CN103319326A - Preparation method for vanadyl oxalate - Google Patents
Preparation method for vanadyl oxalate Download PDFInfo
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- CN103319326A CN103319326A CN2012100792054A CN201210079205A CN103319326A CN 103319326 A CN103319326 A CN 103319326A CN 2012100792054 A CN2012100792054 A CN 2012100792054A CN 201210079205 A CN201210079205 A CN 201210079205A CN 103319326 A CN103319326 A CN 103319326A
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Abstract
The invention relates to a preparation method for vanadyl oxalate. The method comprises the following steps: (1) in the presence of sulfuric acid aqueous solution, contacting a raw material containing vanadium pentoxide with a reducing agent to obtain a tetravalent vanadium solution; (2) contacting the tetravalent vanadium solution obtained in the step (1) with an alkali metal hydroxide to carry out a precipitation reaction, and carrying out solid-liquid separation to obtain a solid product; and (3) contacting the solid product obtained in the step (2) with oxalic acid to obtain vanadyl oxalate. Vanadyl oxalate prepared by the preparation method has the advantages of high conversion rate of the raw material, high product purity and the like; and the preparation method is simple in technical process, and is easy to implement.
Description
Technical field
The present invention relates to a kind of preparation method of oxalic acid vanadyl.
Background technology
The oxalic acid vanadyl is as a kind of industrial important presoma, and its use range is very widely, and for example, functional materials 2007 supplementary issue (38) volume utilizes the method for ammonium solution oxalic acid vanadyl presoma to prepare Emission in Cubic VN powder about median size 50mm.
In view of the needs that utilize approach new to the oxalic acid vanadyl, and the expansion that vanadium resource is utilized the field, developing new oxalic acid vanadyl preparation technology and be inevitable, there is the present situation that feed stock conversion is low, product purity is not high in present oxalic acid vanadyl preparation method.
For example, CN1693212A discloses a kind of preparation method of vanadium dioxide nano powder, wherein mentioned take Vanadium Pentoxide in FLAKES and oxalic acid and prepared precursor oxalic acid vanadyl as raw material direct heating in the aqueous solution reduces, this method is as a kind of precursor with the oxalic acid vanadyl, preparation technology is comparatively simple, but Vanadium Pentoxide in FLAKES low conversion rate in the raw material, and foreign matter content is high in the oxalic acid vanadyl product.
Summary of the invention
Goal of the invention of the present invention is in order to overcome the low conversion rate of Vanadium Pentoxide in FLAKES in the method Raw that adopts prior art to prepare the oxalic acid vanadyl, the high defective of foreign matter content in the oxalic acid vanadyl product for preparing, a kind of preparation method of oxalic acid vanadyl is provided, adopts the inventive method that feed stock conversion raising, product purity are improved.
For achieving the above object, the invention provides a kind of preparation method of oxalic acid vanadyl, the method may further comprise the steps: (1) in the presence of aqueous sulfuric acid, the raw material that will contain Vanadium Pentoxide in FLAKES contacts with reductive agent, obtains the tetravalence vanadium solution; (2) the tetravalence vanadium solution that step (1) is obtained contacts with alkali-metal oxyhydroxide and carries out precipitin reaction, and carries out solid-liquid separation, obtains solid product; (3) solid product that step (2) is obtained contacts with oxalic acid, obtains the oxalic acid vanadyl.
Method of the present invention has following beneficial effect: the Vanadium Pentoxide in FLAKES transformation efficiency is high in the raw material, and the purity of the oxalic acid vanadyl product of preparation is high.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
The method according to this invention, in described step (1), described aqueous sulfuric acid is this area raw material commonly used, act as the Vanadium Pentoxide in FLAKES in the activation raw material, for making activation effect better, preferred, in Vanadium Pentoxide in FLAKES, the raw material and the aqueous sulfuric acid mass ratio that contain Vanadium Pentoxide in FLAKES are 1: 2.5-5, the mass percent concentration of aqueous sulfuric acid can be 20%-85%.
In described step (1), described reductive agent can be this area reductive agent commonly used, reductive agent act as pentavalent vanadium in the raw material is reverted to tetravalence, in order to prevent that vanadium is reduced to lower valence state, preferred, reductive agent is selected from Sulfothiorine, oxalic acid and the formic acid one or more, more preferably in the situation, when adopting Sulfothiorine and/or formic acid, can reduce more fully and obtain the tetravalence vanadium solution, to be conducive to improve the transformation efficiency of raw material.
In described step (1), the selectable range of the consumption of described reductive agent is wider, better carries out in order to make reaction, and is preferred, in Vanadium Pentoxide in FLAKES, describedly contains the raw material of Vanadium Pentoxide in FLAKES and the mol ratio of reductive agent is 1: 1.4-3.2.
In described step (1), in the presence of aqueous sulfuric acid, the raw material that will contain Vanadium Pentoxide in FLAKES contacts the selectable range of the condition of reacting with reductive agent wider, better carry out more being conducive to improve the transformation efficiency of Vanadium Pentoxide in FLAKES for making reduction reaction, to contain the condition that the raw material of Vanadium Pentoxide in FLAKES contacts with reductive agent and comprise that temperature is 95-100 ℃, time is 0.5-5 hour, and further under the preferable case, the time is 0.5-2 hour.
In described step (2), described tetravalence vanadium solution contacts with alkali-metal oxyhydroxide and carries out precipitin reaction, and carries out solid-liquid separation, obtains solid product.This step purpose is to remove the impurity in the raw material and separates the solid product that obtains containing the tetravalence vanadium.It is acid that reaction system is, and the adding of alkali-metal oxyhydroxide makes the tetravalence vanadium generation precipitin reaction in the solution, and better in order to make reaction effect, precipitin reaction is more complete, and preferred, pH is 2-5.
In described step (2), described alkali metal hydroxide can be the common raw material in this area, purpose is the pH value of regulating precipitin reaction, be preferably NaOH and/or KOH, wherein, described alkali-metal oxyhydroxide can use with the form of its pure substance, also can use with the form of its aqueous solution.
In described step (2), the selectable range of described precipitin reaction condition is wider, and is better in order to make reaction effect, and preferred, temperature is 15-80 ℃, and further preferred, temperature is 40-70 ℃, and the time is 0.1-1 hour.
In described step (3), the solid product that step (2) is obtained contacts with oxalic acid, the selectable range of the oxalic acid of required adding and the mass ratio of solid product is wider, considering cost and yield, preferably, in described step (3), the solid product that described step (2) obtains and the mass ratio of oxalic acid are 1: 1-1.4.
In described step (3), the solid product that step (2) is obtained contacts with oxalic acid, obtains the crystallization of oxalic acid vanadyl by the ordinary method crystallization again, separates to obtain the finished product oxalic acid vanadyl.Under the preferable case, the condition that the solid product that described step (2) is obtained contacts with oxalic acid comprises that temperature is 15-40 ℃, and the time is 0.1-0.5 hour.
The method according to this invention, the described raw material that contains Vanadium Pentoxide in FLAKES can for this area raw material commonly used, in order further to improve the purity of the oxalic acid vanadyl for preparing, preferably adopt the higher raw material that contains Vanadium Pentoxide in FLAKES of purity, V in the raw material
2O
5The quality percentage composition be＞99.8%, the quality percentage composition of Si is that the quality percentage composition of＜0.01%, TFe is that the quality percentage composition of＜0.02%, P is＜0.005%, the quality percentage composition of K is that the quality percentage composition of＜0.01%, Na is＜0.01%.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below in conjunction with embodiment the inventive method is described further.
The method for detecting purity of the oxalic acid vanadyl product that following embodiment and Comparative Examples prepare is to take by weighing first oxalic acid vanadyl 2.000g, with retort furnace at 300 ℃ of lower roasting 1h, adopt afterwards GB 8639.1-1988 vanadium chemistry analytical procedure potassium permanganate-ferrous sulfate to measure TV (total vanadium), then draw oxalic acid vanadyl crystalline content, formula is oxalic acid vanadyl crystalline content %=3.3922 (reduction factor) * TV (taking by weighing the total content of vanadium percentage ratio % in the oxalic acid vanadyl).
Embodiment 1
The present embodiment is used for illustrating the preparation of oxalic acid vanadyl provided by the invention.
20g is contained the raw material of Vanadium Pentoxide in FLAKES (available from climbing steel vanadium products factory, main component (in mass): V
2O
5＞99.8%, Si＜0.01%, TFe＜0.02%, P＜0.005%, K＜0.01%, Na＜0.01%) being that 45% aqueous sulfuric acid mixes with the 75g mass percent concentration, is under 95 ℃ at system temperature, adds 40g Sulfothiorine in described mixture, reaction times is 1 hour, obtain the tetravalence vanadium solution, regulate pH value to 2,0.5 hour reaction times at 70 ℃ of lower NaOH of adding again, generate precipitation, solid-liquid separation is carried out in filtration, and at 25 ℃ of lower vacuum dryings, obtains solid matter 22.02g, then at 25 ℃ of lower oxalic acid 22g that add, with solid matter dissolving, the reaction times is 0.1 hour, and is heated to 85 ℃ of crystallizations and obtains the oxalic acid vanadyl (main component is VOC in mass
2O
4H
2O99.1%, Si＜0.01%, TFe＜0.02%, K＜0.01%, Na＜0.01%) crystal 3 7.48g.
Embodiment 2
The present embodiment is used for illustrating the preparation of oxalic acid vanadyl provided by the invention.
30g is contained the raw material of Vanadium Pentoxide in FLAKES (available from climbing steel vanadium products factory, main component (in mass): V
2O
5＞99.8%, Si＜0.01%, TFe＜0.02%, P＜0.005%, K＜0.01%, Na＜0.01%) be that 20% aqueous sulfuric acid mixes with the 120g mass percent concentration, be under 98 ℃ at system temperature, in described mixture, add 44g oxalic acid, 0.5 hour reaction times, obtain the tetravalence vanadium solution, regulate pH value to 4 at 40 ℃ of lower NaOH of adding again, in 0.1 hour reaction times, filter and carry out solid-liquid separation, and at 25 ℃ of lower vacuum dryings, obtain solid matter 32.86g, then at 15 ℃ of lower oxalic acid 41g that add, solid matter is dissolved, reaction times is 0.4 hour, is heated to 85 ℃ of crystallizations and obtains oxalic acid vanadyl (main component (in mass) VOC
2O
4H
2O98.7%, Si＜0.01%, TFe＜0.02%, K＜0.01%, Na＜0.01%) crystal 5 5.88g.
Embodiment 3
The present embodiment is used for illustrating the preparation of oxalic acid vanadyl provided by the invention.
20g is contained the raw material of Vanadium Pentoxide in FLAKES (available from climbing steel vanadium products factory, main component (in mass): V
2O
5＞99.8%, Si＜0.01%, TFe＜0.02%, P＜0.005%, K＜0.01%, Na＜0.01%) being that 85% aqueous sulfuric acid mixes with the 70g mass percent concentration, is under 100 ℃ at system temperature, adds 16g formic acid in described mixture, 2 hours reaction times, obtain the tetravalence vanadium solution, regulate pH value to 5,1 hour reaction times at 55 ℃ of lower KOH of adding again, generate precipitation, solid-liquid separation is carried out in filtration, and at 25 ℃ of lower vacuum dryings, obtains solid matter 21.88g, then at 40 ℃ of lower oxalic acid 23.4g that add, with solid matter dissolving, the reaction times is 0.5 hour, is heated to 85 ℃ of crystallizations and obtains the oxalic acid vanadyl (main component is VOC in mass
2O
4H
2O99.1%, Si＜0.01%, TFe＜0.02%, K＜0.01%, Na＜0.01%) crystal 3 6.82g.
Embodiment 4
The present embodiment is used for illustrating the preparation of oxalic acid vanadyl provided by the invention.
Method according to embodiment 2 prepares the oxalic acid vanadyl, and different is, only replaces oxalic acid to make reductive agent with 57g Sulfothiorine, obtains at last oxalic acid vanadyl crystal 5 6.28g (VOC in mass
2O
4H
2O99.2%, Si＜0.01%, TFe＜0.02%, K＜0.01%, Na＜0.01%).
Comparative Examples 1
This Comparative Examples is used for the preparation of the oxalic acid vanadyl of explanation prior art.
20g technical grade Vanadium Pentoxide in FLAKES and 30g oxalic acid are put into reaction vessel and added 80mL water, finished reduction reaction in 3 hours at normal pressure, 50 ℃ of stir abouts, obtaining solution is got oxalic acid vanadyl 36.48g (VOC in mass at 85 ℃ of evaporates to dryness
2O
4H
2O 96.1%)
Following table 1 has been listed the content of Vanadium Pentoxide in FLAKES in the raw material that embodiment and Comparative Examples provide and content and the purity of transformation efficiency and product mesoxalic acid vanadyl.
Table 1
The transformation efficiency %=product mesoxalic acid vanadyl content mol/ (pentoxide content mol in 2 * raw material) * 100% of Vanadium Pentoxide in FLAKES in the raw material
Result by embodiment of the invention 1-4 and Comparative Examples 1 as can be known, the feed stock conversion of the oxalic acid vanadyl that the method according to this invention prepares is high, product purity is high.By embodiment 4 and embodiment 2 more as can be known, adopt preferred reductive agent Sulfothiorine, can further improve feed stock conversion and the output of oxalic acid vanadyl.In addition, method technical process provided by the invention is simple, is easy to realize.
Claims (10)
1. the preparation method of an oxalic acid vanadyl is characterized in that, the method may further comprise the steps:
(1) in the presence of aqueous sulfuric acid, the raw material that will contain Vanadium Pentoxide in FLAKES contacts with reductive agent, obtains the tetravalence vanadium solution;
(2) the tetravalence vanadium solution that step (1) is obtained contacts with alkali-metal oxyhydroxide and carries out precipitin reaction, and carries out solid-liquid separation, obtains solid product;
(3) solid product that step (2) is obtained contacts with oxalic acid, obtains the oxalic acid vanadyl.
2. method according to claim 1, wherein, in described step (1), in Vanadium Pentoxide in FLAKES, describedly contain the raw material of Vanadium Pentoxide in FLAKES and the mass ratio of aqueous sulfuric acid is 1: 2.5-5, the mass percent concentration of described aqueous sulfuric acid are 20%-85%.
3. method according to claim 1 wherein, in described step (1), in the presence of aqueous sulfuric acid, will contain the condition that the raw material of Vanadium Pentoxide in FLAKES contacts with reductive agent and comprise that temperature is 95-100 ℃, and the time is 0.5-2 hour.
4. according to claim 1 or 3 described methods, wherein, in described step (1), the reductive agent that described raw material with containing Vanadium Pentoxide in FLAKES contacts is selected from Sulfothiorine, oxalic acid and the formic acid one or more.
5. method according to claim 4 wherein, in described step (1), in Vanadium Pentoxide in FLAKES, describedly contains the raw material of Vanadium Pentoxide in FLAKES and the mol ratio of reductive agent is 1: 1.4-3.2.
6. method according to claim 1, wherein, in described step (2), the tetravalence vanadium solution that step (1) is obtained contacts the condition of carrying out precipitin reaction and comprises that pH is 2-5 with alkali-metal oxyhydroxide, temperature is 15-80 ℃, and the time is 0.1-1 hour.
7. according to claim 1 or 6 described methods, wherein, in described step (2), described alkali-metal oxyhydroxide is NaOH and/or KOH.
8. method according to claim 1, wherein, in described step (3), the solid product that described step (2) obtains and the mass ratio of oxalic acid are 1: 1-1.4.
9. according to claim 1 or 8 described methods, wherein, in described step (3), the condition that the solid product that described step (2) obtains contacts with oxalic acid comprises that temperature is 15-40 ℃, and the time is 0.1-0.5 hour.
10. according to claim 1,2,3 or 5 described methods, wherein, in the described raw material that contains Vanadium Pentoxide in FLAKES, V
2O
5The quality percentage composition be＞99.8%, the quality percentage composition of Si is that the quality percentage composition of＜0.01%, TFe is that the quality percentage composition of＜0.02%, P is＜0.005%, the quality percentage composition of K is that the quality percentage composition of＜0.01%, Na is＜0.01%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923245A (en) * | 2014-05-04 | 2014-07-16 | 中国科学院长春应用化学研究所 | Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof |
| CN103923246A (en) * | 2014-05-04 | 2014-07-16 | 中国科学院长春应用化学研究所 | Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof |
| CN105948121A (en) * | 2016-05-04 | 2016-09-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing highly pure vanadium dioxide |
| CN109321941A (en) * | 2018-11-09 | 2019-02-12 | 成都先进金属材料产业技术研究院有限公司 | The method for preparing vanadium oxalate |
| CN114292180A (en) * | 2021-11-19 | 2022-04-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadyl oxalate by extraction method |
| CN114292180B (en) * | 2021-11-19 | 2024-04-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadyl oxalate by extraction method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103923245A (en) * | 2014-05-04 | 2014-07-16 | 中国科学院长春应用化学研究所 | Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof |
| CN103923246A (en) * | 2014-05-04 | 2014-07-16 | 中国科学院长春应用化学研究所 | Preparation method of catalyst containing trivalent vanadium, vanadium catalyst composition and application thereof |
| CN105948121A (en) * | 2016-05-04 | 2016-09-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing highly pure vanadium dioxide |
| CN109321941A (en) * | 2018-11-09 | 2019-02-12 | 成都先进金属材料产业技术研究院有限公司 | The method for preparing vanadium oxalate |
| CN114292180A (en) * | 2021-11-19 | 2022-04-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadyl oxalate by extraction method |
| CN114292180B (en) * | 2021-11-19 | 2024-04-26 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing high-purity vanadyl oxalate by extraction method |
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