Vanadium-containing mineral synergistic vanadium extraction method

Abstract

This invention discloses a vanadium extraction method using synergistic combinations of vanadium-containing minerals, comprising the following steps: mixing vanadium shale ore, vanadium-titanium magnetite, and additives; grinding the mixture to obtain activated minerals; then reducing and roasting the activated minerals to obtain reduction products; and finally crushing the reduction products to obtain ferrovanadium alloy and titanium-containing slag phase. This vanadium extraction method fully utilizes the high TFe content in vanadium-titanium magnetite and the high carbon content in vanadium shale ore, leveraging their synergistic effect to fully utilize the inherent properties of the minerals, reducing the use of additives, and increasing the metal extraction rate. A simple process can simultaneously extract vanadium metal from two complex ores, vanadium shale ore and vanadium-titanium magnetite, avoiding the complex process routes and pollutant emissions associated with traditional blast furnace smelting for vanadium extraction from vanadium-titanium magnetite and traditional roasting of vanadium shale ore.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of metal mineral smelting, and particularly relates to a vanadium ore processing method. BACKGROUND

[0002] Vanadium is a high-melting-point metal similar in nature to tantalum and niobium. Because vanadium has the property of refining grains, it has the characteristic of increasing the strength of alloys, and advanced titanium-aluminum-vanadium alloys are being used in the aerospace industry.

[0003] With the consumption of vanadium-titanium magnetite, stone coal vanadium ore has gradually become the main raw material of vanadium smelting enterprises. The smelting process of vanadium-titanium magnetite and stone coal vanadium ore is complex, and common means for extracting vanadium include blast furnace smelting and roasting-leaching. Vanadium-titanium magnetite smelting will generate vanadium-containing pig iron, which can be directly used for the production of subsequent vanadium-containing steel, or the molten iron is oxidized, so that vanadium elements enter the slag phase in the form of vanadium oxide, which can be reduced and enriched by silicon or other means. For example, CN111961782A discloses a method and device for reducing smelting of vanadium-titanium magnetite, which uses a reducing agent, fuel and oxygen-enriched air to reduce and smelt the vanadium-titanium magnetite, so as to obtain vanadium-containing iron liquid and liquid slag. Roasting-leaching of vanadium-containing minerals or vanadium-containing slag recovers vanadium in ionic form from the solution, the roasting process can destroy the spinel phase in stone coal vanadium ore, and vanadium elements are dissociated from the octahedral structure, thereby facilitating the subsequent leaching process, and sodium salt, calcium salt, etc. can be used as additives in the roasting process. For example, CN110184452A discloses a method for extracting vanadium from solids, which can process vanadium-containing slag and stone coal vanadium ore. The patent mixes dry vanadium-containing solid powder, calcium hydroxide powder and water to form a block, and then uses oxidation roasting-acid leaching to obtain a vanadium-containing filtrate. The vanadium-containing solution can be used to prepare V2O5 vanadium products by precipitation method.

[0004] The currently disclosed smelting methods for stone coal vanadium ore and vanadium-titanium magnetite mainly change the types and ratios of additives and optimize the process parameters such as temperature control system in traditional technology, which has little improvement on the extraction rate of vanadium in subsequent vanadium ore, and has poor raw material applicability. How to efficiently dissociate silicates and other associated minerals in vanadium-containing minerals under mild conditions, and how to realize clean and efficient short process for high-efficiency extraction of vanadium from difficult-to-process vanadium-containing minerals, the development of new vanadium ore processing methods is imminent. SUMMARY

[0005] The technical problem to be solved by the present application is to overcome the deficiencies and defects mentioned in the above background technology, and to provide a vanadium extraction method with high vanadium extraction rate, short process flow, less additive use and environmental friendliness. To solve the above technical problems, the technical solution provided by the present application is:

[0006] A vanadium-containing mineral synergistic vanadium extraction method, comprising the following steps: mixing stone coal vanadium ore, vanadium-titanium magnetite and additives, obtaining activated minerals through grinding treatment, and obtaining reduction products through reduction roasting of the activated minerals, and obtaining iron-vanadium alloy and titanium-containing slag phase by crushing the reduction products.

[0007] In the above vanadium extraction method, preferably, a stirring medium is also added during the grinding treatment, and the vanadium-titanium magnetite, stone coal vanadium ore and additives are mixed, ground and activated in a stirring tank through mechanical stirring, and then the activated minerals are separated from the stirring medium. The grinding treatment process can reduce the particle size of the minerals, increase the surface energy of the minerals, and facilitate the bonding of the carbonaceous reducing agent in the stone coal vanadium ore and the iron oxides in the vanadium-titanium magnetite during the high-temperature reduction process, thereby improving the synergistic smelting efficiency. The grinding process can also destroy the stable di-octahedral structure of the vanadium ore, which is conducive to the release of vanadium during the reduction roasting process.

[0008] In the above vanadium extraction method, preferably, the stirring medium is steel balls, corundum balls or zirconium dioxide balls, the particle size of the stirring medium is 0.2-1.2 mm, and the amount of the stirring medium added is not more than one-third of the volume of the activation cavity of the stirring tank.

[0009] In the above vanadium extraction method, preferably, the stirring endpoint of mechanical stirring is that the mass fraction of the activated minerals with a particle size of <1 mm is more than 80%. Our research shows that the mechanical activation effect is best when the stirring endpoint is controlled as above, which is more conducive to the synergistic smelting effect of the stone coal vanadium ore and the vanadium-titanium magnetite.

[0010] In the above vanadium extraction method, preferably, the additive is a calcium-containing substance, and the amount of the additive is controlled to make the alkalinity of the activated minerals be 0.8-1.8, and the alkalinity is the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Too high slag alkalinity will cause calcium oxide to combine with vanadium oxide to form calcium vanadate, reducing the recovery rate of vanadium. At the same time, too high alkalinity will result in a large amount of slag, thereby increasing the energy consumption of the smelting process. When the slag alkalinity is low, it is not conducive to slagging and removing impurity elements. More importantly, the main metal oxide components of the stone coal vanadium ore are SiO2 and Al2O3, and the main metal oxide components of the vanadium-titanium magnetite are FeO, Fe2O3, TiO2, CaO, MgO, SiO2 and Al2O3. Controlling the alkalinity to be 0.8-1.8 is more conducive to the formation of oxide slag through the synergistic smelting of the two.

[0011] In the above vanadium extraction method, preferably, the additive is one or both of calcium oxide and calcium carbonate.

[0012] In the aforementioned vanadium extraction method, preferably, the carbon content in the vanadium-bearing shale is not less than 6 wt%, and the vanadium content is 0.3-1.5 wt%; the TFe content in the vanadium-titanium magnetite is not less than 50 wt%, the TiO2 content is greater than 10 wt%, and the vanadium content is 0.3-1.5 wt%. The carbon in the vanadium-bearing shale can act as a reducing agent during the smelting process of vanadium-titanium magnetite, reducing the addition of carbonaceous reducing agents. The iron oxide and ferrous oxide in the vanadium-titanium magnetite are reduced to metallic iron at high temperatures, and increasing the metallic iron content increases the probability of metallic vanadium being captured and incorporated into the molten iron from the vanadium-bearing shale. The determination of the aforementioned carbon and iron contents is beneficial to the synergistic effect of the vanadium-bearing shale and the vanadium-titanium magnetite.

[0013] In the above-mentioned vanadium extraction method, preferably, the mass ratio of vanadium-titanium magnetite to vanadium shale ore is 1:(1-5). The ratio of vanadium-titanium magnetite to vanadium shale ore needs to be determined by considering the content of their components and the mechanism of their synergistic effect. The mass ratio is determined by considering the TFe content in vanadium-titanium magnetite and the carbon content in vanadium shale ore. In the synergistic effect of vanadium-titanium magnetite and vanadium shale ore, the high TFe content in vanadium-titanium magnetite is conducive to increasing the probability of vanadium being captured into molten iron. The carbon in vanadium shale ore can act as a reducing agent to reduce the iron oxide in vanadium-titanium magnetite to generate elemental iron to capture vanadium. A reasonable ratio of vanadium-titanium magnetite to vanadium shale ore can maximize the recovery of vanadium from vanadium-titanium magnetite and vanadium shale ore into pig iron.

[0014] In the aforementioned vanadium extraction method, preferably, when mixing vanadium shale ore, vanadium-titanium magnetite, and additives, a small amount of carbon powder can be added if the reducing agent in the mixed minerals is insufficient. The amount of carbon powder added is controlled so that the total carbon content obtained by adding the carbon powder, vanadium shale ore, and vanadium-titanium magnetite is 1.2-5 times the theoretical carbon consumption of iron oxides in the activated minerals. The amount of carbon powder added is determined based on the content of metal oxides such as iron oxide and ferrous oxide. Excessive reducing agent will cause some TiO2 to be reduced to TiC, which will increase the viscosity of the slag phase, which is not conducive to the vanadium extraction process. A reasonable amount of carbon powder added can maximize the original mineral properties of vanadium-titanium magnetite and vanadium shale ore and promote the recovery of vanadium into pig iron.

[0015] In the above-mentioned vanadium extraction method, preferably, the reduction roasting temperature is 1250-1500℃, and the time is 2-5 hours. The roasting temperature is mainly related to the composition of the mixed minerals of vanadium-titanium magnetite and vanadium shale. When there are more high-melting-point substances such as silica in the mixed minerals, the reduction temperature can be appropriately increased, which will be beneficial to the synergistic effect between the two minerals. However, excessively high reduction temperatures will increase energy consumption, while low temperatures will result in a slower reaction kinetic rate, which is not conducive to the synergistic effect between vanadium shale and vanadium-titanium magnetite.

[0016] The principle of this invention is briefly described as follows: This invention combines the smelting of vanadium-titanium magnetite and vanadium shale ore. The two act synergistically; the carbon in the vanadium shale ore acts as a reducing agent during the smelting process, avoiding the addition of coke. During the reduction smelting process, vanadium ions are reduced to metallic vanadium by the reducing agent, while iron oxide and ferrous oxide in the vanadium-titanium magnetite are reduced to metallic iron at high temperatures. The increased metallic iron content increases the probability of metallic vanadium being captured into the molten iron from the vanadium shale ore, improving the vanadium extraction rate and reducing the use of additives. The combined smelting of vanadium-titanium magnetite and vanadium shale ore in this invention fully utilizes the inherent properties of the minerals, while simultaneously utilizing two mainstream vanadium-bearing minerals for synergistic vanadium extraction. During the synergistic smelting process, vanadium from both the vanadium-titanium magnetite and vanadium shale ore is also enriched into the molten iron. This not only avoids the complex blast furnace smelting of traditional vanadium-titanium magnetite and the traditional roasting of vanadium shale ore, but also ensures the full utilization of iron oxide in the vanadium-titanium magnetite and carbon in the vanadium shale ore. Furthermore, the process is short, clean, and efficient. The additives play multiple roles in the reduction process, specifically as follows: 1. At high temperatures, they can effectively disrupt the illite crystal structure of vanadium shale, causing vanadium ions to be released from the dioctahedron and become free; 2. They remove harmful elements such as sulfur, phosphorus, and arsenic. Since the oxides of these harmful elements are usually acidic substances, calcium oxide can form relatively stable compounds with them; 3. They adjust the alkalinity of the material and reduce the activity of SiO2 in the slag, which is beneficial to the distribution of vanadium in the metal phase.

[0017] Current technologies do not mention the joint smelting of vanadium-titanium magnetite and vanadium shale ore to extract metallic vanadium. This co-smelting process can fully utilize the characteristics of different minerals and is of great significance for the extraction of vanadium-containing minerals and vanadium-containing slag phases. The synergistic use of these two minerals allows for the short-process, low-emission extraction of vanadium from vanadium-titanium magnetite and vanadium shale ore, fully utilizing the characteristics of vanadium-containing minerals. The resulting ferrovanadium alloy can be sold as a product or used as a raw material for further processing, such as smelting vanadium-containing alloys, manufacturing permanent magnets, catalysts, special ceramics, and vanadium-containing batteries. The waste residue can be used as a building material.

[0018] Compared with existing technologies, the advantages of this invention are:

[0019] 1. The vanadium extraction method of the present invention, which utilizes the high TFe content in vanadium-titanium magnetite and the high carbon content in vanadium shale ore, takes full advantage of their synergistic effect to fully utilize the inherent properties of the minerals, reduce the use of additives, and improve the metal extraction rate. A simple process can simultaneously extract vanadium metal from two complex vanadium shale ore and vanadium-titanium magnetite, avoiding the complex process routes and pollutant emissions of traditional vanadium extraction from vanadium-titanium magnetite and traditional roasting of vanadium shale ore. The metallization rate of iron in this process can reach up to 97.7%, and the vanadium extraction rate can reach up to 91.3%.

[0020] 2. The vanadium extraction method of the present invention, which utilizes the synergistic combination of vanadium-containing minerals, avoids the generation of large amounts of corrosive gases and wastewater in traditional vanadium extraction processes, making it more environmentally friendly. Furthermore, the present invention features a simple process, fast reaction rate, high raw material adaptability, low equipment requirements, and the resulting iron-vanadium alloy can be sold directly or used as a raw material for preparing vanadium-containing alloys. The slag phase during the reduction process can be used as a building material. Overall, the present invention achieves efficient and clean extraction of vanadium from vanadium-titanium magnetite and vanadium shale coal using a shorter process flow, and has excellent application prospects. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a process flow diagram of the vanadium extraction method based on the synergistic combination of vanadium-containing minerals according to the present invention. Detailed Implementation

[0023] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments.

[0024] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0025] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0026] The composition range of the vanadium-titanium magnetite and vanadium shale ore used in the following examples is shown in Table 1. The main phases are iron oxide, ferrous oxide, silicon dioxide, and carbon. The purity of the calcium additives and carbon powder used is greater than 99%. Using traditional blast furnace smelting or sulfation roasting-water leaching treatment, the vanadium recovery rate is generally below 80%.

[0027] Table 1: Composition and Content of Vanadium-Titanium Magnetite and Vanadium Sand Ore

[0028]

[0029] Note: "-" indicates that the substance is almost entirely absent, and the same applies below.

[0030] Example 1:

[0031] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale ore, and calcium oxide. The composition of the raw materials in this embodiment is shown in Table 2. Since the carbon content of the vanadium shale ore in this embodiment is high, there is no need to add additional carbon powder.

[0032] Table 2: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0033]

[0034] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0035] S1: Mix 100g of vanadium-titanium magnetite and 100g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.0, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with corundum balls with a diameter of 10mm, then add the mixture to a stirring tank. Mechanical stirring is used to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0036] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0037] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 2 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0038] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0039] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0040] Weighing the product revealed a mass loss of 6.1 wt%, primarily caused by the reduction product CO. ICP analysis of the iron-vanadium alloy showed an iron metallization rate of 82.6% and a vanadium metallization rate of 78.9%. Based on the mass of vanadium entering the iron-vanadium alloy, the extraction rate was calculated to be 78.9%.

[0041] Example 2:

[0042] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, calcium oxide, and carbon powder. The raw material composition of this embodiment is shown in Table 3.

[0043] Table 3: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0044]

[0045] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0046] S1: Mix 100g of vanadium-titanium magnetite, 100g of vanadium shale ore, and 10g of carbon powder. Add calcium oxide until the basicity of the mixed ore is 1.6, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with steel balls of 10mm diameter, then add the mixture to a mixing tank. Mechanical stirring is used to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0047] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0048] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1250°C at a rate of 20°C / min, and held at 1250°C for 5 hours. After holding, the temperature is cooled to 500°C at a rate of 10°C / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0049] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0050] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0051] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 84.6%, and the vanadium metallization rate was 82.5%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 82.5%.

[0052] Example 3:

[0053] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, carbon powder and calcium oxide. The raw material composition of this embodiment is shown in Table 4.

[0054] Table 4: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0055]

[0056] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0057] S1: Mix 100g of vanadium-titanium magnetite, 100g of vanadium shale ore, and 20g of carbon powder. Add calcium carbonate until the basicity of the mixed ore is 1.6. Convert the calcium carbonate to an equimolar amount of calcium oxide to calculate the basicity, which is expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with 10mm diameter zirconia balls, then add the mixture to a stirring tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0058] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0059] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1400℃ at a rate of 20℃ / min, and held at 1400℃ for 3 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0060] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0061] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0062] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 93.1%, and the vanadium metallization rate was 88.5%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 88.5%.

[0063] Example 4:

[0064] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this embodiment is shown in Table 5.

[0065] Table 5: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0066]

[0067] likeFigure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0068] S1: Mix 50g of vanadium-titanium magnetite and 100g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.8, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls with a diameter of 10mm, then add the mixture to a stirring tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0069] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0070] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 4 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0071] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0072] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0073] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 90.2%, and the vanadium metallization rate was 87.5%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 87.5%.

[0074] Example 5:

[0075] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this embodiment is shown in Table 6.

[0076] Table 6: Composition and Content of Vanadium-Titanium Magnetite and Vanadium Sand Ore

[0077]

[0078] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0079] S1: Mix 50g of vanadium-titanium magnetite and 150g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.6, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls with a diameter of 10mm, then add the mixture to a stirring tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0080] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0081] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 4 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0082] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0083] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0084] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 89.7%, and the vanadium metallization rate was 86.5%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 86.5%.

[0085] Example 6:

[0086] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this embodiment is shown in Table 7.

[0087] Table 7: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0088]

[0089] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0090] S1: Mix 40g of vanadium-titanium magnetite and 160g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.2, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls of 10mm diameter, then add the mixture to a stirring tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0091] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0092] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 5 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0093] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0094] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0095] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 92.7%, and the vanadium metallization rate was 89.3%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 89.3%.

[0096] Example 7:

[0097] The raw materials processed in this embodiment are vanadium-titanium magnetite, vanadium shale coal, carbon powder and calcium oxide. The raw material composition of this embodiment is shown in Table 8.

[0098] Table 8: Composition and Content of Vanadium-Titanium Magnetite and Vanadium-Shale Ore

[0099]

[0100] like Figure 1 As shown, the vanadium extraction method using the synergistic combination of vanadium-containing minerals in this embodiment includes the following steps:

[0101] S1: Mix 50g of vanadium-titanium magnetite and 100g of vanadium shale ore. Add 5g of carbon powder and calcium oxide until the basicity of the mixed ore is 1.6. The basicity is expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls with a diameter of 10mm. After mixing, add the mixture to a mixing tank and use mechanical stirring to achieve mixing and grinding of the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0102] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0103] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1400℃ at a rate of 20℃ / min, and held at 1400℃ for 5 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0104] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0105] The vanadium-titanium magnetite and vanadium shale ore in this embodiment were processed using a co-smelting method, and the processing results are as follows:

[0106] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 97.7%, and the vanadium metallization rate was 91.3%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 91.3%.

[0107] Comparative Example 1:

[0108] The raw materials used in this comparative example are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this comparative example is the same as that in Example 4.

[0109] The vanadium extraction method based on the synergistic combination of vanadium-bearing minerals in this comparative example includes the following steps:

[0110] S1: Mix 50g of vanadium-titanium magnetite and 100g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.8. The basicity is expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3).

[0111] S2: Remove the mixed minerals from step S1 and place them into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated minerals in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 4 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0112] S3: The reduction product from step S2 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0113] The processing effect is as follows:

[0114] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 72.2%, and the vanadium metallization rate was 63.1%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 63.1%.

[0115] Comparative Example 2:

[0116] The raw materials used in this comparative example are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this comparative example is the same as that in Example 4.

[0117] The vanadium extraction method based on the synergistic combination of vanadium-bearing minerals in this comparative example includes the following steps:

[0118] S1: Mix 150g of vanadium-titanium magnetite and 50g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 1.8, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls with a diameter of 10mm, then add the mixture to a stirring tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0119] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0120] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 4 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0121] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0122] The processing effect is as follows:

[0123] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 34.5%, and the vanadium metallization rate was 21.5%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 21.5%.

[0124] Comparative Example 3:

[0125] The raw materials used in this comparative example are vanadium-titanium magnetite, vanadium shale coal, and calcium oxide. The raw material composition of this comparative example is the same as that in Example 4.

[0126] The vanadium extraction method based on the synergistic combination of vanadium-bearing minerals in this comparative example includes the following steps:

[0127] S1: Mix 50g of vanadium-titanium magnetite and 100g of vanadium shale ore. Add calcium oxide until the basicity of the mixed ore is 3, expressed as the mass ratio of (CaO+MgO) / (SiO2+Al2O3). Mix the mixed ore with alumina balls of 10mm diameter, then add the mixture to a mixing tank. Use mechanical stirring to mix and grind the vanadium-titanium magnetite and vanadium shale ore to obtain mechanically activated minerals.

[0128] S2: Use a sieve to separate the stirring medium from the activated minerals, with the activated minerals having a final particle size of less than 1 mm.

[0129] S3: Remove the activated mineral from step S2 and place it into an alumina crucible. Open the tube furnace and place the alumina crucible containing the activated mineral in the middle of the furnace. Place refractory bricks at both ends of the tube furnace to prevent excessive heat loss at high temperatures and maintain the furnace temperature range. Inert gas is introduced into the furnace for protection, and the temperature is increased to 1500℃ at a rate of 20℃ / min, and held at 1500℃ for 4 hours. After holding, the temperature is cooled to 500℃ at a rate of 10℃ / min, and then allowed to cool naturally. The reduction product is obtained after cooling.

[0130] S4: The reduction product from step S3 is placed in a jaw crusher for crushing to obtain ferrovanadium alloy and titanium-containing slag.

[0131] The processing results of this comparative example are as follows:

[0132] Based on weighing and ICP analysis of the iron-vanadium alloy, the iron metallization rate was calculated to be 35.2%, and the vanadium metallization rate was 18.6%. The extraction rate, calculated based on the mass of vanadium entering the iron-vanadium alloy, was 18.6%. Due to excessive alkalinity, some calcium ferrite and calcium vanadate were generated, resulting in a lower amount of iron-vanadium alloy formed and a poorer vanadium recovery rate.

Claims

1. A method for vanadium extraction using the synergistic combination of vanadium-containing minerals, characterized in that, Includes the following steps: The vanadium shale, vanadium-titanium magnetite and additives are mixed and ground to obtain activated minerals. The activated minerals are then reduced and roasted to obtain reduction products. The reduction products are crushed to obtain iron-vanadium alloy and titanium-containing slag phase. The additive is a calcium-containing substance, and the amount of the additive is used to control the alkalinity of the activated mineral to be 0.8-1.8, with the alkalinity being the mass ratio of (CaO+MgO) / (SiO2+Al2O3). The carbon content in the vanadium-carbon shale is not less than 6 wt%, and the vanadium content is 0.3-1.5 wt%; the TFe content in the vanadium-titanium magnetite is not less than 50 wt%, the TiO2 content is greater than 10 wt%, and the vanadium content is 0.3-1.5 wt%. The mass ratio of the vanadium-titanium magnetite to the vanadium shale coal is 1:(1-5).

2. The vanadium extraction method according to claim 1, characterized in that, During the grinding process, a stirring medium is added. In the mixing tank, vanadium-titanium magnetite, vanadium shale coal, and additives are mixed, ground, and activated to obtain activated minerals through mechanical stirring.

3. The vanadium extraction method according to claim 2, characterized in that, The stirring medium is steel balls, corundum balls, or zirconium dioxide balls, with a particle size of 0.2-1.2 mm. The amount of stirring medium added does not exceed one-third of the activation chamber of the stirring tank.

4. The vanadium extraction method according to claim 2, characterized in that, The mechanical stirring endpoint is when the mass percentage of the activated mineral with a particle size <1mm is above 80%.

5. The vanadium extraction method according to any one of claims 1, characterized in that, The additive is one or both of calcium oxide and calcium carbonate.

6. The vanadium extraction method according to any one of claims 1-5, characterized in that, When vanadium shale, vanadium-titanium magnetite, and additives are mixed, carbon powder is also added. The amount of carbon powder added is controlled to ensure that the total carbon content obtained by adding the carbon powder, vanadium shale, and vanadium-titanium magnetite is 1.2-5 times the theoretical carbon consumption of iron oxides in the activated minerals.

7. The vanadium extraction method according to any one of claims 1-5, characterized in that, The reduction calcination temperature is 1250-1500℃, and the time is 2-5h.

Images