CN113732297A - High-purity vanadium purification process - Google Patents
High-purity vanadium purification process Download PDFInfo
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- CN113732297A CN113732297A CN202111034661.2A CN202111034661A CN113732297A CN 113732297 A CN113732297 A CN 113732297A CN 202111034661 A CN202111034661 A CN 202111034661A CN 113732297 A CN113732297 A CN 113732297A
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Abstract
A high-purity vanadium purification process comprises the following steps: s1, weighing and batching; s2, fine grinding and mixing to obtain a mixed raw material; s3, carrying out reduction reaction; s4, ball milling; s5, soaking the activated carbon in an acid washing solution, and then sequentially carrying out acid washing and alkali washing on the powdery material obtained in the step S4; s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder. The invention adopts ultraviolet irradiation to assist dehydrogenation, can improve the activity of the material for dehydrogenation reaction, can accelerate the reaction speed, and can not introduce foreign impurities, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher. The purity of the vanadium metal obtained by the method is more than or equal to 99.9 percent and even can reach 99.99 percent.
Description
Technical Field
The invention relates to the field of vanadium purification, in particular to a high-purity vanadium purification process.
Background
Vanadium is a metal and an important additive for producing alloy, and trace vanadium can improve the performance of the alloy, so vanadium is an important resource, although the content of vanadium in earth crust is very rich, the vanadium has larger dispersibility, in vanadium ore from which vanadium can be extracted, a large amount of minerals need to be processed to obtain a small amount of vanadium, the existing vanadium is mainly prepared by reducing vanadium pentoxide, and the crude vanadium has higher content of non-metal impurities such as oxygen, nitrogen, carbon and the like and poor plasticity. The metal vanadium refining refers to a process of removing impurities in crude metal vanadium and producing high-purity metal vanadium, and is a component of a vanadium metallurgy process. After refining and removing impurities, the plasticity of the metal vanadium can be improved. But the purity of the vanadium obtained by the existing vanadium refining still can not meet the requirement.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a high-purity vanadium purification process, wherein the purity of the obtained vanadium is high.
The technical scheme adopted by the invention for solving the technical problems is that the high-purity vanadium purification process comprises the following steps:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then sequentially washing and drying the powdery material after alkali washing with water and ethanol (airing or drying) to obtain a mixture after impurities are removed;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
Preferably, in step S1, the weight ratio of the vanadium pentoxide powder, the sodium salt powder and the reducing agent is 1: 0.1-0.3: 3 to 4. The reducing agent is calcium hydride. The sodium salt powder is preferably at least one of sodium carbonate and sodium bicarbonate. Research shows that the addition of a small amount of sodium salt is beneficial to the reduction of vanadium pentoxide by a reducing agent. And the sodium carbonate and the sodium bicarbonate are easy to remove in the subsequent alkali washing and acid washing processes.
Preferably, in step S2, the vanadium pentoxide powder, the sodium salt powder, and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of the particles per gram weight should not be less than 600 square meters. Research shows that the particle size of the raw materials is controlled, which is beneficial to the subsequent reaction.
Preferably, in step S3, the inert gas is nitrogen. And (3) during the reduction reaction of the mixed raw materials, pressurizing the mixed raw materials by using nitrogen in the heating furnace, keeping the nitrogen pressure at 1.2-1.5 atmospheric pressures, heating at 700-800 ℃ for 3-5 hours.
Preferably, in step S3, before the heating reduction reaction, the mixed raw material is heated to 400 ℃ for preheating, and the preheating time is 15-20 minutes. The raw materials are preheated firstly, which is beneficial to the uniform rise of the temperature, can fully activate the raw materials, is beneficial to the full implementation of the reduction reaction and is beneficial to improving the purity of the obtained vanadium.
Preferably, in step S3, after the reduction reaction is completed, the nitrogen pressure is maintained until the temperature in the furnace is reduced to 400 ℃. At the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted at the final heating stage.
Preferably, in step S4, the ball milling is performed by dry milling until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size is controlled, which is beneficial to the subsequent reaction.
Preferably, in step S5, the amount of activated carbon is 0.3 to 0.5 times the weight of the raw material vanadium pentoxide powder. Stirring is carried out in the processes of alkali washing and acid washing so as to improve the adsorption effect of the activated carbon on impurities. The acid washing solution is hydrochloric acid aqueous solution. The concentration of the aqueous hydrochloric acid solution is preferably 0.1 to 0.5 mol/L. The amount of the pickling solution is 1-5 times of the mass of the powdery material. The alkaline washing solution is sodium hydroxide aqueous solution. The concentration of the sodium hydroxide aqueous solution is 0.1-0.5 mol/L. The amount of the alkaline washing solution is 1 to 5 times of the mass of the powdery material. The consumption of the acid washing solution or the alkali washing solution is not enough, which is not beneficial to impurity removal; too much, the impurity removal effect is improved to a limited extent, the raw materials are wasted, and the economic purpose is not met.
Preferably, in step S6, a catalyst iron oxide or a dehydrogenating agent sulfur may be added. The addition amount of the catalyst iron oxide or the dehydrogenating agent sulfur is 10-20% of the mass of the raw material vanadium pentoxide powder. Heating to 600-650 ℃, and keeping the temperature for 1-1.5 hours.
Preferably, in step S6, during dehydrogenation heating, the heating is performed to 300 ℃ for preheating, and the preheating time is 10 to 15 minutes.
Preferably, in step S6, the power of the uv light source used during uv light irradiation is 200-500W. The time of ultraviolet irradiation is the time of dehydrogenation reaction, and is preferably 1-1.5 hours. Researches show that the ultraviolet irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be increased, and no foreign impurities can be introduced, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
The invention has the beneficial effects that:
1. according to the invention, vanadium pentoxide and other raw materials are subjected to ball milling and then reduction reaction, and ball milling is carried out again after the reduction reaction, so that subsequent reaction is facilitated, the reduction process and the subsequent reaction process are stable and reliable, and impurities are removed more fully by subsequent acid washing and alkali washing;
2. in the reduction heating step and the dehydrogenation heating step, the preheating step is arranged, so that the difference of the internal temperature rise and the external temperature rise of the heated material is reduced through preheating, the uniform temperature rise is facilitated, the raw material can be fully activated, the full reduction reaction is facilitated, and the purity of the obtained vanadium is improved;
3. the method uses the activated carbon in the steps of acid washing and alkali washing, so that impurities in a detergent, impurities in a material subjected to ball milling and impurities washed by the acid washing and the alkali washing are adsorbed by the activated carbon, the impurities and the material are easy to separate, and impurity residues are further reduced;
4. in the step of heating under the protection of nitrogen atmosphere, the nitrogen pressure is kept until the temperature in the furnace is reduced to below 400 ℃, at the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted in the final heating stage;
5. the ultraviolet light irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be accelerated, no foreign impurities can be introduced, the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
6. The purity of the vanadium metal obtained by the method is more than or equal to 99.9 percent and even can reach 99.99 percent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
The high-purity vanadium purification process of the embodiment comprises the following steps:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then washing and airing the powdery material after alkali washing with water and ethanol in sequence to obtain a mixture after impurity removal;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
In step S1, the weight ratio of the vanadium pentoxide powder, the sodium salt powder, and the reducing agent is 1: 0.1: 3. the reducing agent is calcium hydride. The sodium salt powder is sodium carbonate.
In step S2, the vanadium pentoxide powder, the sodium salt powder, and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of the particles per gram weight is not less than 600 square meters.
In step S3, the inert gas is nitrogen. And (3) during the reduction reaction of the mixed raw materials, pressurizing the heating furnace by adopting nitrogen, keeping the pressure of the nitrogen at 1.2 atmospheric pressure, heating at 700 ℃ and heating for 3 hours.
In step S3, the mixed raw materials are preheated by heating to 400 ℃ for 15 minutes before the heating reduction reaction. The raw materials are preheated firstly, which is beneficial to the uniform rise of the temperature, can fully activate the raw materials, is beneficial to the full implementation of the reduction reaction and is beneficial to improving the purity of the obtained vanadium.
In step S3, after the reduction reaction is completed, the nitrogen pressure needs to be maintained until the temperature in the furnace drops to 400 ℃. At the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted at the final heating stage.
In step S4, the ball milling is performed by dry milling until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size is controlled, which is beneficial to the subsequent reaction.
In step S5, the amount of activated carbon is 0.3 times the weight of the raw material vanadium pentoxide powder. Stirring is carried out in the processes of alkali washing and acid washing so as to improve the adsorption effect of the activated carbon on impurities. The acid washing solution is hydrochloric acid aqueous solution. The concentration of the hydrochloric acid aqueous solution was 0.1 mol/L. The amount of pickling solution used is 1 time the mass of the material in powder form. The alkaline washing solution is sodium hydroxide aqueous solution. The concentration of the aqueous sodium hydroxide solution was 0.1 mol/L. The amount of the alkaline cleaning solution used was 1 time the mass of the powdery material.
In step S6, the temperature is raised to 600 ℃ and the heating time is kept for 1 hour.
In step S6, during dehydrogenation heating, the reaction mixture is heated to 300 ℃ and preheated for 10 minutes.
In step S6, the power of the ultraviolet light source used for the ultraviolet light irradiation is 200W. The time of ultraviolet irradiation is the time of dehydrogenation reaction, and is 1 hour. Researches show that the ultraviolet irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be increased, and no foreign impurities can be introduced, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
The purity of the vanadium metal obtained in this example was 99.92%.
Example 2
The high-purity vanadium purification process of the embodiment comprises the following steps:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then washing and airing the powdery material after alkali washing with water and ethanol in sequence to obtain a mixture after impurity removal;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
In step S1, the weight ratio of the vanadium pentoxide powder, the sodium salt powder, and the reducing agent is 1: 0.3: 4. the reducing agent is calcium hydride. The sodium salt powder is sodium bicarbonate.
In step S2, the vanadium pentoxide powder, the sodium salt powder, and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size of the raw materials is controlled, which is beneficial to the subsequent reaction.
In step S3, the inert gas is nitrogen. And (3) during the reduction reaction of the mixed raw materials, pressurizing the heating furnace by adopting nitrogen, keeping the pressure of the nitrogen at 1.2 atmospheric pressure, heating at 800 ℃ and heating for 3 hours.
In step S3, the mixed raw materials are preheated by heating to 400 ℃ for 15 minutes before the heating reduction reaction. The raw materials are preheated firstly, which is beneficial to the uniform rise of the temperature, can fully activate the raw materials, is beneficial to the full implementation of the reduction reaction and is beneficial to improving the purity of the obtained vanadium.
In step S3, after the reduction reaction is completed, the nitrogen pressure needs to be maintained until the temperature in the furnace drops to 400 ℃. At the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted at the final heating stage.
In step S4, the ball milling is performed by dry milling until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size is controlled, which is beneficial to the subsequent reaction.
In step S5, the amount of activated carbon is 0.5 times the weight of the raw material vanadium pentoxide powder. Stirring is carried out in the processes of alkali washing and acid washing so as to improve the adsorption effect of the activated carbon on impurities. The acid washing solution is hydrochloric acid aqueous solution. The concentration of the hydrochloric acid aqueous solution was 0.5 mol/L. The amount of pickling solution used is 5 times the mass of the corresponding powdery material. The alkaline washing solution is sodium hydroxide aqueous solution. The concentration of the aqueous sodium hydroxide solution was 0.5 mol/L. The amount of alkaline washing solution used was 5 times the mass of the powdery material. The consumption of the acid washing solution or the alkali washing solution is not enough, which is not beneficial to impurity removal; too much, the impurity removal effect is improved to a limited extent, the raw materials are wasted, and the economic purpose is not met.
In step S6, the temperature is raised to 600 ℃ and the heating time is kept for 1.2 hours.
In step S6, during dehydrogenation heating, the reaction mixture is heated to 300 ℃ and preheated for 15 minutes.
In step S6, the power of the ultraviolet light source used for the ultraviolet light irradiation is 300W. The time of ultraviolet irradiation is the time of dehydrogenation reaction, and is 1.2 hours. Researches show that the ultraviolet irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be increased, and no foreign impurities can be introduced, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
The purity of the vanadium metal obtained in this example was 99.95%.
Example 3
The high-purity vanadium purification process of the embodiment comprises the following steps:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then washing and drying the powdery material after alkali washing with water and ethanol in sequence to obtain a mixture after impurity removal;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
In step S1, the weight ratio of the vanadium pentoxide powder, the sodium salt powder, and the reducing agent is 1: 0.2: 3. the reducing agent is calcium hydride. The sodium salt powder is sodium bicarbonate.
In step S2, the vanadium pentoxide powder, the sodium salt powder, and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size of the raw materials is controlled, which is beneficial to the subsequent reaction.
In step S3, the inert gas is nitrogen. And (3) during the reduction reaction of the mixed raw materials, pressurizing the heating furnace by adopting nitrogen, keeping the pressure of the nitrogen at 1.3 atmospheric pressures, heating at 800 ℃ and heating for 3 hours.
In step S3, the mixed raw materials are preheated by heating to 400 ℃ for 20 minutes before the heating reduction reaction. The raw materials are preheated firstly, which is beneficial to the uniform rise of the temperature, can fully activate the raw materials, is beneficial to the full implementation of the reduction reaction and is beneficial to improving the purity of the obtained vanadium.
In step S3, after the reduction reaction is completed, the nitrogen pressure needs to be maintained until the temperature in the furnace drops to 400 ℃. At the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted at the final heating stage.
In step S4, the ball milling is performed by dry milling until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size is controlled, which is beneficial to the subsequent reaction.
In step S5, the amount of activated carbon is 0.4 times the weight of the raw material vanadium pentoxide powder. Stirring is carried out in the processes of alkali washing and acid washing so as to improve the adsorption effect of the activated carbon on impurities. The acid washing solution is hydrochloric acid aqueous solution. The concentration of the hydrochloric acid aqueous solution was 0.3 mol/L. The amount of pickling solution used is 2 times the mass of the material in powder form. The alkaline washing solution is sodium hydroxide aqueous solution. The concentration of the aqueous sodium hydroxide solution was 0.2 mol/L. The amount of alkaline washing solution used was 3 times the mass of the powdery material. The consumption of the acid washing solution or the alkali washing solution is not enough, which is not beneficial to impurity removal; too much, the impurity removal effect is improved to a limited extent, the raw materials are wasted, and the economic purpose is not met.
In step S6, a catalyst iron oxide is added. The addition amount of the catalyst iron oxide is 10 percent of the mass of the raw material vanadium pentoxide powder. Heating to 620 ℃, and keeping the temperature for 1.5 hours.
In step S6, during dehydrogenation heating, the reaction mixture is heated to 300 ℃ and preheated for 12 minutes.
In step S6, the power of the ultraviolet light source used for the ultraviolet light irradiation is 400W. The time of ultraviolet irradiation is the time of dehydrogenation reaction, and is 1.5 hours. Researches show that the ultraviolet irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be increased, and no foreign impurities can be introduced, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
The purity of the vanadium metal obtained in this example was 99.98%.
Example 4
The high-purity vanadium purification process of the embodiment comprises the following steps:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then washing and drying the powdery material after alkali washing with water and ethanol in sequence to obtain a mixture after impurity removal;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
In step S1, the weight ratio of the vanadium pentoxide powder, the sodium salt powder, and the reducing agent is 1: 0.3: 4. the reducing agent is calcium hydride. The sodium salt powder is preferably at least one of sodium carbonate and sodium bicarbonate. Research shows that the addition of a small amount of sodium salt is beneficial to the reduction of vanadium pentoxide by a reducing agent. And the sodium carbonate and the sodium bicarbonate are easy to remove in the subsequent alkali washing and acid washing processes.
In step S2, the vanadium pentoxide powder, the sodium salt powder, and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size of the raw materials is controlled, which is beneficial to the subsequent reaction.
In step S3, the inert gas is nitrogen. And (3) during the reduction reaction of the mixed raw materials, pressurizing the heating furnace by adopting nitrogen, keeping the pressure of the nitrogen at 1.5 atmospheric pressure, heating at 800 ℃ and heating for 5 hours.
In step S3, the mixed raw materials are preheated by heating to 400 ℃ for 15 minutes before the heating reduction reaction. The raw materials are preheated firstly, which is beneficial to the uniform rise of the temperature, can fully activate the raw materials, is beneficial to the full implementation of the reduction reaction and is beneficial to improving the purity of the obtained vanadium.
In step S3, after the reduction reaction is completed, the nitrogen pressure needs to be maintained until the temperature in the furnace drops to 400 ℃. At the moment, the nitrogen protection is removed, and the materials in the furnace can not react with air, so that the materials are prevented from being polluted at the final heating stage.
In step S4, the ball milling is performed by dry milling until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters. Research shows that the particle size is controlled, which is beneficial to the subsequent reaction.
In step S5, the amount of activated carbon is 0.5 times the weight of the raw material vanadium pentoxide powder. Stirring is carried out in the processes of alkali washing and acid washing so as to improve the adsorption effect of the activated carbon on impurities. The acid washing solution is hydrochloric acid aqueous solution. The concentration of the hydrochloric acid aqueous solution was 0.5 mol/L. The amount of pickling solution used is 5 times the mass of the corresponding powdery material. The alkaline washing solution is sodium hydroxide aqueous solution. The concentration of the aqueous sodium hydroxide solution was 0.5 mol/L. The amount of alkaline washing solution used was 5 times the mass of the powdery material. The consumption of the acid washing solution or the alkali washing solution is not enough, which is not beneficial to impurity removal; too much, the impurity removal effect is improved to a limited extent, the raw materials are wasted, and the economic purpose is not met.
In step S6, a dehydrogenating agent sulfur is added. The addition amount of the dehydrogenating agent sulfur is equal to 20 percent of the mass of the raw material vanadium pentoxide powder. Heating to 650 ℃, and keeping the temperature for 1.5 hours.
In step S6, during dehydrogenation heating, the reaction mixture is heated to 300 ℃ and preheated for 10 minutes.
In step S6, the power of the ultraviolet light source used for the ultraviolet light irradiation is 500W. The time of ultraviolet irradiation is the time of dehydrogenation reaction, and is 1.5 hours. Researches show that the ultraviolet irradiation is adopted to assist dehydrogenation, so that the activity of the material for dehydrogenation reaction can be improved, the reaction speed can be increased, and no foreign impurities can be introduced, so that the reaction is more complete, the impurity content in the purified vanadium is low, and the purity of the vanadium is higher.
The purity of the vanadium metal obtained in this example was 99.99%.
Comparative example 1
This comparative example was conducted in the same manner as example 4 except that ultraviolet light irradiation was not used in step S6. The purity of the vanadium metal obtained in this example was 99.20%.
Comparative example 2
This comparative example was conducted in the same manner as example 4 except that ball milling was not conducted in step S2. The purity of the vanadium metal obtained in this example was 99.50%.
Comparative example 3
This comparative example was conducted in the same manner as example 4 except that no activated carbon was added in step S5. The purity of the vanadium metal obtained in this example was 99.32%.
Comparative example 4
This comparative example was conducted in the same manner as example 4 except that the acid washing and the alkali washing were not conducted in step S5. The purity of the vanadium metal obtained in this example was 99.35%.
Claims (10)
1. The high-purity vanadium purification process is characterized by comprising the following steps of:
s1, weighing and proportioning vanadium pentoxide powder, sodium salt powder and a reducing agent;
s2, putting the vanadium pentoxide powder, the sodium salt powder and the reducing agent into a ball mill for further fine grinding and mixing to obtain a mixed raw material;
s3, putting the mixed raw materials into a sealed heating furnace, and heating under the protection of inert gas to perform reduction reaction on the mixed raw materials to obtain a reduced material;
s4, putting the obtained reduced material into the ball mill again for ball milling, and grinding the sintered block part into powder to obtain a powder material;
s5, soaking the activated carbon in an acid washing solution, adding the powdery material obtained in the step S4 into the acid washing solution for acid washing to remove impurities, adding the powdery material after acid washing into an alkali washing solution for alkali washing to further remove impurities, and then washing and drying the powdery material after alkali washing with water and ethanol in sequence to obtain a mixture after impurity removal;
s6, dehydrogenating the mixture obtained in the step S5 after impurity removal under the condition of ultraviolet light irradiation and heating to obtain vanadium powder.
2. The process for purifying high-purity vanadium according to claim 1, wherein in the step S1, the weight ratio of the vanadium pentoxide powder to the sodium salt powder to the reducing agent is 1: 0.1-0.3: 3-4; the reducing agent is calcium hydride; the sodium salt powder is at least one of sodium carbonate and sodium bicarbonate.
3. The process of claim 1 or 2, wherein in step S2, the vanadium pentoxide powder, the sodium salt powder and the reducing agent are finely ground to a particle diameter of 200 mesh or less, and the total area of particles per gram weight is not less than 600 square meters.
4. The process of purifying high purity vanadium according to claim 1 or 2, wherein in step S3, the inert gas is nitrogen; and (3) during the reduction reaction of the mixed raw materials, pressurizing the mixed raw materials by using nitrogen in the heating furnace, keeping the nitrogen pressure at 1.2-1.5 atmospheric pressures, heating at 700-800 ℃ for 3-5 hours.
5. The purification process of high-purity vanadium according to claim 1 or 2, wherein in step S3, the mixed raw materials are preheated by heating to 400 ℃ for 15-20 minutes before the heating reduction reaction.
6. The process of claim 1 or 2, wherein in step S3, after the reduction reaction is completed, the nitrogen pressure is maintained until the temperature in the furnace is reduced to below 400 ℃.
7. The process of claim 1 or 2, wherein in the step S4, the ball milling is performed in a dry milling manner until the particle diameter is less than 200 meshes, and the total area of the particles per gram weight is not less than 600 square meters.
8. The purification process of high purity vanadium according to claim 1 or 2, wherein in step S5, the amount of activated carbon is 0.3 to 0.5 times the weight of the raw material vanadium pentoxide powder; the pickling solution is hydrochloric acid aqueous solution; the concentration of the hydrochloric acid aqueous solution is 0.1-0.5 mol/L; the dosage of the pickling solution is 1 to 5 times of the mass of the powdery material; the alkali washing solution is sodium hydroxide aqueous solution; the concentration of the sodium hydroxide aqueous solution is 0.1-0.5 mol/L; the amount of the alkaline washing solution is 1 to 5 times of the mass of the powdery material.
9. The purification process of high purity vanadium according to claim 1 or 2, wherein in step S6, a catalyst of iron oxide or a dehydrogenating agent of sulfur is added; the addition amount of the catalyst iron oxide or the dehydrogenating agent sulfur is 10-20% of the mass of the raw material vanadium pentoxide powder.
10. The process for purifying high-purity vanadium according to claim 1 or 2, wherein in the step S6, the power of the ultraviolet light source used for irradiating ultraviolet light is 200-500W.
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