable.
Preferably, step (2) the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material.
In the present invention, in step (2) lolute crystallization rate can reach 70~80%, such as 70%, 72%, 74%, 76%,
78% or 80% etc., and dissolve out the general excessive addition of lye when reacting, then after lolute crystallization, can still it be deposited in the second dissolution fluid
In lye and uncrystallized vanadate, phosphate, the dissolution that step (1) is re-used for vanadium-containing material is returned it into, it can also be again
It is secondary that uncrystallized vanadium is recycled.
In addition, the tailings that step (1) obtains usually is stained with the ion in dissolution fluid, washed, after washing
Tailings liquid can be with the common return step of the second dissolution fluid (1).
As currently preferred technical solution, step (3) the calcification agent includes calcium oxide, calcium hydroxide, calcium chloride
Any one in calcium nitrate or at least two combination, the combination is typical but non-limiting example has: calcium oxide and hydrogen-oxygen
Change the combination of calcium, the combination of calcium hydroxide and calcium chloride, calcium oxide, calcium hydroxide and combination of calcium nitrate etc..
Preferably, it is (1.2~2) that the additional amount of step (3) the calcification agent, which meets calcium vanadium molar ratio: 1, such as 1.2:1,
1.3:1,1.5:1,1.6:1,1.8:1 or 2:1 etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
As currently preferred technical solution, the temperature of step (3) described reaction is 80~100 DEG C, such as 80 DEG C, 84
DEG C, 88 DEG C, 90 DEG C, 93 DEG C, 96 DEG C or 100 DEG C etc., it is not limited to cited numerical value, other are not arranged in the numberical range
The numerical value of act is equally applicable.
Preferably, step (3) the solid precipitating includes calcium vanadate and calcium phosphate.
In the present invention, vanadic acid root and phosphate radical are precipitated by the addition of calcification agent, in the reaction temperature and alkalinity
Under the conditions of, vanadic acid root can generally be converted into metavanadic acid root, generate the separation for being convenient for subsequent vanadium and phosphorus after precipitating.
Preferably, after step (3) described reaction, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium.
Preferably, the mother liquor of precipitation of ammonium returns to the dissolution for mixed crystal in step (3).
As currently preferred technical solution, slurries are made using water in step (4) the solid precipitating.
Preferably, the concentration of the slurries be 20~30g/L, such as 20g/L, 22g/L, 24g/L, 25g/L, 27g/L,
28g/L or 30g/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (4) the ammonium agent includes ammonium carbonate and/or ammonium hydrogen carbonate.
Preferably, it is (1.2~1.6) that the additional amount of step (4) the ammonium agent, which meets ammonium vanadium molar ratio: 1, such as 1.2:
1,1.3:1,1.4:1,1.5:1 or 1.6:1 etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable.
In the present invention, calcium vanadate is converted to by using ammonium agent the calcium precipitation of more indissoluble, to obtain metavanadic acid
Ammonium, the characteristic changed greatly using ammonium metavanadate solubility with temperature are separated it with calcium precipitations such as calcium phosphate.
Preferably, step (4) heating temperature is not less than 80 DEG C, such as 80 DEG C, 83 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 93
DEG C, 96 DEG C, 98 DEG C, 100 DEG C or 102 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable, and preferably 80~100 DEG C.
In the present invention, the hybrid solid that step (4) obtains mainly includes calcium phosphate and calcium carbonate, can be used after washing
Make basic chemical industry raw material.
As currently preferred technical solution, step (5) described ammonium metavanadate solution is cooled to 40 DEG C or less and is tied
Crystalline substance, such as 40 DEG C, 36 DEG C, 32 DEG C, 30 DEG C, 27 DEG C, 25 DEG C or 20 DEG C etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.
Preferably, solid-liquor separation after step (5) described crystallization, gained liquid phase return step (4) are used as solid precipitating preparation
Water phase when slurries.
As currently preferred technical solution, the temperature of step (5) described calcination processing is 400~550 DEG C, such as
400 DEG C, 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 520 DEG C or 550 DEG C etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.
Preferably, the time of step (5) described calcination processing be 0.5~3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h or
3h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, the described method comprises the following steps:
(1) the high phosphorus vanadium-containing material that phosphorus pentoxide content is 3~45wt% is mixed with lye, the concentration of the lye
For 10~80wt%, the liquid-solid ratio of the lye and high phosphorus vanadium-containing material is (3~8): 1, then carry out dissolution reaction, reaction temperature
Degree is 80~260 DEG C, and the time is 0.5~6h, and reaction pressure is 0~1.5MPa, and solid-liquor separation obtains the first dissolution fluid and tailings；
(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), the temperature of crystallisation by cooling is 10~45 DEG C, then not good liquor
Gu isolated mixed crystal and the second dissolution fluid, the second dissolution fluid return step (1) is molten for high phosphorus vanadium-containing material
Out；
(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, the calcification agent includes calcium oxide, hydrogen
Any one in calcium oxide, calcium chloride or calcium nitrate or at least two combination, reaction generates solid precipitating, and the temperature of reaction is
80~100 DEG C, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium after reaction；
(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, the ammonium agent includes ammonium carbonate
And/or ammonium hydrogen carbonate, heating condition are reacted to 80 DEG C or more, and ammonium metavanadate solution and hybrid solid are obtained；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C or less to crystallize, then calcination processing, is forged
Burning temperature is 400~550 DEG C, and the time is 0.5~3h, obtains vanadic anhydride product.
Compared with prior art, the invention has the following advantages:
(1) present invention dissolves out high phosphorus vanadium-containing material using alkali liquor efficient first, and the dissolution rate of vanadium reaches 93% or more, then leads to
Calcification precipitating and ammoniumization transition are crossed, realizes efficiently separating for vanadium and phosphorus, the purity of vanadic anhydride product obtained reaches
98.5% or more；
(2) the method for the invention is easy to operate, it can be achieved that medium recycles, having industry can grasp mild condition
The property made.
Detailed description of the invention
Fig. 1 is the technique stream by high phosphorus vanadium-containing material production vanadic anhydride method that the specific embodiment of the invention 1 provides
Cheng Tu.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
Bright but following embodiment is only simple example of the invention, does not represent or limit the scope of the present invention, this hair
Bright protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, institute
State method the following steps are included:
(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tail
Slag；
(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and second molten again
Liquid out；
(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；
(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted, obtain under heating condition
Ammonium metavanadate solution and hybrid solid；
(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
Present embodiments provide a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
For a kind of waste catalyst, essential element composition is as shown in table 1.
The composition of waste catalyst essential element described in 1 embodiment 1 of table
| Element composition | Al | Ca | Cr | Fe | Mg | Mn | P | Si | V |
| Content (wt%) | 0.0306 | 0.044 | 0.0912 | 0.016 | 0.0126 | 0.02 | 19.48 | 0.057 | 30.45 |
The process flow chart of the method is as shown in Figure 1, comprising the following steps:
(1) it is dissolved out after mixing above-mentioned waste catalyst 100g with the sodium hydroxide solution 400g that concentration is 30wt%
Reaction, reacts 2h under 100 DEG C, condition of normal pressure, the first dissolution fluid and tailings is obtained by filtration；
(2) the first dissolution fluid that step (1) obtains is cooled to 45 DEG C to crystallize, is obtained by filtration again containing sodium phosphate
With the mixed crystal and the second dissolution fluid of sodium vanadate, the second dissolution fluid return step (1) is used for the dissolution of waste catalyst；
(3) solution of the 25g/L containing vanadium is obtained after dissolving the mixed crystal that step (2) obtains, solution is heated to 80 DEG C,
Calcium oxide is added by calcium vanadium molar ratio 2:1, reaction generates calcium vanadate and calcium phosphate solid precipitating；
(4) the solid precipitating that step (3) obtains being broken into slurries using water, concentration of slurry 20wt% is heated to 80 DEG C,
Ammonium hydrogen carbonate is added by ammonium vanadium molar ratio 1.5:1, obtains ammonium metavanadate solution and the hybrid solid containing calcium carbonate and calcium phosphate；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C to crystallize, obtains ammonium metavanadate crystal, so
Calcination processing 1.5h under the conditions of 500 DEG C afterwards, obtains vanadic anhydride product.
In the present embodiment, the dissolution rate of vanadium can reach 93.2% in step (1), and the dissolution rate of phosphorus is 94.1%, step (5)
The purity of middle vanadic anhydride reaches 99.1%.
Embodiment 2:
Present embodiments provide a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
It is in the same manner as in Example 1, it the described method comprises the following steps:
(1) dissolve out after mixing above-mentioned vanadium-containing material 100g with the potassium hydroxide solution 300g that concentration is 50wt% anti-
It answers, reacts 1h under the conditions of 140 DEG C, 0.5MPa, the first dissolution fluid and tailings is obtained by filtration；
(2) the first dissolution fluid that step (1) obtains is cooled to 30 DEG C to crystallize, is obtained by filtration again containing sodium phosphate
With the mixed crystal and the second dissolution fluid of sodium vanadate, the second dissolution fluid return step (1) is used for the dissolution of vanadium-containing material；
(3) solution of the 30g/L containing vanadium is obtained after dissolving the mixed crystal that step (2) obtains, solution is heated to 90 DEG C,
Calcium hydroxide is added by calcium vanadium molar ratio 1.6:1, reaction generates calcium vanadate and calcium phosphate solid precipitating；
(4) the solid precipitating that step (3) obtains being broken into slurries using water, concentration of slurry 25wt% is heated to 90 DEG C,
Ammonium carbonate is added by ammonium vanadium molar ratio 1.3:1, obtains ammonium metavanadate solution and the hybrid solid containing calcium carbonate and calcium phosphate；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 30 DEG C to crystallize, obtains ammonium metavanadate crystal, so
Calcination processing 2.5h under the conditions of 450 DEG C afterwards, obtains vanadic anhydride product.
In the present embodiment, the dissolution rate of vanadium can reach 95.4% in step (1), and the dissolution rate of phosphorus is 96.3%, step (5)
The purity of middle vanadic anhydride reaches 99.3%.
Embodiment 3:
Present embodiments provide a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
It is in the same manner as in Example 1, it the described method comprises the following steps:
(1) dissolve out after mixing above-mentioned vanadium-containing material 100g with the sodium hydroxide solution 800g that concentration is 10wt% anti-
It answers, reacts 0.5h under the conditions of 180 DEG C, 1.0MPa, the first dissolution fluid and tailings is obtained by filtration；
(2) the first dissolution fluid that step (1) obtains is cooled to 15 DEG C to crystallize, is obtained by filtration again containing sodium phosphate
With the mixed crystal and the second dissolution fluid of sodium vanadate, the second dissolution fluid return step (1) is used for the dissolution of vanadium-containing material；
(3) solution of the 20g/L containing vanadium is obtained after dissolving the mixed crystal that step (2) obtains, solution is heated to 100
DEG C, calcium chloride is added by calcium vanadium molar ratio 1.2:1, reaction generates calcium vanadate and calcium phosphate solid precipitating；
(4) the solid precipitating that step (3) obtains is broken into slurries using water, concentration of slurry 30wt% is heated to 100
DEG C, ammonium hydrogen carbonate is added by ammonium vanadium molar ratio 1.2:1, obtains ammonium metavanadate solution and the mixing containing calcium carbonate and calcium phosphate is consolidated
Body；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 20 DEG C to crystallize, obtains ammonium metavanadate crystal, so
Calcination processing 0.5h under the conditions of 550 DEG C afterwards, obtains vanadic anhydride product.
In the present embodiment, the dissolution rate of vanadium can reach 96.2% in step (1), and the dissolution rate of phosphorus is 96.1%, step (5)
The purity of middle vanadic anhydride reaches 99.5%.
Embodiment 4:
Present embodiments provide a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
For high phosphorus slag, composition is as shown in table 2.
The composition of high phosphorus slag described in 2 embodiment 4 of table
| Ingredient | V2O5 | CaO | TiO2 | MnO2 | Cr2O3 | FeO | Al2O3 | SiO2 | MgO | P2O5 |
| Content (wt%) | 2.57 | 41.91 | 1.90 | 1.57 | 1.23 | 24.28 | 1.85 | 7.94 | 11.90 | 3.45 |
It the described method comprises the following steps:
(1) dissolve out after mixing above-mentioned vanadium-containing material 100g with the sodium hydroxide solution 400g that concentration is 40wt% anti-
It answers, reacts 4h under the conditions of 80 DEG C, 1.5MPa, the first dissolution fluid and tailings is obtained by filtration；
(2) the first dissolution fluid that step (1) obtains is cooled to 40 DEG C to crystallize, is obtained by filtration again containing sodium phosphate
With the mixed crystal and the second dissolution fluid of sodium vanadate, the second dissolution fluid return step (1) is used for the dissolution of vanadium-containing material；
(3) solution of the 30g/L containing vanadium is obtained after dissolving the mixed crystal that step (2) obtains, solution is heated to 85 DEG C,
Calcium hydroxide is added by calcium vanadium molar ratio 1.8:1, reaction generates calcium vanadate and calcium phosphate solid precipitating；
(4) the solid precipitating that step (3) obtains being broken into slurries using water, concentration of slurry 25wt% is heated to 90 DEG C,
Ammonium hydrogen carbonate is added by ammonium vanadium molar ratio 1.4:1, obtains ammonium metavanadate solution and the hybrid solid containing calcium carbonate and calcium phosphate；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C to crystallize, obtains ammonium metavanadate crystal, so
Calcination processing 2h under the conditions of 500 DEG C afterwards, obtains vanadic anhydride product.
In the present embodiment, the dissolution rate of vanadium can reach 93.3% in step (1), and the dissolution rate of phosphorus is 84.5%, step (5)
The purity of middle vanadic anhydride reaches 98.7%.
Embodiment 5:
Present embodiments provide a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
It is in the same manner as in Example 4, it the described method comprises the following steps:
(1) dissolve out after mixing above-mentioned vanadium-containing material 100g with the potassium hydroxide solution 300g that concentration is 60wt% anti-
It answers, reacts 3h under the conditions of 120 DEG C, 0.2MPa, the first dissolution fluid and tailings is obtained by filtration；
(2) the first dissolution fluid that step (1) obtains is cooled to 35 DEG C to crystallize, is obtained by filtration again containing sodium phosphate
With the mixed crystal and the second dissolution fluid of sodium vanadate, the second dissolution fluid return step (1) is used for the dissolution of vanadium-containing material；
(3) solution of the 30g/L containing vanadium is obtained after dissolving the mixed crystal that step (2) obtains, solution is heated to 90 DEG C,
Calcium nitrate is added by calcium vanadium molar ratio 1.4:1, reaction generates calcium vanadate and calcium phosphate solid precipitating；
(4) the solid precipitating that step (3) obtains being broken into slurries using water, concentration of slurry 25wt% is heated to 80 DEG C,
Ammonium carbonate is added by ammonium vanadium molar ratio 1.5:1, obtains ammonium metavanadate solution and the hybrid solid containing calcium carbonate and calcium phosphate；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C to crystallize, obtains ammonium metavanadate crystal, so
Calcination processing 3h under the conditions of 400 DEG C afterwards, obtains vanadic anhydride product.
In the present embodiment, the dissolution rate of vanadium can reach 93% in step (1), and the dissolution rate of phosphorus is 86%, five in step (5)
The purity of V 2 O reaches 98.5%.
Comparative example 1:
This comparative example provides a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, the high phosphorus vanadium-containing material
In the same manner as in Example 1, the method is only that referring to the method in embodiment 1, difference: not including step (2), i.e. step
(1) the first dissolution fluid obtained directly carries out step (3).
In this comparative example, due to not carrying out vanadate and phosphatic crystallization treatment after the dissolution of high phosphorus vanadium-containing material, at this time
The basicity of dissolution fluid is higher, is directly added into calcification agent, and the rate of deposition of vanadium greatly reduces, only 34% so that the rate of recovery of vanadium and
The yield of vanadic anhydride is substantially reduced.
It can be seen that the present invention with comparative example based on the above embodiments and dissolve out high phosphorus object containing vanadium by using alkali liquor efficient
Material, the dissolution rate of vanadium reach 93% or more, then are made the transition by calcification precipitating and ammoniumization, realize efficiently separating for vanadium and phosphorus, make
The purity of the vanadic anhydride product obtained reaches 98.5% or more；The method is easy to operate, and mild condition is, it can be achieved that medium
It recycles, has industrial operability.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
It is limited to above-mentioned method detailed, that is, does not mean that the present invention must rely on the above method and could implement.The technology of technical field
Personnel are it will be clearly understood that any improvement in the present invention, to the raw materials used in the present invention, the equivalence replacement of operation and auxiliary material, behaviour
The addition of work, the selection etc. of concrete mode, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, which is characterized in that the described method comprises the following steps:
(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tailings；
(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and the second dissolution again
Liquid；
(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；
(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted under heating condition, obtain inclined vanadium
Acid ammonium solution and hybrid solid；
(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.
2. the method according to claim 1, wherein phosphorus pentoxide in step (1) the high phosphorus vanadium-containing material
Content be 3~45wt%；
Preferably, step (1) described lye includes sodium hydroxide solution and/or potassium hydroxide solution；
Preferably, the concentration of step (1) described lye is 10~80wt%；
Preferably, it is (3~8) that step (1) lye and the liquid of high phosphorus vanadium-containing material, which consolidate mass ratio: 1.
3. method according to claim 1 or 2, which is characterized in that step (1) it is described dissolution reaction temperature be 80~
260℃；
Preferably, the time of step (1) the dissolution reaction is 0.5~6h；
Preferably, step (1) the dissolution reaction pressure is 0~1.5MPa；
Preferably, when step (1) dissolution is reacted, it is passed through oxidizing gas；
Preferably, the oxidizing gas includes oxygen and/or air.
4. method according to claim 1-3, which is characterized in that the temperature of step (2) described crystallisation by cooling is
10~45 DEG C；
Preferably, step (2) the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material.
5. method according to claim 1-4, which is characterized in that step (3) the calcification agent include calcium oxide,
Any one in calcium hydroxide, calcium chloride or calcium nitrate or at least two combination；
Preferably, it is (1.2~2) that the additional amount of step (3) the calcification agent, which meets calcium vanadium molar ratio: 1.
6. method according to claim 1-5, which is characterized in that the temperature of step (3) described reaction be 80~
100℃；
Preferably, step (3) the solid precipitating includes calcium vanadate and calcium phosphate；
Preferably, after step (3) described reaction, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium；
Preferably, the mother liquor of precipitation of ammonium returns to the dissolution for mixed crystal in step (3).
7. method according to claim 1-6, which is characterized in that step (4) the solid precipitating uses water system
At slurries；
Preferably, the concentration of the slurries is 20~30g/L；
Preferably, step (4) the ammonium agent includes ammonium carbonate and/or ammonium hydrogen carbonate；
Preferably, it is (1.2~1.6) that the additional amount of step (4) the ammonium agent, which meets ammonium vanadium molar ratio: 1；
Preferably, step (4) heating temperature is not less than 80 DEG C, preferably 80~100 DEG C.
8. method according to claim 1-7, which is characterized in that step (5) ammonium metavanadate solution is cooling
It is crystallized to 40 DEG C or less；
Preferably, solid-liquor separation after step (5) described crystallization, gained liquid phase return step (4) are used as solid precipitating and prepare slurries
When water phase.
9. method according to claim 1-8, which is characterized in that the temperature of step (5) described calcination processing is
400~550 DEG C；
Preferably, the time of step (5) described calcination processing is 0.5~3h.
10. -9 described in any item methods according to claim 1, which is characterized in that the described method comprises the following steps:
(1) the high phosphorus vanadium-containing material that phosphorus pentoxide content is 3~45wt% is mixed with lye, the concentration of the lye is 10
It is (3~8) that the liquid of~80wt%, the lye and high phosphorus vanadium-containing material, which consolidates mass ratio: 1, then carry out dissolution reaction, reaction temperature
Degree is 80~260 DEG C, and the time is 0.5~6h, and reaction pressure is 0~1.5MPa, and solid-liquor separation obtains the first dissolution fluid and tailings；
(2) temperature of the first dissolution fluid crystallisation by cooling for obtaining step (1), crystallisation by cooling is 10~45 DEG C, then not good liquor divides admittedly
From mixed crystal and the second dissolution fluid is obtained, the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material；
(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, the calcification agent includes calcium oxide, hydroxide
Any one in calcium, calcium chloride or calcium nitrate or at least two combination, reaction generates solid precipitating, the temperature of reaction is 80~
100 DEG C, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium after reaction；
(4) solid that step (3) obtains precipitating is made after slurries and mix with ammonium agent, the ammonium agent include ammonium carbonate with/
Or ammonium hydrogen carbonate, heating condition are reacted to 80 DEG C or more, and ammonium metavanadate solution and hybrid solid are obtained；
(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C or less to crystallize, then calcination processing, calcining temperature
Degree is 400~550 DEG C, and the time is 0.5~3h, obtains vanadic anhydride product.
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| CN112174204A (en) * | 2020-09-11 | 2021-01-05 | 河钢承德钒钛新材料有限公司 | Method for producing vanadium pentoxide by using waste VPO catalyst |
| CN112251618A (en) * | 2020-09-11 | 2021-01-22 | 河钢承德钒钛新材料有限公司 | Method for producing ammonium metavanadate from waste VPO catalyst |
| CN112266017A (en) * | 2020-09-11 | 2021-01-26 | 河钢承德钒钛新材料有限公司 | Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste |
| WO2024045513A1 (en) * | 2022-08-29 | 2024-03-07 | 广东邦普循环科技有限公司 | Method for recovering sodium vanadium phosphate positive electrode material |
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| CN112174204A (en) * | 2020-09-11 | 2021-01-05 | 河钢承德钒钛新材料有限公司 | Method for producing vanadium pentoxide by using waste VPO catalyst |
| CN112251618A (en) * | 2020-09-11 | 2021-01-22 | 河钢承德钒钛新材料有限公司 | Method for producing ammonium metavanadate from waste VPO catalyst |
| CN112266017A (en) * | 2020-09-11 | 2021-01-26 | 河钢承德钒钛新材料有限公司 | Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste |
| CN112266017B (en) * | 2020-09-11 | 2023-08-15 | 河钢承德钒钛新材料有限公司 | Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste |
| WO2024045513A1 (en) * | 2022-08-29 | 2024-03-07 | 广东邦普循环科技有限公司 | Method for recovering sodium vanadium phosphate positive electrode material |
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