CN110306044B - Method for leaching vanadium from vanadium-containing mineral of vanadium-iron spinel by hydrothermal oxalic acid complexation - Google Patents
Method for leaching vanadium from vanadium-containing mineral of vanadium-iron spinel by hydrothermal oxalic acid complexation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
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- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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Abstract
The invention providesA method for leaching vanadium from vanadium-containing minerals of ferrovanadium spinel by hydrothermal oxalic acid complexation belongs to the field of leaching vanadium from vanadium-containing minerals of ferrovanadium spinel type by hydrothermal method. The method takes vanadium-iron spinel vanadium-containing minerals as raw materials, iron powder as a reducing agent and oxalic acid solution as a leaching agent, the vanadium-iron spinel vanadium-containing minerals and the iron powder are mixed into slurry and reacted under the hydrothermal condition; and (3) carrying out solid-liquid separation on the slurry obtained after the reaction to obtain a clean vanadium-containing leaching solution and a ferrous oxalate byproduct. The method utilizes the strong complexation of oxalate ions to respectively form [ V (C) with vanadium and iron in the ferrovanadium spinel2O4)3]3‑，[Fe(C2O4)3]3‑Entering a solution; formed [ Fe (C) ]2O4)3]3‑And ferrous oxalate precipitation is generated with Fe powder, so that the leaching reaction is facilitated, and the leaching reaction rate is accelerated. The method provided by the invention realizes the high-efficiency vanadium extraction of vanadium from vanadium-containing minerals of vanadium-iron spinel, realizes the vanadium-iron separation in the leaching process, simplifies the process steps, and obtains a byproduct with high added value, namely ferrous oxalate.
Description
Technical Field
The invention belongs to the field of vanadium leaching from vanadium-iron spinel type vanadium-containing minerals by a hydrothermal method. In particular to a method for obtaining vanadium-containing leaching liquid and ferrous oxalate byproducts by utilizing stronger complexation of oxalate ions and high-pressure reduction conditions so as to accelerate the leaching reaction rate.
Background
Vanadium is an important metal element and is widely applied to industries such as machinery, aviation, electronic technology, national defense industry and the like, so that vanadium is called metal vitamin. The vanadium resources in China mainly comprise vanadium-titanium magnetite and vanadium-containing stone coal, and the two different vanadium-containing resources can be converted into vanadium-containing minerals with vanadium-iron spinel phases through a metallurgical method.
At present, the pressurizing wet-process metallurgy process has the characteristics of strong applicability to raw materials, capability of being carried out at higher temperature, improved process dynamics conditions, accelerated leaching speed, shortened reaction time and the like, so that a lot of workers apply the pressurizing wet-process leaching process to the vanadium extraction field, for example, Chinese patents CN107236871A, CN102531056A, CN105420517A and the like carry out vanadium extraction from vanadium-containing minerals through the pressurizing leaching metallurgy process, and finally obtain vanadium-containing leachate. The method is characterized in that strong alkaline solution is used as a leaching agent, oxygen is introduced under the conditions of certain temperature and pressure, and high-temperature high-pressure oxidation leaching reaction is carried out, so as to obtain vanadium-containing leaching solution. However, a large amount of silicon enters the solution and affects the purity of the final vanadium product, so that CaO is added for desiliconization, and the cost is increased; in addition, the strong alkaline solution has strong corrosivity to high-pressure equipment, high maintenance cost and short service life. Therefore, to solve the defects caused by the strong alkali leaching agent, a metallurgist selects oxalic acid as the leaching agent, and the oxalic acid belongs to weak acid, is relatively weak in corrosivity and has relatively strong complexing property. The Chinese patent CN105624435A takes fluoride and oxalic acid as leaching agents to selectively leach vanadium in stone coal, but the leaching rate is low, and the fluoride pollutes the environment and has great harm to people. The method comprises the following steps of carrying out experimental study on leaching behavior of vanadium extraction tailings by schleph et al (schleph. experimental study on leaching behavior of vanadium extraction tailings [ D ]. university of northeast, 2012.), and under a pressurizing condition, controlling the addition of oxalic acid to avoid excessive dissolution of iron, wherein a vanadium-containing phase in the vanadium extraction tailings is mainly vanadium ferrite, so that dissolution of iron is inhibited, and leaching of vanadium is prevented inevitably, so that the leaching rate is low and reaches about 66% at most. And a large amount of un-leached vanadium and chromium elements exist in the leaching residue, so that the leaching residue cannot be discharged randomly, and the leaching tailings are difficult to treat. In order to solve the problems, the invention provides a brand new metallurgical route for extracting vanadium from vanadium-containing minerals of ferrovanadium spinel, oxalic acid is used as a leaching agent, iron powder is used as a reducing agent, the vanadium-containing minerals of the ferrovanadium spinel are used as raw materials, the three are mixed into slurry, the vanadium and iron in the ferrovanadium spinel are leached together under the condition of low temperature and pressurization, ferric iron soaked in the solution forms ferrous oxalate precipitation under the action of the iron powder and the action of reducing the iron powder, the separation of vanadium and iron in the leaching solution is realized, and clean vanadium-containing leaching solution is obtained.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a method for leaching vanadium in vanadium-containing minerals of vanadium-iron spinel by hydrothermal oxalic acid complexation, namely, the vanadium-iron spinel vanadium-containing minerals are used as raw materials, iron powder is used as a reducing agent, and oxalic acid solution is used as a leaching agent, the three are mixed into slurry, and the slurry is reacted under the condition of low temperature and pressurization; and (3) carrying out solid-liquid separation on the slurry obtained after the reaction to obtain a clean vanadium-containing leaching solution and a ferrous oxalate byproduct.
Compared with the existing method for extracting vanadium by high-pressure oxidation leaching, the method utilizes the strong complexation of oxalate ions to respectively form [ V (C) with vanadium and iron in ferrovanadium spinel2O4)3]3-，[Fe(C2O4)3]3-Entering a solution; formed [ Fe (C) ]2O4)3]3-And ferrous oxalate precipitation is generated with Fe powder, so that the leaching reaction is facilitated, and the leaching reaction rate is accelerated.
A method for leaching vanadium from vanadium-containing minerals of ferrovanadium spinel by hydrothermal oxalic acid complexation is characterized by comprising the following steps:
(1) mixing a mixture of vanadium-iron spinel vanadium-containing minerals and iron powder with an oxalic acid solution to form slurry, placing the slurry in a reaction kettle, and reacting under a pressurized condition;
(2) carrying out solid-liquid separation on the slurry obtained after the reaction in the step (1) to obtain vanadium-containing leaching solution and a filter cake, and drying the filter cake;
(3) and (3) washing the filter cake dried in the step (2) with deionized water, and obtaining a ferrous oxalate byproduct and leaching residue according to different densities of the ferrous oxalate and the leaching residue.
Further, the vanadium-iron spinel type vanadium-containing mineral in the step (1) has a particle size of less than 0.074 mm; the iron powder is used as a reducing agent; the oxalic acid solution is used as a leaching agent, and the mass concentration of the oxalic acid solution is 10-40%.
Further, the mass ratio of the iron powder to the vanadium-containing iron spinel in the step (1) is (2-5): 1.
further, the reaction temperature in the step (1) is 105-135 ℃, the reaction pressure is 1-5 Mpa, the reaction time is 15-120 min, and the reaction stirring speed is 500 rpm. The following reaction may occur during the reaction in step (1):
2Fe2VO4+8H2C2O4+Fe→5FeC2O4↓+V2(C2O4)3+8H2O
Fe+8H2C2O4→FeC2O4↓+H2
H2C2O4→CO+CO2+H2O
further, after the reaction in the step (2) is finished, the temperature of solid-liquid separation is 30-40 ℃.
Compared with the prior art, the technical scheme adopted by the invention has the following advantages:
1. the invention provides a method for leaching vanadium from vanadium-containing minerals of ferrovanadium spinel by hydrothermal oxalic acid complexation, which utilizes stronger complexation of oxalate ions to form [ V (C) with vanadium and iron in the ferrovanadium spinel respectively2O4)3]3-，[Fe(C2O4)3]3-Into solution.
2. Under the action of reduced iron powder, [ Fe (C)2O4)3]3-Ferrous oxalate precipitation is formed with iron powder, so that the separation of vanadium and iron is realized in the leaching process, the process steps are simplified, and the leaching reaction rate is accelerated.
3. The method requires low temperature, thereby reducing energy consumption; in addition, a ferrous oxalate byproduct is obtained and can be used as a raw material of lithium iron phosphate serving as a battery anode material.
4. Compared with the traditional pressure oxidation leaching process, the method does not need to introduce oxidizing gas, has simple equipment and low cost; the addition of an oxidant is not needed, and the leaching solution is clean; the reduced iron powder is non-toxic and harmless, and the tailings are simple to treat.
Drawings
FIG. 1 is a process diagram of vanadium extraction according to the present invention.
Fig. 2 is an XRD pattern of the obtained ferrous oxalate.
Detailed Description
In order to verify the feasibility of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. All such modifications made in accordance with the spirit of the present invention are intended to be included within the scope of the present invention.
Example 1:
vanadium trioxide and ferric oxide are used as initial raw materials, and roasting is carried out for 48 hours at 1200 ℃ in a reducing atmosphere to obtain pure Fe2VO4. Pure Fe will be obtained2VO4Grinding the materials to the particle size of below 0.074mm, weighing 0.2g of ball-milled vanadium iron spinel and 0.6g of reduced iron powder, mixing the materials together, putting the mixture into a reaction kettle, adding 20ml of oxalic acid solution with the mass fraction of 30% into the reaction kettle to form mixed slurry, carrying out leaching reaction at the reaction temperature of 135 ℃ for 120min and at the stirring speed of 500rpm, carrying out solid-liquid separation after the reaction is finished to obtain vanadium-containing leachate and a filter cake, washing the filter cake, and obtaining a ferrous oxalate byproduct and leaching residues according to an elutriation method. And finally measuring the concentration of vanadium in the leachate to be 2.2g/L by ICP-AES, and measuring the concentration of iron in the leachate to be 95 mg/L.
Example 2:
according to the method of Chinese patents CN106011456A and CN107641723A, stone coal is used as an initial raw material, ferric oxide is used as an additive, roasting is carried out at 1200 ℃ in a reducing atmosphere, and magnetic separation is carried out to obtain the vanadium-iron spinel type vanadium-containing concentrate. Ball-milling the obtained vanadium-iron spinel type vanadium-containing concentrate until the particle size is below 0.074mm, weighing 0.2g of the ball-milled vanadium concentrate and 0.6g of reduced iron powder, mixing the mixture together, putting the mixture into a reaction kettle, adding 20ml of oxalic acid solution with the mass fraction of 30% into the reaction kettle to form mixed slurry, carrying out leaching reaction at the reaction temperature of 135 ℃ for 120min and the stirring speed of 500rpm, carrying out solid-liquid separation after the reaction is finished to obtain vanadium-containing leachate and filter cake, washing the filter cake, and obtaining ferrous oxalate byproducts and leaching residues according to an elutriation method. Finally, the concentration of vanadium in the leachate is measured to be 637.5mg/L through ICP-AES, the leaching rate is 98 percent, and the concentration of iron in the leachate is measured to be 80.5 mg/L.
Example 3:
vanadium slag is used as an initial raw material, and the particle size of the vanadium slag is ball-milled to be less than 0.074 mm. Weighing 0.2g of ball-milled vanadium slag and 0.6g of reduced iron powder, mixing the weighed materials together, putting the mixture into a reaction kettle, adding 20ml of oxalic acid solution with the mass fraction of 30% into the reaction kettle to form mixed slurry, carrying out leaching reaction at the reaction temperature of 135 ℃, the time of 120min and the stirring speed of 500rpm, carrying out solid-liquid separation after the reaction is finished to obtain vanadium-containing leachate and filter cakes, washing the filter cakes, and obtaining ferrous oxalate byproducts and leaching residues according to an elutriation method. And finally, measuring the concentration of vanadium in the leachate to be 497mg/L and the leaching rate to be 89% by ICP-AES, and measuring the concentration of iron in the leachate to be 75 mg/L.
Claims (4)
1. A hydrothermal method for leaching vanadium from vanadium-containing minerals of ferrovanadium spinel by oxalic acid complexation is characterized in that the vanadium-containing minerals of ferrovanadium spinel are used as raw materials, iron powder is used as a reducing agent, oxalic acid solution is used as a leaching agent, the three are mixed into slurry, and the slurry is reacted under the condition of low temperature and pressurization; carrying out solid-liquid separation on the slurry obtained after the reaction to obtain clean vanadium-containing leaching solution and a ferrous oxalate byproduct; the method utilizes the strong complexation of oxalate ions to respectively form [ V (C) with vanadium and iron in the ferrovanadium spinel2O4)3]3-，[Fe(C2O4)3]3-Entering a solution; formed [ Fe (C) ]2O4)3]3-Ferrous oxalate precipitation is generated with Fe powder, so that the leaching reaction is facilitated, and the leaching reaction rate is accelerated; meanwhile, the separation of vanadium and iron is realized in the leaching process; the method comprises the following steps:
(1) mixing a mixture of vanadium-iron spinel vanadium-containing minerals and iron powder with an oxalic acid solution to form slurry, placing the slurry in a reaction kettle, and reacting under a pressurized condition;
(2) carrying out solid-liquid separation on the slurry obtained after the reaction in the step (1) to obtain vanadium-containing leaching solution and a filter cake, and drying the filter cake;
(3) washing the filter cake dried in the step (2) with deionized water, and obtaining a ferrous oxalate byproduct and leaching residue according to different densities of ferrous oxalate and the leaching residue;
the vanadium-iron spinel type vanadium-containing mineral in the step (1) has a particle size of less than 0.074 mm; the iron powder is used as a reducing agent; the oxalic acid solution is used as a leaching agent, and the mass concentration of the oxalic acid solution is 10-40%.
2. The hydrothermal oxalic acid complex leaching method for vanadium in vanadium-containing minerals of ferrovanadium spinel as claimed in claim 1, wherein the mass ratio of the iron powder to the vanadium-containing minerals of ferrovanadium spinel in the step (1) is (2-5): 1.
3. the hydrothermal oxalic acid complex leaching method for vanadium in vanadium-containing minerals of vanadium-containing ferrospinel as claimed in claim 1, wherein the reaction temperature in the step (1) is 105-135 ℃, the reaction pressure is 1-5 MPa, the reaction time is 15-120 min, and the reaction stirring speed is 500 rpm.
4. The hydrothermal method for oxalic acid complex leaching of vanadium from vanadium-containing minerals in vanadium-containing ferrospinel as claimed in claim 1, wherein the temperature of solid-liquid separation after the reaction in step (2) is 30-40 ℃.
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| CN110747358B (en) * | 2019-10-16 | 2020-10-16 | 北京科技大学 | Method for precipitating vanadium from vanadium-containing oxalic acid leaching mother liquor by hydrothermal method |
| CN111041200B (en) * | 2019-11-18 | 2021-02-19 | 北京科技大学 | Method for leaching vanadium, titanium and chromium from vanadium, titanium and chromium raw materials by organic acid through hydrothermal method |
| CN111519026B (en) * | 2020-04-30 | 2022-01-18 | 西安建筑科技大学 | Method for leaching secondary coated gold hematite |
| CN112342399B (en) * | 2020-10-16 | 2022-06-28 | 北京科技大学 | Method for simultaneously extracting vanadium, titanium and chromium from vanadium slag |
| CN112941327B (en) * | 2021-03-09 | 2022-06-10 | 河南理工大学 | Method for selectively separating vanadium and iron from red mud |
| CN113787085A (en) * | 2021-10-14 | 2021-12-14 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for extracting Fe, Zn and Pb from electric furnace dust removal ash and realizing high-value utilization |
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| CN105695738A (en) * | 2016-03-25 | 2016-06-22 | 武汉科技大学 | Deironing method for vanadium-bearing stone coal lixivium |
| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
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| CN102560115A (en) * | 2012-02-07 | 2012-07-11 | 九江佰盾钒技术贸易有限公司 | Method for extracting vanadium from stone coal vanadium mine extraction |
| CN105695738A (en) * | 2016-03-25 | 2016-06-22 | 武汉科技大学 | Deironing method for vanadium-bearing stone coal lixivium |
| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
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