Method for preparing high-purity vanadium pentoxide through composite extraction
By using a composite extraction agent and ammonium carbonate solution, the problems of high acidity stripping solution and high alkali consumption in the prior art are solved, and efficient extraction and purification of high-purity vanadium pentoxide are achieved, reducing production costs and improving product purity.
Patent Information
- Application Number
- CN202411888038.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-20
- Publication Date
- 2025-03-28
AI Technical Summary
In the prior art, when preparing high-purity vanadium pentoxide, the stripping solution has high acidity, high alkali consumption, high production cost, and high salt content in the vanadium mother liquor, which affects product purity and sewage treatment.
Compound extraction agents, including primary amines and hydroxime extractants, were used to extract with diluent sulfonated kerosene, followed by back-extraction using ammonium carbonate solution, adjust the pH and add a precipitant to obtain high-purity vanadium pentoxide through high-temperature oxygen-rich calcination.
It improves the extraction rate and purity of vanadium, reduces the consumption of alkali, reduces production costs, and improves the purity and added value of the product.
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Figure CN119706935A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of vanadium metallurgy, and in particular to a method for preparing high-purity vanadium pentoxide by composite extraction. Background Art
[0002] Vanadium has special chemical properties and multiple oxidation states. It is widely used in iron and steel metallurgy, chemical catalysts, battery materials, aerospace and other fields. It is an important strategic resource in my country. In recent years, with the continuous and rapid development of the new energy industry, all-vanadium liquid flow batteries have the characteristics of "instant charging" by replacing the electrolyte, safety and environmental protection, strong scalability, and long cycle life. In the new energy industry, it has become a new trend for large-scale energy storage. Most of the electrolytes of all-vanadium liquid flow batteries in my country are made of high-purity vanadium pentoxide (purity greater than 99.5%).
[0003] A lot of research has been done on the solvent extraction process of vanadium at home and abroad, and many effective methods for extracting and separating vanadium from solvents have been developed under different conditions. However, there are major problems with the existing technology process: since the stripping ability of dioctyl phosphate is not strong, strong acidic conditions are required in the stripping process, and the acidity of the stripping solution used is relatively high, about 1.5-2.5 mol / L sulfuric acid solution, and the small phase ratio (volume ratio of organic phase to aqueous phase) needs to be controlled to achieve a high stripping rate. The sulfuric acid concentration in the vanadium-rich solution obtained after stripping is relatively high, and a large amount of alkali is required to neutralize the sulfuric acid during the vanadium precipitation process, which wastes a large amount of acid and alkali, increasing the production cost of the process. At the same time, the salt content in the vanadium precipitation mother liquor is relatively high, which not only affects the purity of the product, but also increases a lot of costs for sewage treatment.
[0004] Therefore, there is a need in the prior art for improving the method for preparing high-purity vanadium pentoxide. Summary of the invention
[0005] In view of this, the purpose of the embodiment of the present invention is to propose a method for preparing high-purity vanadium pentoxide by composite extraction, using a composite extractant with strong extraction and stripping capabilities to extract acidic vanadium liquid, which can not only improve the extraction rate and purity of vanadium, thereby improving the yield and purity of vanadium pentoxide products, but also reduce the consumption of alkali and reduce production costs.
[0006] Based on the above purpose, the embodiment of the present invention provides a method for preparing high-purity vanadium pentoxide by composite extraction, comprising the following steps: S1: taking a composite extractant and a diluent sulfonated kerosene and mixing them evenly to prepare an organic phase, then adding an acidic vanadium solution, stirring and performing an extraction operation to obtain a vanadium-rich organic phase; S2 uses ammonium carbonate solution to strip the vanadium-rich organic phase to obtain a vanadium-rich solution; S3 adds sulfuric acid to the vanadium-rich solution and adjusts the pH of the solution, adds a precipitant to react to obtain a vanadium precipitate, washes the vanadium precipitate with dilute sulfuric acid, and filters and dries it; S4 high temperature oxygen-rich calcination of vanadium precipitation to produce vanadium pentoxide.
[0007] In some embodiments, in S1, the composite extractant includes: a primary amine extractant, a hydroxyoxime extractant, a hydroxyoxime extractant and the rest are modifiers.
[0008] In some embodiments, the composite extractant includes: 50% to 60% of primary amine N1923 extractant, 10% to 20% of hydroxyl oxime M5640 extractant, 10% to 20% of hydroxyl oxime Lix984 extractant, and the rest is a modifier, which is one or more of the alkyl alcohols having a carbon number between 8 and 13.
[0009] In some embodiments, in S1, the total vanadium content of the acidic vanadium liquid is 1-50 g / L, Mn≤12 g / L, P≤0.05 g / L, Si≤0.5 g / L, and Fe≤0.1 g / L.
[0010] In some embodiments, in S1, the mixing ratio of the composite extractant and the diluent sulfonated kerosene is 1:4-1:5, the volume ratio of the organic phase to the aqueous phase during extraction is (1-1.5):1, and 2-6 levels of countercurrent extraction are used.
[0011] In some embodiments, in S2, the volume ratio of the vanadium-rich organic phase to the ammonium carbonate aqueous solution is 2-3:1, and the stripping is carried out at a temperature of 25-40°C for 10-20 minutes, and the vanadium-rich aqueous stripping solution is obtained after standing for phase separation.
[0012] In some embodiments, the mass percentage of the aqueous ammonium carbonate solution is 40 g / L to 100 g / L.
[0013] In some embodiments, in S3, the precipitant is a mixture of hexamethylenetetramine and ethylenediamine in a mass ratio of 1:1, and the amount of the precipitant is 0.2-0.3 of the mass of vanadium in the vanadium-rich solution.
[0014] In some embodiments, in S3, the pH of the solution is adjusted to 2-2.3, the solution temperature during the reaction is controlled to be 65-80° C., and the reaction time is 30-60 min.
[0015] In some embodiments, in S4, the calcination temperature of the high-temperature oxygen-enriched calcination is 500-550°C.
[0016] The present invention has at least the following beneficial technical effects: 1. The composite extractant obtained by compounding primary amine organic matter and hydroxime organic matter has not only strong extraction ability, but also strong stripping ability, and can strip vanadium under relatively low alkaline conditions, and the modifier can effectively prevent emulsification or the formation of a third phase during extraction or stripping; the composite extractant can enrich vanadium-containing solutions with relatively low concentrations, and by improving the extraction and stripping rates of vanadium, the vanadium extraction rate can be effectively improved, and the vanadium extraction rate can reach more than 97%; 2. The present invention adopts an extraction method to directly extract vanadium from acidic vanadium liquid, so that impurities are removed to the greatest extent and high-purity vanadium products are prepared. The purity of high-purity vanadium can reach more than 99.8%, which can increase the added value of the product and have significant economic benefits; 3. The present invention has low requirements on equipment and is simple to operate. The key extraction reagent has good thermal stability and is insensitive to acid and alkali. The regeneration and circulation methods are simple and easy to realize industrialization. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.
[0018] Figure 1 This is a schematic diagram of an embodiment of the method for preparing high-purity vanadium pentoxide by composite extraction provided by the present invention. DETAILED DESCRIPTION
[0019] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the embodiments of the present invention are further described in detail below in combination with specific embodiments and with reference to the accompanying drawings.
[0020] The terms "including" and "having" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions; the terms "first", "second", etc. in the specification and claims of the present invention or the above-mentioned drawings are used to distinguish different objects rather than to describe a specific order. "Multiple" means two or more, unless otherwise clearly and specifically defined.
[0021] In addition, reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present invention. The appearance of the phrase in various places in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.
[0022] like Figure 1 The present invention provides a method for preparing high-purity vanadium pentoxide by composite extraction, which comprises the following steps: S1: taking a composite extractant and a diluent sulfonated kerosene and mixing them evenly to prepare an organic phase, then adding an acidic vanadium solution, stirring and performing an extraction operation to obtain a vanadium-rich organic phase; S2 uses ammonium carbonate solution to strip the vanadium-rich organic phase to obtain a vanadium-rich solution; S3 adds sulfuric acid to the vanadium-rich solution and adjusts the pH of the solution, adds a precipitant to react to obtain a vanadium precipitate, washes the vanadium precipitate with dilute sulfuric acid, and filters and dries it; S4 high temperature oxygen-rich calcination of vanadium precipitation to produce vanadium pentoxide.
[0023] Further, in S1, the composite extractant includes: a primary amine extractant, a hydroxime extractant, a hydroxime extractant, and the rest is a modifier. Preferably, the composite extractant includes: 50% to 60% of a primary amine N1923 extractant, 10% to 20% of a hydroxime M5640 extractant, 10% to 20% of a hydroxime Lix984 extractant, and the rest is a modifier, and the modifier is one or more of the alkyl alcohols having a carbon number between 8 and 13.
[0024] Furthermore, in S1, the total vanadium content of the acidic vanadium solution is 1-50 g / L, Mn≤12 g / L, P≤0.05 g / L, Si≤0.5 g / L, and Fe≤0.1 g / L. The mixing ratio of the composite extractant and the diluent sulfonated kerosene is 1:4-1:5, the volume ratio of the organic phase to the aqueous phase during extraction is (1-1.5):1, and 2-6 levels of countercurrent extraction are used.
[0025] Further, in S2, the volume ratio of the vanadium-rich organic phase to the ammonium carbonate aqueous solution is 2-3:1, and the stripping is carried out at a temperature of 25-40°C for 10-20 minutes, and the vanadium-rich aqueous solution is obtained after standing for phase separation. In some embodiments, the mass percentage of the ammonium carbonate aqueous solution is 40g / L-100g / L.
[0026] Further, in S3, the precipitant is a mixture of hexamethylenetetramine and ethylenediamine in a mass ratio of 1:1, and the amount of the precipitant is 0.2-0.3 of the mass of vanadium in the vanadium-rich solution. The pH of the solution is adjusted to 2-2.3, the solution temperature during the reaction is controlled to 65-80°C, and the reaction time is 30-60 minutes.
[0027] Furthermore, in S4, the calcination temperature of the high-temperature oxygen-enriched calcination is 500-550°C.
[0028] The present invention will be further explained below in conjunction with specific embodiments.
[0029] S1: taking a composite extractant and a diluent sulfonated kerosene and mixing them evenly to prepare an organic phase, then adding an acidic vanadium solution, stirring and performing an extraction operation to obtain a vanadium-rich organic phase; Preferably, the composite extractant in S1 is a mixture of primary amine N1923 (R1R2CHNH2, R1+R2=C18~22), hydroxyoxime M5640, hydroxyoxime Lix984 and a modifier, and heated to 65°C-90°C, stirred for 40min-80min to obtain a composite extractant, and the composite extractant is used to extract the acidic vanadium solution to obtain a vanadium-containing loaded organic phase; by volume fraction, the composite extractant The primary amine N1923 extractant accounts for 50%-60%, the hydroxyoxime M5640 extractant is 10%-20%, the hydroxyoxime Lix984 extractant is 10%-20%, and the rest is a modifier, which is one or more of the alkyl alcohols with a carbon number between 8 and 13. The mixing ratio of the composite extractant and the diluent sulfonated kerosene is 1:4~1:5. During extraction, the volume ratio of the organic phase to the aqueous phase is 1-1.5:1, and 2-6 levels of countercurrent extraction are adopted.
[0030] S2 uses ammonium carbonate solution to strip the vanadium-rich organic phase to obtain a vanadium-rich solution; Preferably, an ammonium carbonate aqueous solution with a solution mass percentage of 40g / L~100g / L is added to the vanadium-rich organic phase in S2, the volume ratio of the vanadium-rich organic phase to the ammonium carbonate aqueous solution is 2~3:1, the stripping time is 10~20min at 25~40°C, and the vanadium-rich aqueous stripping solution is obtained after standing for phase separation.
[0031] S3 adds sulfuric acid to the vanadium-rich solution and adjusts the pH of the solution, adds a precipitant to react to obtain a vanadium precipitate, washes the vanadium precipitate with dilute sulfuric acid, and filters and dries it; Preferably, the precipitant in S3 is a mixture of hexamethylenetetramine and ethylenediamine in a mass ratio of 1:1, and the amount used is 0.2-0.3 of the mass of vanadium in the solution.
[0032] S4 high temperature oxygen-rich calcination of vanadium precipitation to produce vanadium pentoxide.
[0033] Example 1 The concentrations of the components in the acidic vanadium solution in this embodiment are shown in Table 1: Table 1 Concentration of components in acidic vanadium solution
[0034] The ore dressing process of this embodiment is as follows Figure 1 As shown, the specific steps are as follows: (1) Primary amine N1923, hydroxime M5640, hydroxime Lix984 and undecanol were mixed in a volume ratio of 3:1:1 (750 mL, 250 mL, 250 mL); heated to 70°C, stirred for 50 min to obtain a composite extractant, and then 5 L of sulfonated kerosene was added for dilution, and then the diluted composite extractant was used to extract the acidic vanadium solution (5 L), and a vanadium-rich organic phase was obtained by a three-stage countercurrent extraction method; (2) adding 3 L of an ammonium carbonate aqueous solution with a mass percentage of 50 g / L to the vanadium-rich organic phase, stripping for 15 min at 30° C., and allowing to stand for phase separation to obtain a vanadium-rich aqueous stripping solution; (3) Mix 12 g of hexamethylenetetramine and 13 g of ethylenediamine and add them to the vanadium-rich aqueous reverse extract. Control the solution temperature at 70°C and react for 45 minutes to obtain a precipitate. Wash the precipitate twice with dilute sulfuric acid, filter and dry. (4) Vanadium pentoxide is obtained by calcining vanadium precipitate in oxygen-rich water at 550°C.
[0035] In this example, the V2O5 content is 99.9%, the contents of the main impurities Mn, Ti, and Fe are all less than 0.001%, and the vanadium recovery rate is 98.1%.
[0036] Example 2 The concentrations of the components in the acidic vanadium solution in this embodiment are shown in Table 2: Table 2 Concentration of components in acidic vanadium solution
[0037] The ore dressing process of this embodiment is as follows Figure 1 As shown, the specific steps are as follows: (1) Primary amine N1923, hydroxime M5640, hydroxime Lix984 and undecanol were mixed in a volume ratio of 3:1:1 (750 mL, 250 mL, 250 mL); heated to 70°C, stirred for 50 min to obtain a composite extractant, and then 5 L of sulfonated kerosene was added for dilution, and then the diluted composite extractant was used to extract the acidic vanadium solution (5 L), and a vanadium-rich organic phase was obtained by a three-stage countercurrent extraction method; (2) adding 2.7 L of an ammonium carbonate aqueous solution with a mass percentage of 50 g / L to the vanadium-rich organic phase, stripping for 15 min at 30 °C, and allowing to stand for phase separation to obtain a vanadium-rich aqueous stripping solution; (3) Mix 11 g of hexamethylenetetramine and 14 g of ethylenediamine and add them to the vanadium-rich aqueous reverse extract. Control the solution temperature at 70°C and react for 45 minutes to obtain a precipitate. Wash the precipitate twice with dilute sulfuric acid, filter and dry. (4) Vanadium pentoxide is obtained by calcining vanadium precipitate in oxygen-rich water at 550°C.
[0038] In this example, the V2O5 content is 99.8%, the contents of the main impurities Mn, Ti, and Fe are all less than 0.001%, and the vanadium recovery rate is 97.9%.
[0039] Example 3 The concentrations of the components in the acidic vanadium solution in this embodiment are shown in Table 3: Table 3 Concentration of components in acidic vanadium solution
[0040] The ore dressing process of this embodiment is as follows Figure 1 As shown, the specific steps are as follows: (1) Primary amine N1923, hydroxime M5640, hydroxime Lix984 and undecanol were mixed in a volume ratio of 3:1:1 (750 mL, 250 mL, 250 mL); heated to 70°C, stirred for 50 min to obtain a composite extractant, and then 5 L of sulfonated kerosene was added for dilution, and then the diluted composite extractant was used to extract the acidic vanadium solution (5 L), and a vanadium-rich organic phase was obtained by a three-stage countercurrent extraction method; (2) adding 2.7 L of an ammonium carbonate aqueous solution with a mass percentage of 50 g / L to the vanadium-rich organic phase, stripping for 15 min at 30 °C, and allowing to stand for phase separation to obtain a vanadium-rich aqueous stripping solution; (3) Mix 11 g of hexamethylenetetramine and 14 g of ethylenediamine and add them to the vanadium-rich aqueous reverse extract. Control the solution temperature at 70°C and react for 45 minutes to obtain a precipitate. Wash the precipitate twice with dilute sulfuric acid, filter and dry. (4) Vanadium pentoxide is obtained by calcining vanadium precipitate in oxygen-rich water at 550°C.
[0041] In this example, the V2O5 content is 99.9%, the contents of the main impurities Mn, Ti, and Fe are all less than 0.001%, and the vanadium recovery rate is 98.2%.
[0042] Compared with the prior art, the beneficial effects of the present invention are: 1. The composite extractant obtained by compounding primary amine organic matter and hydroxyoxime organic matter not only has strong extraction ability, but also has strong stripping ability, and can strip vanadium under relatively low alkaline conditions, and the modifier can effectively prevent emulsification or the formation of a third phase during extraction or stripping; the composite extractant can enrich vanadium-containing solutions with relatively low concentrations, and by improving the extraction and stripping rates of vanadium, the vanadium extraction rate can be effectively improved, and the vanadium extraction rate can reach more than 97%.
[0043] 2. The present invention adopts an extraction method to directly extract vanadium from acidic vanadium liquid, so that impurities are removed to the greatest extent and high-purity vanadium products are prepared. The purity of the high-purity vanadium can reach more than 99.8%, which can increase the added value of the product and has significant economic benefits.
[0044] 3. The present invention has low requirements on equipment and is simple to operate. The key extraction reagent has good thermal stability and is insensitive to acid and alkali. The regeneration and circulation methods are simple and easy to realize industrialization.
[0045] The above are exemplary embodiments disclosed in the present invention, but it should be noted that various changes and modifications may be made without departing from the scope disclosed in the embodiments of the present invention as defined in the claims. The functions, steps and / or actions of the method claims according to the disclosed embodiments described herein do not need to be performed in any particular order. In addition, although the elements disclosed in the embodiments of the present invention may be described or required in individual form, they may also be understood as multiple unless explicitly limited to the singular.
[0046] It should be understood that, as used herein, the singular forms "a", "an" are intended to include the plural forms as well, unless the context clearly supports an exception. It should also be understood that, as used herein, "and / or" refers to any and all possible combinations including one or more of the associated listed items.
[0047] The serial numbers of the embodiments disclosed in the above embodiments of the present invention are only for description and do not represent the advantages or disadvantages of the embodiments.
[0048] A person skilled in the art should understand that the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of the disclosure of the embodiments of the present invention (including the claims) is limited to these examples; under the concept of the embodiments of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and there are many other changes in different aspects of the above embodiments of the present invention, which are not provided in detail for the sake of simplicity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the embodiments of the present invention should be included in the protection scope of the embodiments of the present invention.
Claims
1. A method for preparing high-purity vanadium pentoxide by composite extraction, characterized in that: include: S1: taking a composite extractant and a diluent sulfonated kerosene and mixing them evenly to prepare an organic phase, then adding an acidic vanadium solution, stirring and performing an extraction operation to obtain a vanadium-rich organic phase; S2. stripping the vanadium-rich organic phase with an ammonium carbonate solution to obtain a vanadium-rich solution; S3 adds sulfuric acid to the vanadium-rich solution and adjusts the pH of the solution, adds a precipitant to react to obtain a vanadium precipitate, washes the vanadium precipitate with dilute sulfuric acid, and filters and dries it; S4 high temperature oxygen-rich calcination of vanadium precipitation to produce vanadium pentoxide.
2. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S1, the composite extractant includes: a primary amine extractant, a hydroxyoxime extractant, a hydroxyoxime extractant and the rest are modifiers.
3. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 2, characterized in that: The composite extractant comprises: 50% to 60% of primary amine N1923 extractant, 10% to 20% of hydroxyl oxime M5640 extractant, 10% to 20% of hydroxyl oxime Lix984 extractant, and the rest is a modifier, which is one or more of alkyl alcohols with a carbon number between 8 and 13.
4. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S1, the total vanadium content of the acidic vanadium solution is 1-50 g / L, Mn≤12 g / L, P≤0.05 g / L, Si≤0.5 g / L, and Fe≤0.1 g / L.
5. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S1, the mixing ratio of the composite extractant and the diluent sulfonated kerosene is 1:4-1:5, the volume ratio of the organic phase to the aqueous phase during extraction is (1-1.5):1, and 2-6 levels of countercurrent extraction are used.
6. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S2, the volume ratio of the vanadium-rich organic phase to the ammonium carbonate aqueous solution is 2-3:1, and the stripping is carried out at a temperature of 25-40°C for 10-20 minutes, and after standing for phase separation, a vanadium-rich aqueous stripping solution is obtained.
7. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 6, characterized in that: The mass percentage of the ammonium carbonate aqueous solution is 40 g / L to 100 g / L.
8. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S3, the precipitant is a mixture of hexamethylenetetramine and ethylenediamine in a mass ratio of 1:1, and the amount of the precipitant is 0.2-0.3 of the mass of vanadium in the vanadium-rich solution.
9. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S3, the pH of the solution is adjusted to 2-2.3, the solution temperature during the reaction is controlled to be 65-80°C, and the reaction time is 30-60 min.
10. The method for preparing high-purity vanadium pentoxide by composite extraction according to claim 1, characterized in that: In S4, the calcination temperature of the high-temperature oxygen-enriched calcination is 500-550°C.