CN111266597B - Preparation method of metal vanadium powder - Google Patents
Preparation method of metal vanadium powder Download PDFInfo
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Abstract
The invention discloses a preparation method of metal vanadium powder, and belongs to the technical field of vanadium metallurgy. The invention provides a preparation method of metal vanadium powder for improving the grade of metal vanadium and directly obtaining a powdery product, which comprises the following steps: using vanadium-containing powder as vanadium source and chlorine gas as chlorination mediumCarrying out boiling chlorination to obtain a primary product of vanadium chloride; distilling the primary vanadium chloride product in two steps to obtain a vanadium chloride intermediate product; heating and gasifying the intermediate product, and mixing with high-purity H2Mixing, then contacting with a reaction carrier to carry out reduction reaction, and obtaining the high-purity superfine vanadium metal powder. The method can realize the preparation of high-purity vanadium chloride with low content of interstitial impurities, can also perform gas-gas reaction at relatively low temperature to obtain metal vanadium powder with nanometer size, and is favorable for industrial production and application.
Description
Technical Field
The invention belongs to the technical field of vanadium metallurgy, and particularly relates to a preparation method of metal vanadium powder.
Background
The vanadium metal has the characteristics of high melting point, good processing performance, strong corrosion resistance, small fast neutron absorption cross section and the like. With the development of the aerospace industry, the atomic energy industry, the electronic industry and the superconducting industry in the world, the application range of vanadium products is rapidly expanded from the steel industry, and the demand of functional materials taking metal vanadium as a raw material is gradually increased. The preparation of the high-purity vanadium metal is mainly obtained by refining after primary vanadium metal is prepared by a vacuum thermal reduction process. At present, relevant documents can detect that the preparation method of primary metal vanadium comprises non-metal thermal reduction processes such as carbothermic process and silicothermic process and metallothermic reduction processes such as aluminothermic process, magnesiothermic process and calcithermic process, and the main raw materials are oxides and chlorides of vanadium. Commonly used refining methods include molten salt electrolysis, vacuum refining, thermal decomposition of iodide, and the like.
CN201310395114 provides a method for preparing metal vanadium by taking vanadium oxide as a vanadium-containing raw material and aluminum powder as a reducing agent, and the grade of the obtained product is 94-97% of the metal vanadium, so that the method has the characteristics of simple process and low cost. CN201580078650 provides a method for preparing high-purity vanadium metal by using a calcium-reduced vanadium compound generated by electrolyzing part of inorganic molten salt in an electrolytic cell, and the vanadium metal obtained by the method has the advantage of high purity. 201910721720 provides a method for preparing vanadium metal by acid dissolution of ferrovanadium alloy, which has the characteristics of short process flow and low equipment requirement. 201811157105 discloses a method for preparing vanadium powder by metal gas-based reduction, which takes active metal gas as a reducing agent to carry out thermal reduction with raw materials, and then obtains high-purity vanadium powder by acid washing, filtering and drying.
The metal vanadium prepared by the method is low in grade, and has interstitial impurity elements such as carbon, hydrogen, oxygen and the like, so that the metal vanadium is high in hardness, poor in thermoplasticity and not beneficial to subsequent processing; meanwhile, the obtained metal vanadium product can be subjected to a further powder preparation process to obtain superfine metal vanadium powder, so that the popularization and application of the metal vanadium powder as a raw material for preparing a vanadium-based functional/structural material are limited.
Disclosure of Invention
The invention provides a preparation method of metal vanadium powder for solving the technical problems, which comprises the following steps:
A. chlorination of vanadium-containing powder: boiling and chlorinating by taking vanadium-containing powder as a vanadium source and chlorine as a chlorination medium to obtain a primary vanadium chloride product;
B. primary purification of vanadium chloride: performing two-step distillation on the primary vanadium chloride product at 110-140 ℃ and 160-180 ℃, and collecting distillate obtained during distillation at 160-180 ℃ to obtain a high-purity vanadium chloride intermediate product;
C. high-temperature reduction of vanadium chloride: heating and gasifying vanadium chloride intermediate product, and mixing with high-purity H2Mixing, then contacting with a reaction carrier to carry out reduction reaction, and obtaining the high-purity superfine vanadium metal powder.
In the preparation method of the metal vanadium powder, in the step A, the high-purity vanadium-containing powder is vanadium-containing intermediate alloy powder, the purity of the vanadium-containing intermediate alloy powder is more than or equal to 99.0%, the granularity of the vanadium-containing intermediate alloy powder is less than or equal to 50 meshes, the contents of non-metallic inclusions of O, Si, C, P and S are respectively not higher than 0.20%, 0.40%, 0.10%, 0.05% and 0.05%, and the contents of other impurities are not higher than 0.2%.
Preferably, in the preparation method of the metal vanadium powder, in the step a, the high-purity vanadium-containing powder is high-grade vanadium-containing intermediate alloy powder such as FeV80, AlV85 and the like.
In the preparation method of the metal vanadium powder, in the step A, the purity of the chlorine is more than or equal to 99.8%.
In the preparation method of the metal vanadium powder, in the step A, the boiling chlorination temperature is 400-700 ℃.
In the preparation method of the metal vanadium powder, in the step C, the temperature for heating and gasifying the vanadium chloride is 500-700 ℃.
Wherein the preparation method of the metal vanadium powder comprises the following stepsIn C, vanadium chloride gas and high-purity CH are sprayed by a spray gun4And H2The temperature of the wall of the spray gun is 500-700 ℃, and the pressure is 0.5-2.0 MPa.
In the preparation method of the metal vanadium powder, in the step C, H is added before mixing2Preheating to 300-500 ℃.
In the step C, the reaction carrier is a multilayer inert metal high-temperature net, and the temperature of the reaction carrier is 1100-1400 ℃.
The invention has the beneficial effects that:
the invention takes high-purity vanadium-containing intermediate alloy as a raw material, converts all vanadium in the raw material into vanadium chloride by a chlorination process, avoids introducing process oxygen from the source, obtains a high-purity vanadium chloride intermediate by two-step distillation, realizes the molecular mixing of the raw materials by the gas phase contact between the gasified vanadium chloride and a reducing agent, reduces the reaction diffusion distance, is beneficial to the rapid nucleation of a product in a non-equilibrium state, accelerates the reaction process, can realize the preparation of high-purity vanadium chloride with low content of interstitial impurities, can also carry out gas-gas reaction at relatively low temperature to obtain metal vanadium powder with nanometer size, and is beneficial to industrial production and application.
Detailed Description
Specifically, the preparation method of the metal vanadium powder comprises the following steps:
A. chlorination of vanadium-containing powder: boiling and chlorinating by taking vanadium-containing powder as a vanadium source and chlorine as a chlorination medium to obtain a primary vanadium chloride product;
B. primary purification of vanadium chloride: performing two-step distillation on the primary vanadium chloride product at 110-140 ℃ and 160-180 ℃, and collecting distillate obtained during distillation at 160-180 ℃ to obtain a high-purity vanadium chloride intermediate product;
C. high-temperature reduction of vanadium chloride: heating and gasifying vanadium chloride intermediate product, and mixing with high-purity H2Mixing, then contacting with a reaction carrier to carry out reduction reaction, and obtaining the high-purity superfine vanadium metal powder.
Because the binding capacity of vanadium and oxygen is very strong, the conventional preparation process mainly takes vanadium oxide as a raw material to prepare metal vanadium powder, and the metal vanadium powder is purified by means of deoxidation, dealumination and the like in the modes of further impurity removal and the like; the vanadium oxide is generally obtained by chlorinating a vanadium-containing mineral (the occurrence state of vanadium is generally a vanadium oxide or a spinel structure) to obtain a vanadium oxychloride, and the oxychloride needs to be further separated and purified by a hydrometallurgical process, so that the simple substance vanadium cannot be directly obtained.
The method provides a high-quality intermediate raw material for the subsequent preparation of the metal vanadium. In the step A, high-purity vanadium-containing intermediate alloy is used as a raw material, and vanadium in the raw material is completely converted into vanadium chloride through a chlorination process, so that the introduction of process oxygen is avoided from the source. Wherein, the high-purity vanadium-containing powder is high-grade vanadium-containing intermediate alloy powder, the purity of the high-purity vanadium-containing powder is more than or equal to 99.0 percent, the granularity of the high-purity vanadium-containing intermediate alloy powder is less than or equal to 50 meshes, the non-metal impurity contents of O, Si, C, P and S are respectively not higher than 0.20 percent, 0.40 percent, 0.10 percent, 0.05 percent and 0.05 percent, and the other impurity contents are not higher than 0.2 percent; the high-grade alloy can reduce chlorine consumption and control the later separation effect, so that the high-grade alloy such as FeV80, AlV85 and the like has the best effect. Boiling chlorination has no strict requirements on the reactor, but the fluidized bed is the best choice for powder chlorination effect.
In the step A, the purity of the chlorine is more than or equal to 99.8 percent; the temperature of the boiling chlorination is 400-700 ℃.
Chlorination products obtained in the chlorination process are different metal chlorides, the boiling points and the saturated vapor pressures of the different metal chlorides are obviously different, wherein the boiling point of the vanadium chloride is 140-160 ℃, low-boiling-point chlorides in the mixed chlorides can be removed through low-temperature distillation, then high-temperature distillation and two-step distillation are carried out to obtain high-purity vanadium chloride, and the residual substances in the fluidized bed are high-melting-point metal chlorides (the boiling points are more than or equal to 180 ℃); the purity of the obtained high-purity vanadium chloride can reach more than 99.5 percent.
In the step C, vanadium chloride is heated and gasified at 500-700 ℃, and then the vanadium chloride is mixed with H by a spray gun with the wall temperature of 500-700 ℃ under the pressure of 0.5-2.0 MPa2Mixing; the main purpose of controlling the wall temperature is to ensure that the raw materials are in a gasification state and simultaneously achieve a certain preheating effect; the pressure is controlled mainlyThe flow rate in the reaction process and the temperature of a reaction interface are ensured to be stable; simultaneously adding H2Preheating to 300-500 ℃, ensuring the gasification state of vanadium chloride and avoiding normal temperature H2Leading to cold liquefaction of the vanadium chloride.
And C, performing reduction reaction on the reaction system on a reaction carrier of a plurality of layers of inert metal high-temperature nets at the temperature of 1100-1400 ℃. The multilayer inert metal high-temperature net has the functions of meeting the stable temperature condition required by reduction, and increasing the contact reaction area of gas under the high-temperature condition; in addition, the gasified vanadium chloride and the reducing agent are in gas phase contact, so that the raw materials are mixed at a molecular level, and the reaction diffusion distance is reduced, thereby being beneficial to the rapid nucleation of products in a non-equilibrium state and accelerating the reaction process; therefore, the reduction temperature is lower than the conventional reduction temperature (generally equal to or more than 1500 ℃).
In the present invention, unless otherwise specified, the purity and the content are both in mass percent.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
Performing chlorination reaction on ferrovanadium powder with the purity of 99.6 percent, the average particle size of 50 meshes and the vanadium mass fraction of 80.5 percent and chlorine with the purity of 99.9 percent in a fluidized bed at the temperature of 400 ℃, performing distillation operation twice on the collected liquid chlorination products at the temperature of 110 ℃ and 180 ℃ respectively, and collecting a high-purity vanadium chloride intermediate product at a second distillation condensation port. Heating and gasifying the obtained vanadium chloride intermediate product at 500 ℃, and passing through a spray gun with the wall temperature of 500 ℃ and the spray gun pressure of 0.5MPa and high-purity H with the preheating temperature of 300 DEG C2Mixing, and then contacting and reacting with a reaction carrier with the surface temperature of 1100 ℃ to obtain the metal vanadium powder.
Through the operation, the purity of the obtained high-purity vanadium chloride intermediate product is 99.5%, and the loss rate of vanadium chloride is 47.9%; the purity of the obtained vanadium metal powder is 99.6%, the average particle size of the powder is 20nm, and the loss rate of the reduced vanadium is 42.5%. The comprehensive vanadium yield is 30.2 percent (the reduction temperature is low, the reduction effect is poor, the yield is low, but the powder granularity is finest, the raw material purity is low, the temperature difference of secondary distillation is large, and the product purity is relatively low).
Example 2
Performing chlorination reaction on ferrovanadium powder with the purity of 99.8 percent, the average particle size of 100 meshes and the vanadium mass fraction of 81.0 percent and chlorine with the purity of 99.9 percent in a fluidized bed at the temperature of 500 ℃, performing distillation operation twice on the obtained liquid chlorination products at the temperature of 125 ℃ and 170 ℃ respectively, and collecting the high-purity vanadium chloride intermediate product at a second distillation condensation port. Heating and vaporizing the obtained vanadium chloride intermediate product at 600 ℃, and passing through a spray gun with the wall temperature of 600 ℃ and the spray gun pressure of 1.0MPa and high-purity H with the preheating temperature of 400 DEG C2Mixing, and then contacting and reacting with a reaction carrier with the surface temperature of 1250 ℃ to obtain the metal vanadium powder.
Through the operation, the purity of the obtained high-purity vanadium chloride intermediate product is 99.7%, and the loss rate of vanadium chloride is 21.2%; the purity of the obtained vanadium metal powder is 99.8%, the average particle size of the powder is 32nm, and the loss rate of the reduced vanadium is 14.0%. The overall vanadium yield was 67.9%.
Example 3
Performing chlorination reaction on ferrovanadium powder with the purity of 99.8 percent, the average particle size of 200 meshes and the vanadium mass fraction of 80.8 percent and chlorine with the purity of 99.9 percent in a fluidized bed at the temperature of 600 ℃, performing distillation operation twice on the obtained liquid chlorination products at the temperature of 140 ℃ and 160 ℃ respectively, and collecting the high-purity vanadium chloride intermediate product at a second distillation condensation port. Heating and vaporizing the obtained vanadium chloride intermediate product at 700 ℃, and passing through a spray gun with the wall temperature of 700 ℃ and the spray gun pressure of 2.0MPa and high-purity H with the preheating temperature of 500 DEG C2Mixing, and then carrying out catalytic reaction with a reactor carrier with the surface temperature of 1400 ℃ to obtain the metal vanadium powder.
Through the operation, the purity of the obtained high-purity vanadium chloride intermediate product is 99.9 percent, and the loss rate of vanadium chloride is 5.3 percent; the purity of the obtained vanadium metal powder is 99.9%, the average particle size of the powder is 45nm, and the loss rate of the reduced vanadium is 4.8%. The overall vanadium yield was 90.1%.
Example 4
Performing chlorination reaction on vanadium-aluminum alloy powder with the purity of 99.9 percent, the average particle size of 200 meshes and the vanadium mass fraction of 85.1 percent and chlorine with the purity of 99.9 percent in a fluidized bed at the temperature of 500 ℃, performing distillation operation twice on the obtained liquid chlorination product at the temperature of 125 ℃ and 170 ℃ respectively, and collecting the high-purity vanadium chloride intermediate product at a second distillation condensation port. Heating and vaporizing the obtained vanadium chloride intermediate product at 500 ℃, and passing through a spray gun with the wall temperature of 700 ℃ and the spray gun pressure of 1.0MPa and high-purity H with the preheating temperature of 500 DEG C2Mixing, and then contacting and reacting with a reaction carrier with the surface temperature of 1400 ℃ to obtain the metal vanadium powder.
Through the operation, the purity of the obtained high-purity vanadium chloride intermediate product is 99.8 percent, and the loss rate of vanadium chloride is 15.2 percent; the purity of the obtained vanadium metal powder is 99.7%, the average particle size of the powder is 45nm, and the loss rate of the reduced vanadium is 5.9%. The overall vanadium yield was 79.8%.
Example 5
Performing chlorination reaction on vanadium-aluminum alloy powder with the purity of 99.9 percent, the average particle size of 200 meshes and the vanadium mass fraction of 85.2 percent and chlorine with the purity of 99.9 percent in a fluidized bed at the temperature of 600 ℃, performing distillation operation twice on the obtained liquid chlorination product at the temperature of 140 ℃ and 160 ℃ respectively, and collecting the high-purity vanadium chloride intermediate product at a second distillation condensation port. Heating and vaporizing the obtained vanadium chloride intermediate product at 700 ℃, and passing through a spray gun with the wall temperature of 700 ℃ and the spray gun pressure of 2.0MPa and high-purity H with the preheating temperature of 500 DEG C2Mixing, and then contacting and reacting with a reaction carrier with the surface temperature of 1200 ℃ to obtain the metal vanadium powder.
Through the operation, the purity of the obtained high-purity vanadium chloride intermediate product is 99.9 percent, and the loss rate of vanadium chloride is 8.9 percent; the purity of the obtained vanadium metal powder is 99.9%, the average particle size of the powder is 28nm, and the loss rate of the reduced vanadium is 5.9%. The overall vanadium yield was 85.7%.
Claims (4)
1. The preparation method of the metal vanadium powder is characterized by comprising the following steps: the method comprises the following steps:
A. chlorination of vanadium-containing powder: boiling and chlorinating by taking vanadium-containing powder as a vanadium source and chlorine as a chlorination medium to obtain a primary vanadium chloride product;
B. primary purification of vanadium chloride: performing two-step distillation on the primary vanadium chloride product at 110-140 ℃ and 160-180 ℃, and collecting distillate obtained during distillation at 160-180 ℃ to obtain a high-purity vanadium chloride intermediate product;
C. high-temperature reduction of vanadium chloride: heating and gasifying vanadium chloride intermediate product, and mixing with high-purity H2Mixing, then contacting with a reaction carrier to perform a reduction reaction to obtain high-purity superfine metal vanadium powder;
in the step A, the vanadium-containing powder is vanadium-containing intermediate alloy powder, the purity of the vanadium-containing intermediate alloy powder is more than or equal to 99.0 percent, the granularity of the vanadium-containing intermediate alloy powder is less than or equal to 50 meshes, the content of nonmetal impurities of O, Si, C, P and S is respectively not higher than 0.20 percent, 0.40 percent, 0.10 percent, 0.05 percent and 0.05 percent, and the content of other impurities is not higher than 0.2 percent;
in the step C, vanadium chloride gas and high-purity H are mixed by a spray gun2Mixing, wherein the wall temperature of the spray gun is 500-700 ℃, and the pressure is 0.5-2.0 MPa;
in step C, before mixing, H is added2Preheating to 300-500 ℃;
in the step C, the reaction carrier is a multilayer inert metal high-temperature net, and the temperature of the reaction carrier is 1100-1400 ℃.
2. The method for preparing metal vanadium powder according to claim 1, characterized in that: in the step A, the purity of the chlorine is more than or equal to 99.8 percent.
3. The method for preparing metal vanadium powder according to claim 1, characterized in that: in the step A, the boiling chlorination temperature is 400-700 ℃.
4. The method for preparing metal vanadium powder according to claim 1, characterized in that: in the step C, the heating and gasifying temperature of the vanadium chloride intermediate product is 500-700 ℃.
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