A system and method for preparing high-purity low-valent vanadium oxides by chlorination

Abstract

The invention belongs to the field of chemical industry and metallurgy, and provides a system and a method for preparing a high-purity and low-valent vanadium oxide through a chlorination method. According to the method, an industrial grade vanadium oxide is converted into vanadium oxytrichloride by using fluidization chlorination; two-stage dust removing and three-stage leaching are performed toobtain crude vanadium oxytrichloride; and rectification, catalytic oxidation and precise reduction control are performed to obtain the high-purity and low-valent vanadium oxide, wherein the average valence of vanadium can be any one selected from 3.0-4.5. According to the present invention, the furnace temperature is controlled by spraying the vanadium oxytrichloride mud into the chlorination fluidized bed; the reaction efficiency is improved by arranging the inner member on the catalytic oxidation fluidized bed; the reduction degree is regulated by arranging the vertical baffle and the material discharging ports with different heights on the reduction fluidized bed so as to obtain the high-purity and low-valent vanadium oxide with the specific valence; and the system and the method have advantages of strong raw material adaptability, no pollution, low production energy consumption, low operation cost, stable product quality and the like, are suitable for the large-scale industrial production of high-purity and low-valent vanadium oxide with more than 4N, and have good economic and social benefits.

Description

technical field

[0001] The invention belongs to the fields of chemical industry and metallurgy, and particularly relates to a system and method for preparing high-purity and low-valent vanadium oxide by a chlorination method. Background technique

[0002] Low-valent vanadium oxides, including vanadium trioxide and vanadium dioxide, are important industrial vanadium products and are widely used in the production of alloy additives such as ferrovanadium and vanadium nitride, as well as catalysts, colorants, and cemented carbide additives. With the continuous development of new energy technologies, the battery industry has an increasingly strong demand for high-purity and low-priced vanadium oxides (purity above 3N5), including all-vanadium redox flow batteries (VRBs) with good large-scale energy storage performance and electric vehicles. Vanadate-based lithium-ion batteries, etc. However, the existing industrial technology can usually only prepare low-valent vanadium oxides w...

Examples

Embodiment 1

[0075] The chlorination method used in this embodiment prepares the system of high-purity low-valent vanadium oxide, such as figure 1 As shown, it includes feeding section 1, chlorination section 2, dedusting and rinsing section 3, rectification and purification section 4, catalytic oxidation section 5, catalytic oxidation product feeding section 6, preheating and dust removal section 7, control reduction section 8, first-level Cooling section 9, secondary cooling section 10, high-purity low-price vanadium oxide silo 11, tail gas leaching absorption tower 12, induced draft fan 13, chimney 14;

[0076] The feeding section 1 includes an industrial-grade vanadium oxide silo 1-1, an industrial-grade vanadium oxide screw feeder 1-2, a carbon source silo 1-3, and a carbon source screw feeder 1-4;

[0077] The chlorination section 2 includes a chlorination bed feeder 2-1, a chlorination fluidized bed main body 2-2, a chlorination bed cyclone separator 2-3 and a chlorination bed spira...

Embodiment 2

[0098] The method for preparing high-purity low-valent vanadium oxides using the system described in Example 1 comprises the following steps:

[0099]The industrial-grade vanadium oxide in the industrial-grade vanadium oxide silo 1-1 and the carbon source in the carbon source silo 1-3 pass through the industrial-grade vanadium oxide screw feeder 1-2 and the carbon source screw feeder 1-4 respectively. Enter the chlorination fluidized bed main body 2-2 after entering the chlorination bed feeder 2-1 mixing simultaneously; From the chlorine of the chlorine gas source main pipe, the nitrogen of the nitrogen gas source main pipe through the chlorination fluidized bed main body 2-2 bottom The air inlet enters the main body 2-2 of the chlorinated fluidized bed to maintain the fluidization of industrial-grade vanadium oxide and carbon source and chemically react with it. The chlorine gas and carbon source work together to produce industrial-grade vanadium oxide and a small amount of im...

Embodiment 3

[0106] In this example, powdered industrial-grade vanadium pentoxide (purity: 98.50%) is used as raw material, and the method described in Example 2 is used to prepare high-purity and low-valent vanadium oxide. Industrial grade vanadium pentoxide (purity 98.50%) has a processing capacity of 80kg / h, and is prepared by chlorination, dedusting and rinsing, rectification and purification of vanadium oxychloride, catalytic oxidation, and precise control of reduction to obtain high-purity vanadium trioxide products , with a purity of 99.995wt% (4N5).

[0107] In the main body 2-2 of the chlorination fluidized bed, the amount of petroleum coke added during the chlorination process is 30% of the mass of the industrial-grade vanadium pentoxide powder, the chlorination operating temperature is 600°C, and the operating gas velocity in the fluidization section is 3.0m / s, the mole fraction of chlorine in the chlorine-nitrogen mixed gas entering the air chamber is 20%; in the main body 5-4...

technical field

[0001] The invention belongs to the fields of chemical industry and metallurgy, and particularly relates to a system and method for preparing high-purity and low-valent vanadium oxide by a chlorination method. Background technique

[0002] Low-valent vanadium oxides, including vanadium trioxide and vanadium dioxide, are important industrial vanadium products and are widely used in the production of alloy additives such as ferrovanadium and vanadium nitride, as well as catalysts, colorants, and cemented carbide additives. With the continuous development of new energy technologies, the battery industry has an increasingly strong demand for high-purity and low-priced vanadium oxides (purity above 3N5), including all-vanadium redox flow batteries (VRBs) with good large-scale energy storage performance and electric vehicles. Vanadate-based lithium-ion batteries, etc. However, the existing industrial technology can usually only prepare low-valent vanadium oxides w...

Examples

Embodiment 1

[0075] The chlorination method used in this embodiment prepares the system of high-purity low-valent vanadium oxide, such as figure 1 As shown, it includes feeding section 1, chlorination section 2, dedusting and rinsing section 3, rectification and purification section 4, catalytic oxidation section 5, catalytic oxidation product feeding section 6, preheating and dust removal section 7, control reduction section 8, first-level Cooling section 9, secondary cooling section 10, high-purity low-price vanadium oxide silo 11, tail gas leaching absorption tower 12, induced draft fan 13, chimney 14;

[0076] The feeding section 1 includes an industrial-grade vanadium oxide silo 1-1, an industrial-grade vanadium oxide screw feeder 1-2, a carbon source silo 1-3, and a carbon source screw feeder 1-4;

[0077] The chlorination section 2 includes a chlorination bed feeder 2-1, a chlorination fluidized bed main body 2-2, a chlorination bed cyclone separator 2-3 and a chlorination bed spira...

Embodiment 2

[0098] The method for preparing high-purity low-valent vanadium oxides using the system described in Example 1 comprises the following steps:

[0099]The industrial-grade vanadium oxide in the industrial-grade vanadium oxide silo 1-1 and the carbon source in the carbon source silo 1-3 pass through the industrial-grade vanadium oxide screw feeder 1-2 and the carbon source screw feeder 1-4 respectively. Enter the chlorination fluidized bed main body 2-2 after entering the chlorination bed feeder 2-1 mixing simultaneously; From the chlorine of the chlorine gas source main pipe, the nitrogen of the nitrogen gas source main pipe through the chlorination fluidized bed main body 2-2 bottom The air inlet enters the main body 2-2 of the chlorinated fluidized bed to maintain the fluidization of industrial-grade vanadium oxide and carbon source and chemically react with it. The chlorine gas and carbon source work together to produce industrial-grade vanadium oxide and a small amount of im...

Embodiment 3

[0106] In this example, powdered industrial-grade vanadium pentoxide (purity: 98.50%) is used as raw material, and the method described in Example 2 is used to prepare high-purity and low-valent vanadium oxide. Industrial grade vanadium pentoxide (purity 98.50%) has a processing capacity of 80kg / h, and is prepared by chlorination, dedusting and rinsing, rectification and purification of vanadium oxychloride, catalytic oxidation, and precise control of reduction to obtain high-purity vanadium trioxide products , with a purity of 99.995wt% (4N5).

[0107] In the main body 2-2 of the chlorination fluidized bed, the amount of petroleum coke added during the chlorination process is 30% of the mass of the industrial-grade vanadium pentoxide powder, the chlorination operating temperature is 600°C, and the operating gas velocity in the fluidization section is 3.0m / s, the mole fraction of chlorine in the chlorine-nitrogen mixed gas entering the air chamber is 20%; in the main body 5-4...

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