CN109321941A - The method for preparing vanadium oxalate - Google Patents
The method for preparing vanadium oxalate Download PDFInfo
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- CN109321941A CN109321941A CN201811332868.6A CN201811332868A CN109321941A CN 109321941 A CN109321941 A CN 109321941A CN 201811332868 A CN201811332868 A CN 201811332868A CN 109321941 A CN109321941 A CN 109321941A
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- vanadium
- oxalate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to the methods for preparing vanadium oxalate, belong to the preparation technical field of low price vfanadium compound.Present invention solves the technical problem that being the important function based on lower valency vanadium, there is presently no the reports in relation to vanadium oxalate preparation method, provide a kind of method for preparing vanadium oxalate.The present invention discloses the method for preparing vanadium oxalate, using vanadyl oxalate as raw material, is dissolved in deionized water and vanadyl oxalate solution is made, and obtains oxalic acid vanadium solution by electroreduction, vanadium oxalate product is prepared in then concentrated, crystallization.The present invention prepares vanadium oxalate high income, and free from admixture element introduces in preparation process, the vanadium oxalate purity is high being prepared, and preparation process of the present invention is simple, it is easy to accomplish prepare with scale has expanded the application of vanadium product, improves the added value of vanadium resource.
Description
Technical field
The invention belongs to the preparation technical fields of low price vfanadium compound, and in particular to the method for preparing vanadium oxalate.
Background technique
Vanadium is a kind of important metal, has many excellent performances, has in fields such as steel, Industrial Catalysis, pharmacy
Important application, the vanadium in 90% or more the whole world is applied in steel at present, remaining is applied to the industries such as chemical industry, pharmacy, energy storage.It is low
The vanadium of valence state, which is applied to catalyst, has remarkable result, and wherein vanadium oxalate plays an important role in vanadium organic synthesis, leads to
Frequently as presoma.Have more document at present and describe the application of vanadium oxalate in the industry, but is related to the system of vanadium oxalate
Preparation Method does not have substantially.Therefore, it is necessary to it is a kind of being capable of the mass method for preparing vanadium oxalate.
Summary of the invention
Present invention solves the technical problem that being the important function based on lower valency vanadium, there is presently no the preparations of related vanadium oxalate
The report of method provides a kind of method for preparing vanadium oxalate.
Technical proposal that the invention solves the above-mentioned problems is to provide the method for preparing vanadium oxalate, using vanadyl oxalate as raw material,
It is dissolved in deionized water and vanadyl oxalate solution is made, obtain oxalic acid vanadium solution by electroreduction, then concentrated, crystallization,
Vanadium oxalate product is prepared.
Wherein, vanadyl oxalate purity >=99%, other elements Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na
≤ 0.01%, K≤0.01%.
Wherein, the concentration of vanadyl oxalate solution is 1~2.5mol/L.
Wherein, the process of electroreduction is that vanadyl oxalate solution is placed in electrolytic cell cathode, just extremely sulfuric acid solution, cathode
Trivalent vanadium solution is obtained through constant-current electrolysis.
Wherein, sulfuric acid concentration is 0.5~1mol/L, and electrolytic current density is 10~30mA/cm2。
Wherein, vanadium ion concentration is 2.5~4.0mol/L in solution after concentration.
Wherein, for the mode of concentration using vacuum distillation, vacuum degree is -0.07~-0.09Mpa, and temperature is 60~90 DEG C.
Wherein, it crystallizes under stiring, crystallization temperature is 20~40 DEG C, and the time is 8~12h, and stirring rate is 20~50r/
min。
Wherein, oxalic acid is added after concentration, controls concentration of oxalic acid in 0.2~0.5mol/L, is then crystallized.
Beneficial effects of the present invention:
The present invention provides the methods for preparing vanadium oxalate, using vanadyl oxalate as raw material, electroreduction are first passed through, then through dense
Vanadium oxalate is prepared in contracting, crystallization；The present invention prepares vanadium oxalate high income, and free from admixture element introduces in preparation process, is prepared into
The vanadium oxalate purity is high arrived；Preparation process of the present invention is simple, it is easy to accomplish prepare with scale, before being used as due to lower valency vanadium oxalate
Driving body has important application in fields such as the inorganic compound synthesis, orgnnic comopounds synthesis and complex of vanadium, therefore opens up
The application for having opened up vanadium product improves the added value of vanadium resource.
Specific embodiment
The method that offer of the present invention prepares vanadium oxalate is dissolved in deionized water and oxalic acid is made using vanadyl oxalate as raw material
Vanadyl solution obtains oxalic acid vanadium solution by electroreduction, is then concentrated, crystallizes, and vanadium oxalate is prepared in vacuum drying.
Specifically, can follow the steps below:
(1) a certain amount of vanadyl oxalate is weighed, is dissolved in deionized water and obtains vanadyl oxalate solution, it is negative to be placed in electrolytic cell
Pole, just extremely sulfuric acid solution, obtain trivalent oxalic acid vanadium solution through constant-current electrolysis；
(2) the trivalent oxalic acid vanadium solution of step (1) is subjected to vacuum distillation concentration, obtains vanadium oxalate concentrate；
(3) oxalic acid is added in step (2) vanadium oxalate concentrate, stirs lower crystallization, is separated by solid-liquid separation, is dried in vacuo
To vanadium oxalate product.
Wherein, vanadyl oxalate purity >=99%, other elements Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na
≤ 0.01%, K≤0.01%.
Wherein, the concentration of vanadyl oxalate solution is 1~2.5mol/L.
Wherein, the reaction that step (1) is related to is VO2++e-+2H+→V3++H2O。
Wherein, step (1) sulfuric acid concentration is 0.5~1mol/L, and electrolytic current density is 10~30mA/cm2.Positive solution
The middle electric conductivity that sulfuric acid is added and improves solution, reduces polarization, improves electrolytic efficiency.
Wherein, vanadium ion concentration is 2.5~4.0mol/L in solution after concentration.
Wherein, for the mode of concentration using vacuum distillation, vacuum degree is -0.07~-0.09Mpa, and temperature is 60~90 DEG C.Subtract
Pressure distillation is that trivalent vanadium ion is oxidized in order to prevent.
Wherein, it crystallizes under stiring, crystallization temperature is 20~40 DEG C, and the time is 8~12h, and stirring rate is 20~50r/
min。
Further, in order to promote the formation of vanadium oxalate nucleus, oxalic acid can be added before crystallization as salting-out agents.
Preferably, control concentrate medium-height grass acid concentration is 0.2~0.5mol/L.
Embodiment 1
Weigh 122.5g VOC2O4·5H2O is dissolved in 500mL deionized water, is placed in electrolytic cell cathode, just extremely
0.5mol/L sulfuric acid solution, in 20mA/cm2Constant-current electrolysis under current density, time 2h obtain trivalent vanadium solution, in vacuum degree
For -0.08Mpa, temperature is that concentration is evaporated under reduced pressure at 80 DEG C, until solution vanadium ion concentration is 3.2mol/L, 4g oxalic acid is added,
10h is crystallized at 20 DEG C, obtains 161.2g vanadium oxalate, vanadium yield 80.2%, purity >=99.8%, V of vanadium oxalate4+/ TV=
0.12%, Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na≤0.01%, K≤0.01%.
Embodiment 2
Weigh 150g VOC2O4·5H2O is dissolved in 500mL deionized water, is placed in electrolytic cell cathode, just extremely
0.5mol/L sulfuric acid solution, in 30mA/cm2Constant-current electrolysis under current density, time 1.65h obtain trivalent vanadium solution, in vacuum
Degree is -0.08Mpa, and temperature is that concentration is evaporated under reduced pressure at 70 DEG C, until solution vanadium ion concentration is 3.4mol/L, 6.5g grass is added
Acid crystallizes 12h at 30 DEG C, obtains 210.92g vanadium oxalate, vanadium yield 85.7%, vanadium oxalate purity >=99.5%, V4+/ TV=
0.26%, Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na≤0.01%, K≤0.01%.
Embodiment 3
Weigh 200g VOC2O4·5H2O is dissolved in 500mL deionized water, is placed in electrolytic cell cathode, just extremely
0.5mol/L sulfuric acid solution, in 30mA/cm2Constant-current electrolysis under current density, time 2.2h obtain trivalent vanadium solution, in vacuum degree
For -0.09Mpa, temperature is that concentration is evaporated under reduced pressure at 90 DEG C, until solution vanadium ion concentration is 3.6mol/L, 10g oxalic acid is added,
12h is crystallized at 40 DEG C, obtains 293.05g vanadium oxalate, vanadium yield 89.3%, vanadium oxalate purity >=99.1%, V4+/ TV=
0.86%, Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na≤0.01%, K≤0.01%.
Claims (9)
1. the method for preparing vanadium oxalate, it is characterised in that: using vanadyl oxalate as raw material, be dissolved in deionized water and oxalic acid oxygen is made
Vanadium solution obtains oxalic acid vanadium solution by electroreduction, and vanadium oxalate is prepared in then concentrated, crystallization.
2. the method according to claim 1 for preparing vanadium oxalate, it is characterised in that: vanadyl oxalate purity >=99%,
Other elements Fe≤0.01%, Cr≤0.01%, Si≤0.005%, Na≤0.01%, K≤0.01%.
3. the method according to claim 1 or 2 for preparing vanadium oxalate, it is characterised in that: the vanadyl oxalate solution it is dense
Degree is 1~2.5mol/L.
4. described in any item methods for preparing vanadium oxalate according to claim 1~3, it is characterised in that: the electroreduction
Process is that vanadyl oxalate solution is placed in electrolytic cell cathode, just extremely sulfuric acid solution, and it is molten that cathode through constant-current electrolysis obtains trivalent vanadium
Liquid.
5. the method according to claim 4 for preparing vanadium oxalate, it is characterised in that: the sulfuric acid concentration is 0.5~1mol/
L, electrolytic current density are 10~30mA/cm2。
6. described in any item methods for preparing vanadium oxalate according to claim 1~5, it is characterised in that: solution after the concentration
Middle vanadium ion concentration is 2.5~4.0mol/L.
7. described in any item methods for preparing vanadium oxalate according to claim 1~6, it is characterised in that: the mode of the concentration
Using vacuum distillation, vacuum degree is -0.07~-0.09Mpa, and temperature is 60~90 DEG C.
8. described in any item methods for preparing vanadium oxalate according to claim 1~7, it is characterised in that: crystallize, tie under stiring
Brilliant temperature is 20~40 DEG C, and the time is 8~12h, and stirring rate is 20~50r/min.
9. described in any item methods for preparing vanadium oxalate according to claim 1~8, it is characterised in that: be added after concentration
Oxalic acid controls concentration of oxalic acid in 0.2~0.5mol/L, is then crystallized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811332868.6A CN109321941A (en) | 2018-11-09 | 2018-11-09 | The method for preparing vanadium oxalate |
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| CN201811332868.6A CN109321941A (en) | 2018-11-09 | 2018-11-09 | The method for preparing vanadium oxalate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362684A (en) * | 2008-07-23 | 2009-02-11 | 郑德龙 | Solution containing vanadium oxalate and preparation method thereof |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN106380389A (en) * | 2016-08-31 | 2017-02-08 | 河北钢铁股份有限公司承德分公司 | Method for preparing vanadyl oxalate |
-
2018
- 2018-11-09 CN CN201811332868.6A patent/CN109321941A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362684A (en) * | 2008-07-23 | 2009-02-11 | 郑德龙 | Solution containing vanadium oxalate and preparation method thereof |
| CN103319326A (en) * | 2012-03-23 | 2013-09-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method for vanadyl oxalate |
| CN106380389A (en) * | 2016-08-31 | 2017-02-08 | 河北钢铁股份有限公司承德分公司 | Method for preparing vanadyl oxalate |
Non-Patent Citations (1)
| Title |
|---|
| 冯秀丽等: "V(Ⅲ)一V(Ⅳ)电解液的电解合成", 《合成化学》 * |
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