CN106282563A - A kind of method utilizing solution containing vanadium directly to prepare barium oxide - Google Patents
A kind of method utilizing solution containing vanadium directly to prepare barium oxide Download PDFInfo
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- CN106282563A CN106282563A CN201610771691.4A CN201610771691A CN106282563A CN 106282563 A CN106282563 A CN 106282563A CN 201610771691 A CN201610771691 A CN 201610771691A CN 106282563 A CN106282563 A CN 106282563A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, said method comprising the steps of: (1) carries out calcification precipitation reaction to addition calcium oxide in the solution containing vanadium of remove impurity, and solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；(2) adding water after being mixed homogeneously with oxalic acid by calcium vanadate solid and be configured to reaction paste and carry out reacting by heating, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；(3) adding alkali metal hydroxide aqueous solution in vanadyl oxalate solution and/or ammonia reacts, after reaction, solid-liquid separation obtains vanadium hydroxide solid；(4) carry out calcining prepared barium oxide by vanadium hydroxide solid.The method of the invention utilizes solution containing vanadium, directly prepares barium oxide with oxalic acid for raw material, and the conversion ratio of raw material is high, also ensures that the purity of products obtained therefrom simultaneously, and technique is simple, low cost.
Description
Technical field
The invention belongs to hydrometallurgy and vanadium chemical field, a kind of method relating to barium oxide, particularly relate to a kind of profit
The method directly preparing barium oxide with solution containing vanadium.
Background technology
There is the allotrope of the Molecular segregation phase of various ways in vanadium dioxide, is a kind of typical phase transformation chemical combination
Thing.While undergoing phase transition, the electrical conductivity of vanadium dioxide, infrared light transmittance, reflectance and resistance all can be undergone mutation.This
Plant unique character and become the focus of energy-saving material research, and be widely used in smart window material, gas sensor, photoelectricity
The aspects such as switch and Infrared Detectors.
Xie Yi academician seminar of Chinese University of Science and Technology first Application hydro-thermal method in 2012 is made surfactant with PVP and is controlled to have synthesized 1 μ
The nucleocapsid shape vanadium dioxide D phase microsphere of about m size, and its crystal structure of labor (New J.Chem., 2012,36,
619).But its preparation process needs to add exhibiting high surface activating agent, cause product separating, washing difficulty, add production cost.
Meanwhile, their research is also found that vanadium dioxide D phase has similar generation energy with R phase.Inspired by this, CN 104402050A
It is former for all successively reporting first with ammonium metavanadate and formic acid with document (CrystEngComm, 2015,17,5614-5619)
Material, in the case of being not added with any surfactant, the D phase hypovanadic oxide powder of synthesis nanometer shape；Then at a constant temperature
The lower annealing of degree converts it into M phase, to reach to produce in a large number the purpose of M-phase vanadium dioxide powder.But the method requires strict control
PH value processed, between 1.5-2.5, adds control difficulty；Simultaneously need to react 48h at 200 DEG C, improve energy consumption.
Vanadyl oxalate is as a kind of industrial important presoma, and its range is the most widely.Such as, appoint wise man towering
People have studied a kind of method utilizing ammonolysis vanadyl oxalate to prepare nano vanadium nitride powder-body, and described method has prepared average particle
The Emission in Cubic VN powder body of footpath about 50mm (" ammonolysis vanadyl oxalate prepares nano vanadium nitride powder-body ", Ren Zhezheng, functional material,
Supplementary issue (38) volume in 2007).In view of the needs of the utilization ways new to vanadyl oxalate, and vanadium resource is utilized the expansion in field
Exhibition, it is inevitable for developing new vanadyl oxalate preparation technology, but current vanadyl oxalate preparation method to there is feed stock conversion low
The problem such as the highest with product purity.
CN 1693212A discloses the preparation method of a kind of vanadium dioxide nano powder, it is mentioned that with five oxygen
Changing two vanadium and oxalic acid is that raw material directly heats reduction in aqueous and prepares precursor vanadyl oxalate, the method is by vanadyl oxalate
As a kind of precursor, preparation technology is relatively simple, but in raw material, vanadic anhydride conversion ratio is low, and miscellaneous in vanadyl oxalate product
Matter content is high.
Therefore, a kind of raw material of exploitation is easy to get, with low cost, easy and simple to handle, process is convenient, reaction condition gentleness is prone to industry
The synthetic method of the vanadium dioxide D phase changed is significant.
Summary of the invention
Low for feed stock conversion present in existing preparation technology, product purity is the highest, complicated process of preparation and energy consumption
The problems such as height, the invention provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide.Described method utilizes solution containing vanadium,
Directly prepare barium oxide with oxalic acid for raw material, the conversion ratio of raw material is high, also ensures that the purity of products obtained therefrom, technique letter simultaneously
Single, low cost.
For reaching this purpose, the present invention by the following technical solutions:
The invention provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) carrying out calcification precipitation reaction to addition calcium oxide in the solution containing vanadium of remove impurity, solid-liquid separation obtains calcium vanadate
Solid and deposition vanadium mother liquid；
(2) step (1) being obtained adds water after calcium vanadate solid is mixed homogeneously with oxalic acid is configured to reaction paste and heats
Reaction, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) in the vanadyl oxalate solution that step (2) prepares, add alkali metal hydroxide aqueous solution and/or ammonia is carried out
Reaction, after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) carry out calcining prepared barium oxide by step (3) gained vanadium hydroxide solid.
The principle of the method for the invention is: be initially charged a small amount of calcium additive and the silicon in solution containing vanadium in solution containing vanadium
The impurity reactions such as phosphorus generate solid and carry out remove impurity；After being filtrated to get impurity and purification liquid, it is carried out calcification precipitation reaction and generates vanadium
Acid calcium solid；Calcium vanadate solid mix homogeneously with oxalic acid addition deionization heating occur reduction reaction, separate after having reacted
The vanadyl oxalate solution arrived；In vanadyl oxalate solution, add alkali metal hydroxide aqueous solution or ammonia again, obtain hydrogen-oxygen
Change vanadium, the barium oxide to vanadium hydroxide high-temperature calcination.
, the whole technical process of the present invention produces without waste liquid meanwhile, the most economic and environment-friendly, decrease waste treatment process.
In the present invention, described in step (1), remove impurity is: carry out silicon phosphorus remove impurity to containing addition calcium additive in vanadium；Step
(1) consumption of calcium oxide described in is so that vanadium precipitation is as the criterion completely.Described remove impurity and calcification precipitation process are conventional in this area
Technological means, therefore repeat no more.
Described in step (2), the temperature of reacting by heating is about 20～75 DEG C, but is not limited to this, and it is normal that it is similarly this area
Rule technological means, therefore repeat no more.
Following as currently preferred technical scheme, but the restriction of the technical scheme provided not as the present invention, pass through
Techniques below scheme, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, solution containing vanadium described in step (1) is sodium roasting-water logging vanadium extraction liquid, sky
Any one or the combination of at least two, more preferably sodium in white roasting-ammonia leaching and vanadium extraction liquid or calcification baking scavenging solution
Roasting-water logging vanadium extraction liquid and/or blank roasting-ammonia leaching and vanadium extraction liquid, the most blank roasting-ammonia leaching and vanadium extraction liquid.
In the present invention, described sodium roasting-water logging vanadium extraction liquid, blank roasting-ammonia leaching and vanadium extraction liquid and calcification baking scavenging solution
The method that is in state of the art of preparation method, here is omitted.
As currently preferred technical scheme, oxalic acid described in step (2) is 8～9 with the mol ratio of calcium vanadate, such as
8,8.2,8.4,8.6,8.8 or 9 etc., it is not limited to other numerical value do not enumerated in cited numerical value, this numerical range
Equally applicable.
As currently preferred technical scheme, described in step (2), the concentration of oxalic acid is 15～45g/L, such as 15g/
L, 20g/L, 25g/L, 30g/L, 35g/L or 45g/L etc., it is not limited to cited numerical value, in this numerical range other
The numerical value do not enumerated is equally applicable.
As currently preferred technical scheme, described in step (3), alkali metal hydroxide is sodium hydroxide and/or hydrogen
Potassium oxide, more preferably sodium hydroxide.
As currently preferred technical scheme, described in step (3), the concentration of alkali metal hydroxide aqueous solution is 50
～800g/L, such as 50g/L, 100g/L, 150g/L, 200g/L, 300g/L, 400g/L, 500g/L, 600g/L, 700g/L or
800g/L etc., it is not limited to other numerical value do not enumerated are equally applicable, further in cited numerical value, this numerical range
It is preferably 200～700g/L, particularly preferably 450～600g/L.
Preferably, described in step (3), the concentration of ammonia is 5～25wt%, such as 5wt%, 7wt%, 10wt%,
13wt%, 15wt%, 17wt%, 20wt%, 23wt% or 25wt% etc., it is not limited to cited numerical value, this numerical value
In the range of other numerical value do not enumerated equally applicable.
As currently preferred technical scheme, alkali metal hydroxide aqueous solution described in step (3) and/or ammonia
Addition is: making the mol ratio of v element and hydroxide ion in solution is 1:(1～10), such as 1:1,1:2,1:3,1:4,1:
5,1:6,1:7,1:8,1:9 or 1:10 etc., it is not limited to other numbers do not enumerated in cited numerical value, this numerical range
It is worth equally applicable, more preferably 1:(3～6).
In the present invention, the alkali metal hydroxide aqueous solution of described interpolation and/or ammonia need to make hydroxide ion in solution
Keep within the specific limits with the mol ratio of v element, if exceeding this scope, the purity of D phase hypovanadic oxide can be made to decline, reach not
To requiring；Or the consumption causing alkali additives is excessive, cause waste, increase production cost.
Preferably, described in step (3) reaction reaction temperature be 20～60 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C,
40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C etc., it is not limited to cited numerical value, in this numerical range, other are not enumerated
Numerical value is equally applicable, more preferably 30～50 DEG C.The method of the invention, it is only necessary to carry out precipitation under cryogenic anti-
Should, reaction condition is gentle, it is easy to industrializing implementation, and whole process energy consumption is relatively low.
Preferably, described in step (3), the response time of reaction is 30～60min.
As currently preferred technical scheme, calcine described in step (4) and carry out in Muffle furnace.
Preferably, described in step (4), calcining heat is 400～650 DEG C, such as 400 DEG C, 430 DEG C, 450 DEG C, 470 DEG C,
500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C or 630 DEG C etc., it is not limited to cited numerical value, in this numerical range
Other numerical value do not enumerated are equally applicable.
Preferably, described in step (4), calcination time is 40～80min.
As currently preferred technical scheme, in step (4), gained barium oxide is D phase hypovanadic oxide, its purity >=
99.1wt%, such as 99.1wt%, 99.2wt%, 99.3wt%, 99.4wt%, 99.5wt%, 99.6wt%, 99.7wt%,
99.8wt% or 99.9wt% etc., it is not limited to other numerical value do not enumerated are same in cited numerical value, this numerical range
Sample is suitable for.
As currently preferred technical scheme, said method comprising the steps of:
(1) add calcium additive to solution containing vanadium and carry out remove impurity, then the solution containing vanadium after remove impurity adds calcium oxide and enters
Row calcification precipitation is reacted, and solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) step (1) obtains adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste and enter
Row reacting by heating, wherein, oxalic acid is 8～9 with the mol ratio of calcium vanadate, and the concentration of oxalic acid is 15～45g/L, and after reaction, solid-liquid divides
From obtaining vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is 450～600g/L sodium hydrate aqueous solutions
And/or the ammonia that concentration is 5～25wt% makes the mol ratio of hydroxide ion and v element in solution be 1:(3～6), in 30～
Reacting at 50 DEG C, after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) carry out calcining 40～80min in Muffle furnace at 400～650 DEG C by step (3) gained vanadium hydroxide solid
Prepare the D phase hypovanadic oxide of purity >=99.1wt%.
Compared with prior art, the method have the advantages that
(1) the invention provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, utilize solution containing vanadium, with oxalic acid
Directly prepare barium oxide for raw material, decrease reagent consumption, reduce reaction cost, make raw material have higher conversion ratio, turn
Rate is up to more than 90%；At the same time it can also be ensured that product has higher purity, the purity of gained vanadium dioxide >=
99.1wt%；
(2) the whole technical process of the present invention does not produce waste water, decrease subsequent wastewater treatment link, energy efficient, work
Process flow simplifies, and is more beneficial for commercial introduction.
Accompanying drawing explanation
Fig. 1 is the process chart of the method utilizing solution containing vanadium directly to prepare barium oxide of the present invention.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, below to the present invention the most specifically
Bright.But following embodiment is only the simple example of the present invention, do not represent or limit the scope of the present invention, this
Invention protection domain is as the criterion with claims.
As it is shown in figure 1, the invention provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method bag
Include following steps:
(1) carrying out calcification precipitation reaction to addition calcium oxide in the solution containing vanadium of remove impurity, solid-liquid separation obtains calcium vanadate
Solid and deposition vanadium mother liquid；
(2) step (1) being obtained adds water after calcium vanadate solid is mixed homogeneously with oxalic acid is configured to reaction paste and heats
Reaction, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) in the vanadyl oxalate solution that step (2) prepares, add alkali metal hydroxide aqueous solution and/or ammonia is carried out
Reaction, after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) carry out calcining prepared barium oxide by step (3) gained vanadium hydroxide solid.
It is below present invention typical case but non-limiting example:
Embodiment 1:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) add calcium additive to sodium roasting-water logging vanadium extraction liquid solution containing vanadium and carry out silicon phosphorus remove impurity, then after remove impurity
Solution containing vanadium in add calcium oxide carry out calcification precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) obtain step (1) adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste in
Carrying out reacting by heating 1h at 80 DEG C, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is 450g/L sodium hydrate aqueous solution, makes solution
Middle hydroxide ion is 1:3 with the mol ratio of v element, reacts at 30 DEG C, and after reaction, solid-liquid separation obtains vanadium hydroxide
Solid；
(4) carry out calcining prepared D phase titanium dioxide in Muffle furnace at 450 DEG C by step (3) gained vanadium hydroxide solid
Vanadium.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.15wt%.
Embodiment 2:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) add calcium additive to sodium roasting-water logging vanadium extraction liquid solution containing vanadium and carry out silicon phosphorus remove impurity, then after remove impurity
Solution containing vanadium in add calcium oxide carry out calcification precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) obtain step (1) adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste in
Carrying out reacting by heating 1h at 80 DEG C, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is 500g/L sodium hydrate aqueous solution, makes solution
Middle hydroxide ion is 1:4 with the mol ratio of v element, reacts at 35 DEG C, and after reaction, solid-liquid separation obtains vanadium hydroxide
Solid；
(4) carry out calcining prepared D phase titanium dioxide in Muffle furnace at 500 DEG C by step (3) gained vanadium hydroxide solid
Vanadium.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.22wt%.
Embodiment 3:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) add calcium additive to sodium roasting-water logging vanadium extraction liquid solution containing vanadium and carry out silicon phosphorus remove impurity, then after remove impurity
Solution containing vanadium in add calcium oxide carry out calcification precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) obtain step (1) adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste in
Carrying out reacting by heating 1h at 80 DEG C, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is 550g/L potassium hydroxide aqueous solution, makes solution
Middle hydroxide ion is 1:6 with the mol ratio of v element, reacts at 40 DEG C, and after reaction, solid-liquid separation obtains vanadium hydroxide
Solid；
(4) carry out calcining prepared D phase titanium dioxide in Muffle furnace at 550 DEG C by step (3) gained vanadium hydroxide solid
Vanadium.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.5wt%.
Embodiment 4:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) add calcium additive to sodium roasting-water logging vanadium extraction liquid solution containing vanadium and carry out silicon phosphorus remove impurity, then after remove impurity
Solution containing vanadium in add calcium oxide carry out calcification precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) obtain step (1) adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste in
Carrying out reacting by heating 1h at 80 DEG C, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is 570g/L potassium hydroxide aqueous solution, makes solution
Middle hydroxide ion is 1:3.5 with the mol ratio of v element, reacts at 50 DEG C, and after reaction, solid-liquid separation obtains hydroxide
Vanadium solid；
(4) carry out calcining prepared D phase titanium dioxide in Muffle furnace at 600 DEG C by step (3) gained vanadium hydroxide solid
Vanadium.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.15wt%.
Embodiment 5:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method includes following step
Rapid:
(1) add calcium additive to sodium roasting-water logging vanadium extraction liquid solution containing vanadium and carry out silicon phosphorus remove impurity, then after remove impurity
Solution containing vanadium in add calcium oxide carry out calcification precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) obtain step (1) adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste in
Carrying out reacting by heating 1h at 80 DEG C, after reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) adding concentration in the vanadyl oxalate solution that step (2) prepares is the ammonia of 25wt%, makes hydroxyl in solution
Ion is 1:4 with the mol ratio of v element, reacts at 50 DEG C, and after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) carry out calcining prepared D phase titanium dioxide in Muffle furnace at 650 DEG C by step (3) gained vanadium hydroxide solid
Vanadium.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.12wt%.
Embodiment 6:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method is except step
(3) in add be concentration be that outside 600g/L sodium hydrate aqueous solution, unclassified stores is the most in the same manner as in Example 1 with preparation process,
Prepare D phase hypovanadic oxide.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.21wt%.
Embodiment 7:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method is except step
(3) in add be concentration be that outside 200g/L sodium hydrate aqueous solution, unclassified stores is the most in the same manner as in Example 1 with preparation process,
Prepare D phase hypovanadic oxide.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.11wt%.
Embodiment 8:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method is except step
(3) in add be concentration be that outside 700g/L sodium hydrate aqueous solution, unclassified stores is the most in the same manner as in Example 1 with preparation process,
Prepare D phase hypovanadic oxide.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.19wt%.
Embodiment 9:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method is except step
(3) adding in is that outside the ammonia that concentration is 15wt%, unclassified stores is the most in the same manner as in Example 1 with preparation process, prepares D phase two
Vanadium oxide.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.17wt%.
Embodiment 10:
Present embodiments providing a kind of method utilizing solution containing vanadium directly to prepare barium oxide, described method is except step
(3) adding in is that outside the ammonia that concentration is 5wt%, unclassified stores is the most in the same manner as in Example 1 with preparation process, prepares D phase two
Vanadium oxide.
Through checking and being calculated, in the present embodiment, the purity of gained D phase hypovanadic oxide is 99.14wt%.
Comparative example 1:
This comparative example provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, and described method is except step
(2) in the addition of sodium hydroxide make the mol ratio of hydroxide ion and v element in solution be 1:0.5 (＞ 1:1) outward, other
Material is the most in the same manner as in Example 1 with preparation process, prepares D phase hypovanadic oxide.
Through checking and being calculated, in this comparative example, the purity of gained D phase hypovanadic oxide is 76.31wt%.
Comparative example 2:
This comparative example provides a kind of method utilizing solution containing vanadium directly to prepare barium oxide, and described method is except step
(2) in the addition of sodium hydroxide make the mol ratio of hydroxide ion and v element in solution be 1:16 (＜ 1:10) outward, other
Material is the most in the same manner as in Example 1 with preparation process, prepares D phase hypovanadic oxide.
Through checking and being calculated, in this comparative example, the purity of gained D phase hypovanadic oxide is 99.16wt%.
Result in integrated embodiment 1-10 and comparative example 1-2 utilizes solution containing vanadium it can be seen that the invention provides one
The method directly preparing barium oxide, utilizes solution containing vanadium, directly prepares barium oxide with oxalic acid for raw material, decreases reagent and disappear
Consumption, reduces reaction cost, makes raw material have higher conversion ratio, and conversion ratio is up to more than 90%；At the same time it can also be ensured that product
There is higher purity, the purity >=99.1wt% of gained vanadium dioxide.
Meanwhile, the whole technical process of the present invention does not produce waste water, decrease subsequent wastewater treatment link, energy efficient,
Technological process simplifies, and is more beneficial for commercial introduction.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. one kind utilizes the method that solution containing vanadium directly prepares barium oxide, it is characterised in that said method comprising the steps of:
(1) carrying out calcification precipitation reaction to addition calcium oxide in the solution containing vanadium of remove impurity, solid-liquid separation obtains calcium vanadate solid
And deposition vanadium mother liquid；
(2) step (1) being obtained adds water after calcium vanadate solid is mixed homogeneously with oxalic acid is configured to reaction paste and carries out reacting by heating,
After reaction, solid-liquid separation obtains vanadyl oxalate solution and calcium oxalate solid；
(3) in the vanadyl oxalate solution that step (2) prepares, add alkali metal hydroxide aqueous solution and/or ammonia is carried out instead
Should, after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) carry out calcining prepared barium oxide by step (3) gained vanadium hydroxide solid.
Method the most according to claim 1, it is characterised in that described in step (1), solution containing vanadium is sodium roasting-flooding
Any one or the combination of at least two in vanadium liquid, blank roasting-ammonia leaching and vanadium extraction liquid or calcification baking scavenging solution, further preferably
For sodium roasting-water logging vanadium extraction liquid and/or blank roasting-ammonia leaching and vanadium extraction liquid, the most blank roasting-ammonia leaching and vanadium extraction liquid.
Method the most according to claim 1 and 2, it is characterised in that oxalic acid described in step (2) and the mol ratio of calcium vanadate
It is 8～9.
4. according to the method described in any one of claim 1-3, it is characterised in that described in step (2), the concentration of oxalic acid is 15
～45g/L.
5. according to the method described in any one of claim 1-4, it is characterised in that alkali metal hydroxide described in step (3)
For sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide.
6. according to the method described in any one of claim 1-5, it is characterised in that alkali metal hydroxide described in step (3)
The concentration of aqueous solution is 50～800g/L, more preferably 200～700g/L, and particularly preferably 450～600g/L；
Preferably, described in step (3), the concentration of ammonia is 5～25wt%.
7. according to the method described in any one of claim 1-6, it is characterised in that alkali metal hydroxide described in step (3)
The addition of aqueous solution and/or ammonia is: making the mol ratio of v element and hydroxide ion in solution is 1:(1～10), enter one
Step is preferably 1:(3～6)；
Preferably, described in step (3), the reaction temperature of reaction is 20～60 DEG C, more preferably 30～50 DEG C；
Preferably, described in step (3), the response time of reaction is 30～60min.
8. according to the method described in any one of claim 1-7, it is characterised in that step is calcined in Muffle furnace described in (4)
Carry out；
Preferably, described in step (4), calcining heat is 400～650 DEG C；
Preferably, described in step (4), calcination time is 40～80min.
9. according to the method described in any one of claim 1-8, it is characterised in that in step (4), gained barium oxide is D phase two
Vanadium oxide, its purity >=99.1wt%.
10. according to the method described in any one of claim 1-9, it is characterised in that said method comprising the steps of:
(1) add calcium additive to solution containing vanadium and carry out remove impurity, then the solution containing vanadium after remove impurity adds calcium oxide and carries out calcium
Changing precipitation reaction, solid-liquid separation obtains calcium vanadate solid and deposition vanadium mother liquid；
(2) step (1) obtains adding after calcium vanadate solid is mixed homogeneously with oxalic acid deionized water be configured to reaction paste and add
Thermal response, wherein, oxalic acid is 8～9 with the mol ratio of calcium vanadate, and the concentration of oxalic acid is 15～45g/L, and after reaction, solid-liquid separation obtains
To vanadyl oxalate solution and calcium oxalate solid；
(3) to step (2) prepare vanadyl oxalate solution in add concentration be 450～600g/L sodium hydrate aqueous solutions and/or
Concentration be 5～25wt% ammonia make the mol ratio of hydroxide ion and v element in solution be 1:(3～6), at 30～50 DEG C
Reacting, after reaction, solid-liquid separation obtains vanadium hydroxide solid；
(4) step (3) gained vanadium hydroxide solid carries out in Muffle furnace at 400～650 DEG C calcine 40～80min prepare
The D phase hypovanadic oxide of purity >=99.1wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217727A (en) * | 2018-04-12 | 2018-06-29 | 四川星明能源环保科技有限公司 | A phase hypovanadic oxides and preparation method thereof |
| CN110117714A (en) * | 2019-05-29 | 2019-08-13 | 北京科技大学 | A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium |
| CN110408789A (en) * | 2019-09-11 | 2019-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of sodium is recycled from solution containing vanadium |
| CN112195347A (en) * | 2020-09-27 | 2021-01-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium extraction method of calcified vanadium slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120013648A (en) * | 2010-08-06 | 2012-02-15 | 설영택 | Surface metal oxides for implants, implants or devices using the same and method for producing the implants or devices |
| CN102676817A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院过程工程研究所 | Method for preparing calciferous vanadium oxide from vanadate |
| CN105800689A (en) * | 2016-03-02 | 2016-07-27 | 河北钢铁股份有限公司承德分公司 | Preparation method of ultra-pure vanadium pentoxide |
-
2016
- 2016-08-31 CN CN201610771691.4A patent/CN106282563B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120013648A (en) * | 2010-08-06 | 2012-02-15 | 설영택 | Surface metal oxides for implants, implants or devices using the same and method for producing the implants or devices |
| CN102676817A (en) * | 2011-03-15 | 2012-09-19 | 中国科学院过程工程研究所 | Method for preparing calciferous vanadium oxide from vanadate |
| CN105800689A (en) * | 2016-03-02 | 2016-07-27 | 河北钢铁股份有限公司承德分公司 | Preparation method of ultra-pure vanadium pentoxide |
Non-Patent Citations (1)
| Title |
|---|
| 任哲峥等: ""氨解草酸氧钒制备纳米氮化钒粉体"", 《第六届中国功能材料及其应用学术会议论文集（6）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217727A (en) * | 2018-04-12 | 2018-06-29 | 四川星明能源环保科技有限公司 | A phase hypovanadic oxides and preparation method thereof |
| CN110117714A (en) * | 2019-05-29 | 2019-08-13 | 北京科技大学 | A kind of method of room temperature saturated oxalic acid solution Anodic electrolysis Leaching Vanadium |
| CN110117714B (en) * | 2019-05-29 | 2020-03-17 | 北京科技大学 | Method for leaching vanadium by anode electrolysis in normal-temperature saturated oxalic acid solution |
| CN110408789A (en) * | 2019-09-11 | 2019-11-05 | 攀钢集团攀枝花钢铁研究院有限公司 | The method of sodium is recycled from solution containing vanadium |
| CN112195347A (en) * | 2020-09-27 | 2021-01-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium extraction method of calcified vanadium slag |
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