CN107662946B - Preparation method of vanadium trioxide - Google Patents
Preparation method of vanadium trioxide Download PDFInfo
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Abstract
The invention discloses a preparation method of vanadium trioxide applicable to a vanadium battery, which comprises the following steps: and (3) carrying out liquid phase reduction on ammonium vanadate with the vanadium valence of +5 and oxalic acid or a solvate of oxalic acid in a reaction solvent, evaporating the reaction solution to dryness, and calcining to obtain the catalyst. The method takes cheap and easily-obtained + 5-valent ammonium vanadate as a raw material, and vanadium trioxide with the purity of up to 99 percent can be obtained by oxalic acid reduction and calcination. The production process has the advantages of simple operation, low energy consumption, safety and low equipment requirement, is suitable for industrial large-scale production, and can obviously reduce the production cost of vanadium trioxide.
Description
Technical Field
The invention relates to a preparation method of vanadium trioxide, belonging to the field of chemical material synthesis.
Background
Vanadium trioxide is an important vanadium oxide and is widely applied to the fields of high vanadium iron and vanadium-nitrogen alloy production, sensors, novel electronic components, battery production and the like. The vanadium trioxide has a good application prospect in the production process of the all-vanadium redox flow battery electrolyte, and the method for preparing the 3.5-valent vanadium electrolyte by reducing the vanadium pentoxide by using the vanadium trioxide as a reducing agent is simple in production process, good in reduction effect, free of other impurities, and capable of reducing the production cost of the vanadium electrolyte by combining the advantages of a chemical reduction method and an electrolysis method, so that the method is widely concerned by related industries once being put forward. However, the current method for producing vanadium electrolyte is limited due to high preparation cost and low product purity of vanadium trioxide.
Currently, vanadium trioxide is mainly prepared by reduction of high-valence vanadium compounds. The reduction method comprises reducing with external reductant (such as sulfur, carbon powder, graphite, etc.), and reducing gas (such as H)2CO, etc.), ammonium vanadate decomposition, ammonia cracking reduction, etc. The method for reducing by adding reducing agents such as graphite, carbon and the like has simple production process, but the required reduction temperature is high, and carbon is easy to remain in the product or bring other impurities into the product; h2Or reducing gases such as CO and the like have good reducing effect and high product purity, but have the dangers of combustion, explosion or toxic gas leakage and the like; decomposing ammonium vanadate, cracking generated ammonia gas into H2And N2The method for preparing vanadium trioxide by reduction is clean and environment-friendly, does not need to add any reducing agent, but has incomplete ammonia gas cracking, insufficient reduction and higher requirement on equipment. In addition to the above main preparation methods, vanadium-containing hydrazine salt can be calcined under the condition of protective gas, and vanadium trioxide with uniform and fine particle size can be synthesized by adding an organic reducing agent and then adopting hydrothermal synthesis or solvothermal and other methods, and a good application effect can be obtained in related fields.
Disclosure of Invention
The invention aims to provide a preparation method of vanadium trioxide, which overcomes the defects of high cost and complex operation of the existing production process.
The invention provides a preparation method of vanadium trioxide, which comprises the following steps: and (3) carrying out liquid phase reduction on ammonium vanadate with the vanadium valence of +5 and oxalic acid or a solvate of oxalic acid in a reaction solvent, evaporating the reaction solution to dryness, and calcining to obtain the catalyst.
Further, the ammonium vanadate with the vanadium valence of +5 is ammonium metavanadate or ammonium polyvanadate.
Further, the ratio of the molar weight of vanadium in the ammonium vanadate to the molar weight of oxalic acid is 1: (1.5 to 3).
Further preferably, the ratio of the molar amount of vanadium in the ammonium vanadate to the molar amount of oxalic acid is 1: (1.5-2.5).
Further, the molar amount of vanadium in the ammonium vanadate: the volume of the reaction solvent is 5-12 mol/L.
Further preferably, the molar amount of vanadium in the ammonium vanadate is: the volume of the reaction solvent is 8.5-10 mol/L.
Further, the reaction temperature is 80-100 ℃.
Further preferably, the reaction temperature is 80 to 90 ℃.
Further, the calcination is carried out in a protective atmosphere.
Further, the protective atmosphere is one or a mixture of more than two of nitrogen, helium, argon, ammonia, CO and gaseous alkane.
Further preferably, the protective atmosphere is nitrogen.
Further, the calcining temperature is 700-1000 ℃.
Further preferably, the calcination temperature is 700 to 900 ℃.
Furthermore, the calcination time is 1.5-5 h.
More preferably, the calcination time is 2-4 h.
Further, the reaction solvent is water.
Further, the solvate of oxalic acid is oxalic acid dihydrate.
Further, drying is carried out before calcining; in the drying process, in order to prevent the precursor from caking after drying, the precursor needs to be mechanically stirred every 10-20 min.
The invention provides a preparation method of vanadium trioxide. The method uses cheap and easily available + 5-valent ammonium vanadate as a raw material, and obtains the purity by oxalic acid reduction and calcinationUp to 99% vanadium trioxide, with a yield of 100% (not counting transfer losses). The production process has the advantages of simple operation, low energy consumption, safety and low equipment requirement, is suitable for industrial large-scale production, and can obviously reduce the production cost of vanadium trioxide. Furthermore, V obtained by the process2O3The electrolyte suitable for preparing the all-vanadium redox flow battery is placed in an electrolyte with the effective area of 100cm2The vanadium battery has 40 times of charge-discharge cycles, the coulomb efficiency of the battery is kept above 96%, the energy efficiency is kept above 80%, and the coulomb efficiency and the energy efficiency are almost not attenuated. Has wide application prospect in the production process of the electrolyte of the all-vanadium redox flow battery.
Drawings
FIG. 1 is a schematic view of a process for producing vanadium trioxide according to the present invention;
FIG. 2 is an XRD diffraction pattern of a product obtained by the reaction of ammonium metavanadate and oxalic acid according to the molar ratio of 1:0.5 in comparative example 1;
FIG. 3 is an XRD diffraction pattern of a product obtained by the reaction of ammonium metavanadate and oxalic acid according to the molar ratio of 1:1 in comparative example 1;
FIG. 4 is an XRD diffraction pattern of the product obtained from calcination at 400 ℃ in comparative example 2;
FIG. 5 is an XRD diffraction pattern of the product obtained by calcination at 450 ℃ in comparative example 2;
FIG. 6 is an XRD diffraction pattern of the product obtained by calcination at 500 ℃ in comparative example 2;
FIG. 7 is an XRD diffraction pattern of the product of comparative example 2 calcined at 550 ℃;
FIG. 8 is an XRD diffraction pattern of the product obtained from calcination at 600 ℃ in comparative example 2;
FIG. 9 is an XRD diffraction pattern of the product of comparative example 2 calcined at 650 ℃;
FIG. 10 is an XRD diffraction pattern of the product of comparative example 2 calcined at 700 ℃;
FIG. 11 is a graph of the charge-discharge coulombic efficiency and energy efficiency of the battery in test example 1;
FIG. 12 is an XRD diffraction pattern of a product obtained by reacting ammonium metavanadate and oxalic acid at a molar ratio of 1:1.5 in Experimental example 2;
FIG. 13 is an XRD diffraction pattern of a product obtained by reacting ammonium metavanadate and oxalic acid at a molar ratio of 1:2 in Experimental example 2;
FIG. 14 is an XRD diffraction pattern of a product obtained by reacting ammonium metavanadate and oxalic acid at a molar ratio of 1:2.5 in experimental example 2;
FIG. 15 is an XRD diffraction pattern of a product obtained by reacting ammonium metavanadate and oxalic acid at a molar ratio of 1:3 in Experimental example 2.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
The invention provides a preparation method of vanadium trioxide, which comprises the following steps (a production process schematic diagram is shown in figure 1):
1) mixing ammonium metavanadate or ammonium polyvanadate with oxalic acid (mixing ratio is, molar weight of vanadium: molar amount of oxalic acid 1: 1.5-1: 2.5), adding the mixture into deionized water at the temperature of 80-90 ℃ (the molar weight of vanadium: the volume of water is 8.5-10 mol/L), and carrying out liquid phase reduction;
2) after the ammonium metavanadate or the ammonium polyvanadate is completely dissolved, heating to boil, concentrating and evaporating the solution to dryness to obtain a precursor;
3) and roasting the obtained precursor for 2-4 h under the protection of nitrogen at the temperature of 700-900 ℃, and cooling to room temperature under the protection of nitrogen to obtain vanadium trioxide.
In the production process, the main component is (NH)4)2(VO)2(C2O4)3The preparation process has the obvious advantages that ① vanadium trioxide can be obtained with high purity and high yield, the process stability is strong, the quality of the obtained product is stable, ② vanadium trioxide is very suitable for preparing vanadium electrolyte, the charging and discharging efficiency of the battery is good, and the application effect is good.
In addition, the invention further inspects various parameter conditions in the preparation process, and the result shows that the mutual matching of the oxalic acid dosage and the calcination temperature has obvious influence on the product. When the molar weight ratio of vanadium to oxalic acid is lower than 1:1.5, vanadium trioxide is difficult to obtain; accordingly, under the condition that the calcination temperature is lower than 700 ℃, even if the amount of the oxalic acid is repeatedly adjusted, the purity of the vanadium trioxide is difficult to reach the requirement. Under the specific matching of the two, the purity of the product is finally improved to more than 99 percent, and the yield of the vanadium has no other loss except the transfer loss in the production process.
At present, no report on the preparation of vanadium trioxide by reacting + 5-valent ammonium vanadate with oxalic acid is found. Compared with the prior art, the method has the advantages that the reducing agent (such as sulfur, carbon powder, graphite and the like) or reducing gas (such as H) is added into the external reinforcement body2CO, etc.), the invention has the obvious advantages of low production cost, simple and convenient operation, safety, etc.
Example 1 preparation of vanadium trioxide by the Process of the invention
1) Analytically pure ammonium metavanadate is mixed with analytically pure oxalic acid dihydrate (mixing ratio, molar amount of vanadium: molar amount of oxalic acid 1: 1.5) were added in portions to deionized water at a temperature of 80 ℃ (molar amount of vanadium: water volume is 10mol/L), and liquid phase reduction is carried out;
2) after the ammonium metavanadate is completely dissolved, heating to boiling, concentrating and evaporating the solution to dryness to obtain a precursor;
3) drying the precursor at 160 ℃, roasting for 2.5h under the protection of nitrogen at 700 ℃, and cooling to room temperature under the protection of nitrogen. The purity of the finally prepared vanadium trioxide is 98.8%.
Example 2 vanadium trioxide prepared by the process of the invention
1) Analytically pure ammonium metavanadate is mixed with analytically pure oxalic acid dihydrate (mixing ratio, molar amount of vanadium: molar amount of oxalic acid 1: 2) and added in portions to deionized water at a temperature of 95 ℃ (molar amount of vanadium: the volume of water is 9mol/L), and liquid-phase reduction is carried out;
2) after the ammonium metavanadate is completely dissolved, heating to boiling, concentrating and evaporating the solution to dryness to obtain a precursor;
3) drying the obtained precursor at 100 ℃, roasting for 3h under the protection of nitrogen and at the temperature of 750 ℃, and cooling to room temperature under the protection of nitrogen. The purity of the finally prepared vanadium trioxide is 99.2%.
Example 3 vanadium trioxide prepared by the process of the invention
1) Analytically pure ammonium metavanadate is mixed with analytically pure oxalic acid dihydrate (mixing ratio, molar amount of vanadium: molar amount of oxalic acid 1: 2.5), added in portions to deionized water at a temperature of 85 ℃ (molar amount of vanadium: water volume is 10mol/L), and liquid phase reduction is carried out;
2) after the ammonium metavanadate is completely dissolved, heating to boiling, concentrating and evaporating the solution to dryness to obtain a precursor;
3) drying the obtained precursor at 200 ℃, roasting for 2h under the protection of nitrogen at 800 ℃, and cooling to room temperature under the protection of nitrogen. The purity of the finally prepared vanadium trioxide is 99.4%.
Example 4 vanadium trioxide prepared by the process of the invention
1) Analytically pure ammonium metavanadate is mixed with analytically pure oxalic acid dihydrate (mixing ratio, molar amount of vanadium: molar amount of oxalic acid 1: 3) and added in portions to deionized water at a temperature of 90 ℃ (molar amount of vanadium: the volume of water is 8.5mol/L), and liquid-phase reduction is carried out;
2) after the ammonium metavanadate is completely dissolved, heating to boiling, concentrating and evaporating the solution to dryness to obtain a precursor;
3) drying the obtained precursor at 180 ℃, roasting for 3h under the protection of nitrogen at 900 ℃, and cooling to room temperature under the protection of nitrogen. Finally, the purity of the prepared vanadium trioxide is 99.0%.
Comparative example 1 influence of oxalic acid amount on product in preparation Process
In the experiment, ammonium metavanadate and oxalic acid are reacted at a molar ratio of 1:0.5 and 1:1 respectively, and the prepared precursor is roasted at 700 ℃ under the protection of nitrogen to obtain a product, wherein the specific process conditions are the same as those in example 1. XRD diffraction analysis was performed on the obtained product, and the analysis results are shown in FIGS. 2 and 3.
From the XRD pattern analysis of FIGS. 2 and 3, it can be seen that when the molar ratio of ammonium metavanadate to oxalic acid is 1:0.5 and 1:1, the main component of the obtained product is VO2、V3O5Instead of the target substance V2O3。
In addition, in a comparative experiment, the use amount of oxalic acid is further increased on the basis of the molar ratio of ammonium metavanadate to oxalic acid being 1:3, and as a result, on the premise of not increasing the calcination temperature, the content of amorphous carbon in a product obtained by calcination is increased along with the increase of the addition amount of oxalic acid, and the amorphous carbon diffraction peak impurity peak is more and more obvious in XRD diffraction, which indicates that the purity of the obtained product is obviously reduced.
The above test results show that the consumption of oxalic acid has a significant effect on the final product, and within the range of the consumption determined by the preparation process of the present invention, the ratio of the molar weight of vanadium in ammonium vanadate to the molar weight of oxalic acid is 1: (1.5-3), the target product V can be prepared in high yield and high purity2O3。
Comparative example 2 Effect of calcination temperature on product in preparation Process
The precursor is prepared according to the embodiment 1, the precursor is placed in a tube furnace, nitrogen is introduced for protection, the precursor is roasted for 4 hours at 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and 700 ℃ respectively, and after the roasting is finished, the nitrogen is continuously introduced until the furnace temperature is reduced to the room temperature. XRD diffraction analysis is carried out on the obtained product, and the analysis result is shown in figures 4-10.
As can be seen from FIGS. 4 to 10, V is increased with the rise of the baking temperature2O3The diffraction peak of (A) is more and more obvious, and the miscellaneous peak is weaker and weaker. The results show that when the precursor is roasted at the temperature lower than 700 ℃, the precursor is not completely decomposed, the amorphous carbon content in the product is high, and the product purity is not high; when the calcination temperature is higher than 700 ℃, the precursor is thoroughly decomposed, the carbon in the precursor has stronger reduction capability on vanadium, and high-purity V can be obtained2O3。
The following test examples demonstrate the advantageous effects of the present invention.
Test example 1 preparation of vanadium battery using vanadium trioxide of the present invention as raw material
Mixing vanadium pentoxide with vanadium trioxide prepared according to embodiment 1 of the invention according to a molar ratio of 4.2:1, adding 6mol/L sulfuric acid, reacting at 90 ℃ for 120min, cooling to room temperature, filtering, and determining the content (V) of trivalent vanadium and pentavalent vanadium in the filtrate+3:V+51.04:1), adding deionized water to adjust H in the solution2SO4The concentration is 3mol/L, and the total vanadium concentration is 2 mol/L. Respectively placing the same amount of electrolyte in positive and negative liquid storage tanks of vanadium cell (the effective area of vanadium cell is 100 cm)2) At 40mA/cm2The energy efficiency and the coulombic efficiency of the cell are shown in fig. 11, after 40 constant current charge-discharge cycles.
As can be seen from fig. 11, the coulombic efficiency of the battery was maintained at 96% or more, the energy efficiency was maintained at 80% or more, and the coulombic efficiency and the energy efficiency were hardly attenuated, indicating that the electrolyte had good performance.
The test results show that V prepared by the method of the invention2O3The method is suitable for preparing the electrolyte of the all-vanadium redox flow battery, the purity of the electrolyte can meet the requirement of preparing the vanadium battery, the production cost is obviously reduced, and the method is favorable for further popularization and application of the method for preparing the 3.5-valent vanadium electrolyte by reducing vanadium pentoxide by using vanadium trioxide as a reducing agent.
Test example 2 verification test of the preparation Process of the present invention
Ammonium metavanadate and oxalic acid are reacted at a molar ratio of 1:1.5, 1:2, 1:2.5 and 1:3 respectively, and the prepared precursor is roasted at 700 ℃ under the protection of nitrogen to obtain a reduction product, wherein the process conditions are the same as those of example 1. XRD diffraction analysis is carried out on the obtained product, and the analysis result is shown in figures 12-15.
The XRD pattern analysis of figures 12-15 shows that the main components of the products are V2O3。
The test results show that the preparation process is stable and reliable, and the obtained product has stable quality.
Claims (12)
1. The preparation method of vanadium trioxide is characterized by comprising the following steps: the method comprises the following steps: carrying out liquid phase reduction on ammonium vanadate with vanadium valence of +5 and oxalic acid or a solvate of oxalic acid in a reaction solvent, evaporating the reaction solution to dryness, and calcining to obtain the catalyst; the molar weight ratio of vanadium in the ammonium vanadate to oxalic acid is 1: (1.5-3); the temperature of liquid phase reduction is 80-100 ℃; the calcination temperature is 700-1000 ℃; the solvate of oxalic acid is oxalic acid dihydrate; the calcination is carried out in a protective atmosphere.
2. The method of claim 1, wherein: the ammonium vanadate with the vanadium valence of +5 is ammonium metavanadate or ammonium polyvanadate.
3. The method of claim 1, wherein: the molar weight ratio of vanadium in the ammonium vanadate to oxalic acid is 1: (1.5-2.5).
4. The method according to any one of claims 1 to 3, wherein: the molar weight of vanadium in the ammonium vanadate is as follows: the volume of the reaction solvent is 5-12 mol/L.
5. The method according to any one of claims 1 to 3, wherein: the molar weight of vanadium in the ammonium vanadate is as follows: the volume of the reaction solvent is 8.5-10 mol/L.
6. The method of claim 1, wherein: the temperature of liquid phase reduction is 80-90 ℃.
7. The method of claim 1, wherein: the protective atmosphere is one or a mixture of more than two of nitrogen, helium, argon, ammonia, CO and gaseous alkane.
8. The method of claim 1, wherein: the protective atmosphere is nitrogen.
9. The method of claim 1, wherein: the calcination temperature is 700-900 ℃.
10. The method according to any one of claims 1 and 7 to 9, wherein: the calcination time is 1.5-5 h.
11. The method according to any one of claims 1 and 7 to 9, wherein: the calcination time is 2-4 h.
12. The method of claim 1, wherein: the reaction solvent is water.
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CN108423712A (en) * | 2018-04-12 | 2018-08-21 | 四川星明能源环保科技有限公司 | Vanadium trioxide and preparation method thereof |
CN110857223A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Preparation method of high-purity vanadium trioxide powder |
CN110857222A (en) * | 2018-08-23 | 2020-03-03 | 南京理工大学 | Preparation method of vanadium trioxide powder |
CN110581284B (en) * | 2019-09-30 | 2020-12-08 | 陕西科技大学 | Electrocatalysis function V2O3Preparation method and application of @ Co |
CN112408478B (en) * | 2020-12-02 | 2022-03-15 | 中国科学院过程工程研究所 | Preparation method of vanadium trioxide |
CN114293321B (en) * | 2021-12-30 | 2023-02-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Low-cost room-temperature rapid batch preparation method and equipment for special-shaped vanadium oxide nanofibers and aggregates thereof |
CN114684854A (en) * | 2022-03-30 | 2022-07-01 | 东风汽车集团股份有限公司 | Preparation method of nano vanadium trioxide |
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