CN108358243B - Preparation method of vanadium pentoxide with tetravalent vanadium content less than five hundred thousandths - Google Patents
Preparation method of vanadium pentoxide with tetravalent vanadium content less than five hundred thousandths Download PDFInfo
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Abstract
The invention provides a preparation method of vanadium pentoxide with tetravalent vanadium content less than 0.005 wt%, which comprises the following steps: and heating ammonium metavanadate in an oxidizing atmosphere, carrying out pretreatment at a constant temperature of 150-280 ℃, then continuing heating, and carrying out calcination treatment to obtain vanadium pentoxide with the tetravalent vanadium content of less than 0.005 wt%. According to the method, the purity of the obtained vanadium pentoxide product is further improved compared with that of the traditional process by introducing a pretreatment step before the traditional calcination process, the method can be applied by adjusting the calcination process flow in industrial production without additionally purchasing other equipment, and the method can obtain the vanadium pentoxide product with the purity of more than or equal to 99.95 wt% and the content of tetravalent vanadium of less than 0.005 wt%, and can meet the requirements of various fields on the vanadium pentoxide product with high purity and low content of tetravalent vanadium.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of vanadium pentoxide with tetravalent vanadium content of less than 0.005 wt%.
Background
Vanadium is an important strategic reserve metal and has very wide application, can be used as an additive to be added into metal materials such as steel and the like to enhance the performance of the metal materials, can also be used as a battery material to be used for preparing high-density energy storage materials such as vanadium batteries and the like, and belongs to indispensable raw materials in the fields of aerospace, energy engineering, biomedicine, metal processing and the like. In recent years, with the progress of technology, the industrial production of some vanadium downstream high-end technology products has higher requirements on the quality of vanadium compounds, particularly vanadium pentoxide, and particularly with the development of vanadium batteries and vanadium energy storage equipment, the supply of domestic high-purity vanadium pentoxide can not meet the market demand and mainly depends on import, so that the production of high-purity vanadium pentoxide has wide prospects in China, and the development of the production technology of high-purity vanadium pentoxide has great application value and social significance.
The vanadium pentoxide has the problem of high tetravalent vanadium content except for some conventional impurity metal ions, and few manufacturers are provided for mastering the production process of the vanadium pentoxide with high purity and low tetravalent vanadium content at home at present, so that the technical level of the vanadium pentoxide is far behind compared with that of the vanadium pentoxide at home and the product quality is unstable. The production process of the high-purity vanadium pentoxide mainly comprises two processes, wherein the first process is to carry out deep impurity removal on a vanadium-containing solution, and the second process is to prepare the high-purity vanadium by a calcination method, wherein the preparation of the high-purity vanadium by the calcination method is widely applied and comprises the following steps according to the calcination method and equipment: static electric furnace sintering, dynamic rotary kiln sintering, microwave static sintering, and the like. The static electric furnace calcination method is more traditional, and has the advantages of less equipment investment, simple operation and mature process, but the calcination is usually incomplete, the dynamic rotary kiln calcination method has the advantages of uniform product quality, but large equipment investment, high energy consumption and easy generation of environmental pollution, the microwave static calcination method has the advantages of relatively low energy consumption and stable product quality, but can not carry out industrial production, and the methods have the problem of high tetravalent vanadium content in the product, so the calcination process needs to be improved.
In the prior art, some attempts have been made to obtain high-purity vanadium pentoxide by improving a calcination process, but the purity of the prepared vanadium pentoxide is still low, wherein the content of tetravalent vanadium is still high, for example, CN101811734A discloses a method for preparing vanadium pentoxide by calcining ammonium metavanadate with microwave, wherein ammonium metavanadate with particle size of more than 10 μm and vanadium pentoxide powder are blended, and calcined at a heating rate of 20-100 ℃/min to 500-550 ℃ for 5-30 min by using microwave to obtain vanadium pentoxide with purity of 98.5 wt%, CN102502829A discloses a production process for preparing high-purity vanadium pentoxide by calcining and decomposing ammonium metavanadate, wherein high-purity ammonium metavanadate powder is placed in a stainless steel container, and subjected to dehydration, deamination and calcination oxidation reaction in a reaction furnace in an oxidizing atmosphere under low vacuum degree to obtain high-purity vanadium pentoxide, the content of tetravalent vanadium in the prepared vanadium pentoxide is less than 0.20 wt%, and the content of the vanadium pentoxide can reach 99.5%.
On the basis of the prior art, a person skilled in the art needs to further improve the calcination process of ammonium metavanadate to prepare high-purity vanadium pentoxide with higher purity and less tetravalent vanadium content, and the calcination process is simple and easy to use, has low requirement on equipment, is convenient to operate, has a wide application range and low cost, and has good social and economic benefits.
Disclosure of Invention
In view of the defects in the prior art, one of the objects of the present invention is to provide a method for preparing vanadium pentoxide with a tetravalent vanadium content of less than 0.005 wt% so as to obtain a vanadium pentoxide product with higher purity and less tetravalent vanadium content.
To achieve this object, the preparation method comprises the following steps:
pretreating ammonium metavanadate at a constant temperature of 150-280 ℃ in an oxidizing atmosphere, then heating, and calcining to obtain vanadium pentoxide with the tetravalent vanadium content of less than 0.005 wt%.
Wherein the temperature for constant temperature pretreatment may be 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C or 270 deg.C.
The method leads the ammonium metavanadate to be stably pre-oxidized at the temperature of 150-280 ℃ by introducing the step of constant-temperature pretreatment in an oxidizing atmosphere in the traditional calcining process for preparing the vanadium pentoxide, can remove reducing substances such as ammonia gas generated by decomposing the ammonium metavanadate, effectively avoids the reducing effect of reducing gases such as ammonia gas generated by decomposing the ammonium metavanadate at a higher temperature on the pentavalent vanadium, further reduces the content of the tetravalent vanadium in the product,
the speed of reducing pentavalent vanadium can be increased due to the excessively high temperature of the pretreatment, the effect of oxidizing reducing substances in the pentavalent vanadium cannot be achieved due to the excessively low temperature of the pretreatment, and the temperature of the pretreatment is preferably 180-260 ℃.
In order to achieve the optimal oxidation effect, the pretreatment time is reasonable, the content of nonvolatile impurities in the product is easily increased for a long time, the purity of the vanadium pentoxide product is reduced, the oxidation is not sufficient for a short time, and the content of tetravalent vanadium in the vanadium pentoxide product is increased, preferably, the pretreatment time is 30-180 min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min or 170min, and the like, and further preferably, 60-150 min.
Preferably, the calcination treatment is constant temperature calcination, and the temperature of the calcination treatment is 450 to 590 ℃, for example, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃ or 580 ℃, and more preferably 480 to 550 ℃.
Preferably, the temperature rise is uniform temperature rise, the temperature rise rate of the uniform temperature rise is 1-20 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 15 ℃/min, 17 ℃/min or 19 ℃/min, and the like, and further preferably 4-16 ℃/min.
Preferably, the time of the calcination treatment is 40 to 200min, for example, 60min, 80min, 100min, 120min, 140min, 160min, 180min, 190min, and the like, and more preferably 60 to 120 min.
Preferably, the ammonium metavanadate is ammonium metavanadate powder.
The present invention is more suitable for using ammonium metavanadate powder with larger particle size as raw material than ammonium metavanadate powder with smaller particle size, preferably, the particle size of the ammonium metavanadate powder is 20-100 μm, such as 25 μm, 35 μm, 45 μm, 55 μm, 65 μm, 75 μm, 85 μm, 90 μm or 95 μm.
Preferably, the pretreatment and calcination treatments are carried out in a tube furnace.
Preferably, the oxidizing atmosphere is obtained by introducing oxygen and/or air in a tube furnace.
Preferably, the flow rate of the oxygen and/or air is not more than 1000mL/min, for example, 50mL/min, 100mL/min, 200mL/min, 300mL/min, 400mL/min, 500mL/min, 600mL/min, 700mL/min, 800mL/min, 900mL/min or 950mL/min, and the like, and more preferably 200 to 800 mL/min.
Preferably, the preparation method comprises the following steps:
placing ammonium metavanadate powder with the particle size of 20-100 micrometers in a tubular furnace, introducing oxygen and/or air into the tubular furnace, wherein the flow rate of the oxygen and/or air is 200-800 mL/min, then uniformly heating at the heating rate of 1-20 ℃/min, carrying out pretreatment at the constant temperature of 150-280 ℃ for 30-180 min, then continuously heating at the uniform heating rate of 1-20 ℃/min, and calcining at the constant temperature of 450-590 ℃ for 40-200 min to carry out calcination treatment, thereby obtaining vanadium pentoxide with the tetravalent vanadium content of less than 0.005 wt%.
The second purpose of the invention is to provide vanadium pentoxide prepared by the preparation method, wherein the content of tetravalent vanadium in the vanadium pentoxide prepared by the preparation method is less than 0.005 wt%, which is far less than that of vanadium pentoxide prepared by other prior art.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the step of pretreatment is introduced before the traditional calcination process, and the temperature range of the pretreatment of 150-280 ℃ is selected, so that the purity of the prepared vanadium pentoxide product is further improved compared with that of the traditional preparation process, and in industrial production, the method can be applied by adjusting the calcination process flow without additionally purchasing other equipment, so that the method also has the advantages of good practicability, economy, practicability and the like, and is suitable for large-scale popularization in production;
(2) the method can obtain the vanadium pentoxide product with the purity of more than or equal to 99.95 wt% and the tetravalent vanadium content of less than 0.005 wt%, and can meet the requirements of the high-purity vanadium pentoxide product with low tetravalent vanadium content in the fields of aerospace industry, nuclear industry, solar energy, wind power generation equipment, coating, catalyst, luminescent materials and the like.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following examples and comparative examples, ammonium metavanadate was used which was obtained from Shanghai Aladdin Co., Ltd, and the purity and the content of some impurities thereof were as shown in Table 1:
TABLE 1
| Composition (I) | NH4VO3 | Si | Na | Al | Ti | Fe | Cl | Ca |
| Content (wt%) | 99.9 | 0.002 | 0.001 | 0.002 | 0.001 | 0.002 | 0.001 | 0.001 |
In the following examples and comparative examples, the tube furnaces used were GSL-4Z tube furnaces manufactured by Synechococcus materials technology, Inc.
Example 1
Vanadium pentoxide product 1 was prepared by the following method:
20g of ammonium metavanadate powder with the particle size of 28 mu m is placed in a tubular furnace, pure oxygen is introduced into the tubular furnace, the flow rate of the pure oxygen is 200mL/min, then the temperature is uniformly increased at the heating rate of 1 ℃/min, the temperature is increased to 210 ℃ for constant temperature pretreatment for 60min, then the temperature is continuously increased at the heating rate of 4 ℃/min at the constant temperature, and the constant temperature calcination is carried out at 530 ℃ for 120min for calcination treatment, so that a vanadium pentoxide product 1 is obtained.
Example 2
The vanadium pentoxide product 2 was prepared by the following method:
and (2) placing 20g of ammonium metavanadate powder with the particle size of 28 microns in a tubular furnace, introducing pure oxygen into the tubular furnace, wherein the flow rate of the pure oxygen is 300mL/min, then uniformly heating at a heating rate of 20 ℃/min, heating to 150 ℃ for constant temperature pretreatment for 60min, then continuously heating at a constant temperature at a heating rate of 16 ℃/min, and calcining at 550 ℃ for 60min to obtain a vanadium pentoxide product 2.
Example 3
Vanadium pentoxide product 3 was prepared by the following method:
the only difference from example 1 is that the pretreatment was carried out at a constant temperature of 150 ℃ for a period of 150 min.
Example 3 yielded vanadium pentoxide product 3.
Example 4
Vanadium pentoxide product 4 was prepared by the following method:
the only difference from example 1 is that the temperature at which the pretreatment was carried out at constant temperature was 280 ℃ and the time was 40 min.
Example 4 yielded vanadium pentoxide product 4.
Example 5
Vanadium pentoxide product 5 was prepared by the following method:
the only difference from example 1 is that the calcination treatment was carried out at 460 ℃ for 190 min.
Example 5 yielded vanadium pentoxide product 5.
Example 6
Vanadium pentoxide product 6 was prepared by the following method:
the only difference from example 1 is that the temperature of the calcination treatment was 580 ℃ and the time was 40 min.
Example 6 yielded a vanadium pentoxide product 6.
Example 7
Vanadium pentoxide product 7 was prepared by the following method:
the only difference from example 1 is that the tube furnace was not charged with pure oxygen, but with air, and the flow rate of air was 1000 mL/min.
Example 7 yielded vanadium pentoxide product 7.
Example 8
Vanadium pentoxide product 8 was prepared by the following method:
the only difference from example 1 is that the particle size of the ammonium metavanadate is 100. mu.m.
Example 8 yielded a vanadium pentoxide product 8.
Example 9
Vanadium pentoxide product 9 was prepared by the following method:
the only difference from example 1 is that the pretreatment was carried out at constant temperature for 20 min.
Example 9 yielded a vanadium pentoxide product 9.
Example 10
The vanadium pentoxide product 10 is prepared by the following method:
the only difference from example 1 is that the pretreatment was carried out at constant temperature for 220 min.
Example 10 resulted in a vanadium pentoxide product 10.
Comparative example 1
Vanadium pentoxide product 11 was prepared by the following method:
the only difference from example 1 is that the temperature at which the pretreatment was carried out at constant temperature was 130 ℃.
The vanadium pentoxide product 11 was obtained in comparative example 1.
Comparative example 2
Vanadium pentoxide product 12 was prepared by the following method:
the only difference from example 1 is that the temperature at which the pretreatment is carried out at constant temperature is 305 ℃.
The vanadium pentoxide product 12 was obtained in comparative example 2.
Comparative example 3
The vanadium pentoxide product 13 was prepared by the following method:
20g of ammonium metavanadate powder with the particle size of 50 mu m is placed in a tubular furnace, pure oxygen is introduced into the tubular furnace, the flow rate of the pure oxygen is 300mL/min, then the temperature is raised to 530 ℃ at the average heating rate of 30 ℃/min, and the mixture is calcined for 60min at constant temperature, so that a vanadium pentoxide product 13 is obtained.
Comparative example 4
Vanadium pentoxide product 14 was prepared by the following method:
20g of ammonium metavanadate powder with the particle size of 50 mu m is placed in a tubular furnace, pure oxygen is introduced into the tubular furnace, the flow rate of the pure oxygen is 300mL/min, then the temperature is raised to 530 ℃ at the average heating rate of 5 ℃/min, and the mixture is calcined for 60min at constant temperature, so that a vanadium pentoxide product 14 is obtained.
The purity of the vanadium pentoxide products 1-14 and the content of tetravalent vanadium therein obtained in the above examples and comparative examples were tested by the following test methods, and the test results are listed in table 2:
(1) purity test of vanadium pentoxide product
And (3) determining the purity of the vanadium pentoxide product 1-14 according to the method described in local standard DB 51/T2044-.
(2) Determination of tetravalent vanadium content in vanadium pentoxide product
And (3) determining the content of tetravalent vanadium in the vanadium pentoxide products 1-14 according to the method described in the national standard YB/T4248-2011 'determination differential subtraction method of vanadium pentoxide content'.
TABLE 2 comparison table of purity and tetravalent vanadium content of vanadium pentoxide product 1-14
| Vanadium pentoxide product | Purity (C:wt％) | tetravalent vanadium content (wt%) |
| 1 | 99.98 | 0.0032 |
| 2 | 99.98 | 0.0038 |
| 3 | 99.98 | 0.0034 |
| 4 | 99.97 | 0.0039 |
| 5 | 99.97 | 0.0041 |
| 6 | 99.98 | 0.0035 |
| 7 | 99.98 | 0.0028 |
| 8 | 99.98 | 0.0037 |
| 9 | 99.97 | 0.0049 |
| 10 | 99.95 | 0.0048 |
| 11 | 99.91 | 0.0184 |
| 12 | 99.90 | 0.0243 |
| 13 | 98.89 | 0.4020 |
| 14 | 99.88 | 0.0425 |
As can be seen from Table 2, the purity of the prepared vanadium pentoxide product can be effectively improved and the content of tetravalent vanadium therein can be reduced by introducing a pretreatment step before the conventional calcination process, the content of tetravalent vanadium in the product can be further reduced by properly adjusting the pretreatment conditions, and the purity of the prepared vanadium pentoxide product can be further increased to be more than or equal to 99.95 wt% and the content of tetravalent vanadium therein can be decreased to be less than 0.005 wt% by specifically selecting the pretreatment temperature range of 150-280 ℃.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (13)
1. A preparation method of vanadium pentoxide with tetravalent vanadium content less than 0.005 wt% is characterized by comprising the following steps:
pretreating ammonium metavanadate at a constant temperature of 150-280 ℃ in an oxidizing atmosphere, then heating, and calcining to obtain vanadium pentoxide with the tetravalent vanadium content of less than 0.005 wt%;
the pretreatment and the calcination treatment are carried out in a tubular furnace, the oxidizing atmosphere is obtained by introducing oxygen and/or air into the tubular furnace, and the flow rate of the oxygen and/or air is 50-1000 mL/min; the temperature rise is constant-speed temperature rise, and the temperature rise rate of the constant-speed temperature rise is 1-20 ℃/min.
2. The method according to claim 1, wherein the temperature of the pretreatment is 180 to 260 ℃.
3. The method according to claim 1, wherein the pretreatment time is 30 to 180 min.
4. The method according to claim 3, wherein the pretreatment time is 60 to 150 min.
5. The preparation method according to claim 1, wherein the temperature rise rate of the uniform temperature rise is 4-16 ℃/min.
6. The preparation method according to claim 1, wherein the calcination treatment is constant temperature calcination, and the temperature of the calcination treatment is 450-590 ℃.
7. The method according to claim 6, wherein the calcination treatment is carried out at a temperature of 480 to 550 ℃.
8. The method according to claim 1, wherein the calcination treatment is carried out for 40 to 200 min.
9. The method according to claim 8, wherein the calcination treatment is carried out for 60 to 120 min.
10. The method according to claim 1, wherein the ammonium metavanadate is ammonium metavanadate powder.
11. The method according to claim 10, wherein the particle size of the ammonium metavanadate powder is 20 to 100 μm.
12. The method according to claim 1, wherein the flow rate of the oxygen and/or air is 200 to 800 mL/min.
13. The method according to any one of claims 1 to 12, wherein the method comprises the steps of:
placing ammonium metavanadate powder with the particle size of 20-100 micrometers in a tubular furnace, introducing oxygen and/or air into the tubular furnace, wherein the flow rate of the oxygen and/or air is 200-800 mL/min, then uniformly heating at the heating rate of 1-20 ℃/min, carrying out pretreatment at the constant temperature of 150-280 ℃ for 30-180 min, then continuously heating at the uniform heating rate of 1-20 ℃/min, and calcining at the constant temperature of 450-590 ℃ for 40-200 min to carry out calcination treatment, thereby obtaining vanadium pentoxide with the tetravalent vanadium content of less than 0.005 wt%.
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