CN103319326B - Preparation method for vanadyl oxalate - Google Patents
Preparation method for vanadyl oxalate Download PDFInfo
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- CN103319326B CN103319326B CN201210079205.4A CN201210079205A CN103319326B CN 103319326 B CN103319326 B CN 103319326B CN 201210079205 A CN201210079205 A CN 201210079205A CN 103319326 B CN103319326 B CN 103319326B
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- vanadium pentoxide
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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 vanadyl oxalate.
Background technology
Vanadyl oxalate is as a kind of industrial important presoma, its use range is very widely, such as, functional materials supplementary issue (38) volume in 2007 utilizes the method for ammonium solution vanadyl oxalate presoma to prepare the Emission in Cubic VN powder of about median size 50mm.
In view of the needs to the new utilization ways of vanadyl oxalate, and vanadium resource is utilized to the expansion in field, developing new vanadyl oxalate preparation technology and be inevitable, there is the present situation that feed stock conversion is low, product purity is not high in current vanadyl oxalate preparation method.
Such as, CN1693212A discloses a kind of preparation method of vanadium dioxide nano powder, wherein refer to Vanadium Pentoxide in FLAKES and oxalic acid for raw material in aqueous direct heating reduction prepare precursor vanadyl oxalate, this method is as a kind of precursor using vanadyl oxalate, preparation technology is comparatively simple, but Vanadium Pentoxide in FLAKES low conversion rate in raw material, and in vanadyl oxalate product, foreign matter content is high.
Summary of the invention
Goal of the invention of the present invention is to overcome the low conversion rate adopting prior art to prepare Vanadium Pentoxide in FLAKES in the method Raw of vanadyl oxalate, the defect that in the vanadyl oxalate product prepared, foreign matter content is high, there is provided a kind of preparation method of vanadyl oxalate, feed stock conversion improves, product purity improves to adopt the inventive method to make.
For achieving the above object, the invention provides a kind of preparation method of vanadyl oxalate, the method comprises the following steps: the raw material containing Vanadium Pentoxide in FLAKES, under the existence of aqueous sulfuric acid, contacts with reductive agent by (1), obtains tetravalence vanadium solution; (2) tetravalence vanadium solution step (1) 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) obtains is contacted with oxalic acid, obtain vanadyl oxalate.
Method of the present invention has following beneficial effect: in raw material, Vanadium Pentoxide in FLAKES transformation efficiency is high, and the purity of the vanadyl oxalate product of preparation is high.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to method of the present invention, in described step (1), described aqueous sulfuric acid is that raw material is commonly used in this area, act as the Vanadium Pentoxide in FLAKES in activation raw material, for making activation effect better, preferably, in Vanadium Pentoxide in FLAKES, raw material containing Vanadium Pentoxide in FLAKES and aqueous sulfuric acid mass ratio are 1: 2.5-5, and the mass percent concentration of aqueous sulfuric acid can be 20%-85%.
In described step (1), the reductive agent that described reductive agent can be commonly used for this area, reductive agent act as and pentavalent vanadium in raw material is reverted to tetravalence, in order to prevent vanadium to be reduced to lower valence state, preferably, reductive agent to be selected from Sulfothiorine, oxalic acid and formic acid one or more, more preferably in situation, when adopting Sulfothiorine and/or formic acid, can reduce more fully and obtaining tetravalence vanadium solution, to be conducive to the transformation efficiency improving raw material.
In described step (1), the selectable range of the consumption of described reductive agent is wider, and in order to make reaction better carry out, preferably, in Vanadium Pentoxide in FLAKES, described is 1: 1.4-3.2 containing the raw material of Vanadium Pentoxide in FLAKES and the mol ratio of reductive agent.
In described step (1), under the existence of aqueous sulfuric acid, raw material containing Vanadium Pentoxide in FLAKES is contacted the selectable range carrying out the condition of reacting with reductive agent wider, the transformation efficiency being more conducive to improving Vanadium Pentoxide in FLAKES is better carried out for making reduction reaction, the condition that raw material containing Vanadium Pentoxide in FLAKES contacts with reductive agent being comprised temperature is 95-100 DEG C, time is 0.5-5 hour, and under further 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 object is that the impurity removed in raw material is also separated the solid product obtained containing tetravalence vanadium.Reaction system in acid, alkali-metal oxyhydroxide add the tetravalence vanadium generation precipitin reaction made in solution, in order to make reaction effect better, precipitin reaction is more complete, and preferably, pH is 2-5.
In described step (2), described alkali metal hydroxide can be the common raw material in this area, object is the pH value 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 in order to make reaction effect better, preferably, temperature is 15-80 DEG C, and further preferably, temperature is 40-70 DEG C, and the time is 0.1-1 hour.
In described step (3), the solid product that step (2) obtains is contacted with oxalic acid, needed for the selectable range of mass ratio of the oxalic acid that adds and solid product wider, considering cost and yield, preferably, in described step (3), the mass ratio of the solid product that described step (2) obtains and oxalic acid is 1: 1-1.4.
In described step (3), the solid product that step (2) obtains is contacted with oxalic acid, then obtains vanadyl oxalate crystallization by ordinary method crystallization, be separated and obtain the finished product vanadyl oxalate.Under preferable case, it is 15-40 DEG C that the condition that the solid product that described step (2) obtains contacts with oxalic acid is comprised temperature, and the time is 0.1-0.5 hour.
According to method of the present invention, the described raw material containing Vanadium Pentoxide in FLAKES can commonly use raw material for this area, in order to improve the purity of the vanadyl oxalate prepared further, preferably adopts the raw material containing Vanadium Pentoxide in FLAKES that purity is higher, V in raw material
2o
5mass percentage be > 99.8%, the mass percentage of Si is < 0.01%, the mass percentage of TFe is < 0.02%, the mass percentage of P is < 0.005%, the mass percentage of K is the mass percentage of < 0.01%, Na is < 0.01%.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive 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.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different 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 vanadyl oxalate product that following embodiment and comparative example prepare first takes vanadyl oxalate 2.000g, with retort furnace roasting 1h at 300 DEG C, GB 8639.1-1988 vanadium chemistry analytical procedure potassium permanganate-ferrous sulfate is adopted to measure TV (total vanadium) afterwards, then draw vanadyl oxalate crystalline content, formula is vanadyl oxalate crystalline content %=3.3922 (reduction factor) × TV (taking the total content of vanadium percentage ratio % in vanadyl oxalate).
Embodiment 1
The present embodiment is for illustration of the preparation of vanadyl oxalate provided by the invention.
20g is contained Vanadium Pentoxide in FLAKES raw material (purchased 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 45% aqueous sulfuric acid mixes with 75g mass percent concentration, at system temperature is 95 DEG C, 40g Sulfothiorine is added in described mixture, reaction times is 1 hour, obtain tetravalence vanadium solution, NaOH adjust ph to 2 is added again at 70 DEG C, 0.5 hour reaction times, generate precipitation, solid-liquid separation is carried out in filtration, and at 25 DEG C vacuum drying, obtain solid matter 22.02g, then at 25 DEG C, oxalic acid 22g is added, by solid material dissolves, reaction times is 0.1 hour, and be heated to 85 DEG C of crystallizations and obtain vanadyl oxalate (main component is VOC in mass
2o
4h
2o99.1%, Si < 0.01%, TFe < 0.02%, K < 0.01%, Na < 0.01%) crystal 37.48g.
Embodiment 2
The present embodiment is for illustration of the preparation of vanadyl oxalate provided by the invention.
30g is contained Vanadium Pentoxide in FLAKES raw material (purchased 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 120g mass percent concentration, at system temperature is 98 DEG C, 44g oxalic acid is added in described mixture, 0.5 hour reaction times, obtain tetravalence vanadium solution, NaOH adjust ph to 4 is added again at 40 DEG C, 0.1 hour reaction times, solid-liquid separation is carried out in filtration, and at 25 DEG C vacuum drying, obtain solid matter 32.86g, then at 15 DEG C, oxalic acid 41g is added, by solid material dissolves, reaction times is 0.4 hour, be heated to 85 DEG C of crystallizations and obtain vanadyl oxalate (main component (in mass) VOC
2o
4h
2o98.7%, Si < 0.01%, TFe < 0.02%, K < 0.01%, Na < 0.01%) crystal 55.88g.
Embodiment 3
The present embodiment is for illustration of the preparation of vanadyl oxalate provided by the invention.
20g is contained Vanadium Pentoxide in FLAKES raw material (purchased 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 85% aqueous sulfuric acid mixes with 70g mass percent concentration, at system temperature is 100 DEG C, 16g formic acid is added in described mixture, 2 hours reaction times, obtain tetravalence vanadium solution, KOH adjust ph to 5 is added again at 55 DEG C, 1 hour reaction times, generate precipitation, solid-liquid separation is carried out in filtration, and at 25 DEG C vacuum drying, obtain solid matter 21.88g, then at 40 DEG C, oxalic acid 23.4g is added, by solid material dissolves, reaction times is 0.5 hour, be heated to 85 DEG C of crystallizations to obtain vanadyl oxalate (main component is VOC in mass
2o
4h
2o99.1%, Si < 0.01%, TFe < 0.02%, K < 0.01%, Na < 0.01%) crystal 36.82g.
Embodiment 4
The present embodiment is for illustration of the preparation of vanadyl oxalate provided by the invention.
Vanadyl oxalate is prepared according to the method for embodiment 2, unlike, only replace oxalic acid to make reductive agent with 57g Sulfothiorine, finally obtain vanadyl oxalate crystal 56.28g (VOC in mass
2o
4h
2o99.2%, Si < 0.01%, TFe < 0.02%, K < 0.01%, Na < 0.01%).
Comparative example 1
This comparative example is for illustration of the preparation of the vanadyl oxalate of prior art.
20g technical grade Vanadium Pentoxide in FLAKES and 30g oxalic acid put into reaction vessel and adds 80mL water, within 3 hours, completing reduction reaction at normal pressure, 50 DEG C of stir abouts, obtained solution is obtained vanadyl oxalate 36.48g (VOC in mass at 85 DEG C of evaporates to dryness
2o
4h
2o 96.1%)
Following table 1 lists the content of Vanadium Pentoxide in FLAKES and the content of transformation efficiency and product mesoxalic acid vanadyl and purity in the raw material that embodiment and comparative example provide.
Table 1
Transformation efficiency %=product mesoxalic acid vanadyl content mol/ (in 2 × raw material pentoxide content mol) × 100% of Vanadium Pentoxide in FLAKES in raw material
Known by the result of embodiment of the present invention 1-4 and comparative example 1, the feed stock conversion of the vanadyl oxalate that method according to the present invention prepares is high, and product purity is high.More known by embodiment 4 and embodiment 2, adopts preferred reductive agent Sulfothiorine, can improve feed stock conversion and the output of vanadyl oxalate further.In addition, method technical process provided by the invention is simple, is easy to realize.
Claims (10)
1. a preparation method for vanadyl oxalate, is characterized in that, the method comprises the following steps:
(1) under the existence of aqueous sulfuric acid, the raw material containing Vanadium Pentoxide in FLAKES is contacted with reductive agent, obtain tetravalence vanadium solution;
(2) tetravalence vanadium solution step (1) 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) obtains is contacted with oxalic acid, obtain vanadyl oxalate;
In described step (2), tetravalence vanadium solution step (1) obtained contacts the pH carrying out precipitin reaction with alkali-metal oxyhydroxide be 2-5.
2. method according to claim 1, wherein, in described step (1), in Vanadium Pentoxide in FLAKES, described is 1:2.5-5 containing the raw material of Vanadium Pentoxide in FLAKES and the mass ratio of aqueous sulfuric acid, and the mass percent concentration of described aqueous sulfuric acid is 20%-85%.
3. method according to claim 1, wherein, in described step (1), under the existence of aqueous sulfuric acid, the condition that the raw material containing Vanadium Pentoxide in FLAKES contacts with reductive agent being comprised temperature is 95-100 DEG C, and the time is 0.5-2 hour.
4. the method according to claim 1 or 3, wherein, in described step (1), to be describedly selected from Sulfothiorine, oxalic acid and formic acid one or more with the reductive agent of the contact raw containing Vanadium Pentoxide in FLAKES.
5. method according to claim 4, wherein, in described step (1), in Vanadium Pentoxide in FLAKES, described is 1:1.4-3.2 containing the raw material of Vanadium Pentoxide in FLAKES and the mol ratio of reductive agent.
6. method according to claim 1, wherein, in described step (2), tetravalence vanadium solution step (1) obtained contacts the condition of carrying out precipitin reaction, and to comprise temperature be 15-80 DEG C with alkali-metal oxyhydroxide, and the time is 0.1-1 hour.
7. the method according to claim 1 or 6, 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 mass ratio of the solid product that described step (2) obtains and oxalic acid is 1:1-1.4.
9. the method according to claim 1 or 8, wherein, in described step (3), it is 15-40 DEG C that the condition that the solid product that described step (2) obtains contacts with oxalic acid comprises temperature, and the time is 0.1-0.5 hour.
10. the method according to claim 1,2,3 or 5, wherein, described containing in the raw material of Vanadium Pentoxide in FLAKES, V
2o
5mass percentage be >99.8%, the mass percentage of Si is <0.01%, the mass percentage of TFe is <0.02%, the mass percentage of P is <0.005%, the mass percentage of K is the mass percentage of <0.01%, Na is <0.01%.
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| CN103923245B (en) * | 2014-05-04 | 2016-08-24 | 中国科学院长春应用化学研究所 | Preparation method, vanadium catalyst composition and the application thereof of a kind of catalyst containing trivalent vanadium |
| 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 |
| 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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| CN1491898A (en) * | 2002-09-25 | 2004-04-28 | 攀枝花钢铁有限责任公司钢铁研究院 | Process for preparinbg vanadylic sulfate and use |
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| CN1491898A (en) * | 2002-09-25 | 2004-04-28 | 攀枝花钢铁有限责任公司钢铁研究院 | Process for preparinbg vanadylic sulfate and use |
Non-Patent Citations (1)
| Title |
|---|
| 新型钒氧配合物的合成、表征及生物活性初探;马玖芬;《中国优秀硕士学位论文全文数据库工程科技I辑》;20120315(第03期);B014-127 * |
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