A method for preparing manganese vanadate from vanadium pentoxide
Manganese vanadate was prepared by high-temperature reaction and pH control of vanadium pentoxide with manganese carbonate or manganese oxide, which solved the problem that existing manganese vanadate could not meet the requirements of battery and optoelectronic material applications, and achieved the preparation of high-performance manganese vanadate.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- PANZHIHUA IRON & STEEL RES INST OF PANGANG GROUP
- Filing Date
- 2023-11-21
- Publication Date
- 2026-05-29
AI Technical Summary
Existing methods for preparing manganese vanadate are insufficient to meet practical needs, especially for applications in batteries and optoelectronic materials.
Manganese vanadate powder is prepared by mixing vanadium pentoxide with manganese carbonate or manganese oxide and reacting it at high temperature in an inert gas atmosphere. The pH value is controlled and the powder is treated with ammonia water to ensure its excellent electrochemical and optical properties.
The prepared manganese vanadate exhibits excellent electrochemical and optical properties, making it suitable for batteries and optoelectronic materials and meeting practical application requirements.
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Figure CN117735610B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of inorganic chemical technology, specifically relating to a method for preparing manganese vanadate from vanadium pentoxide. Background Technology
[0002] Vanadium, as an important microalloying element, is widely used in metallurgy, chemical industry, aerospace and other fields, providing crucial support for ensuring the quality of key national projects. In addition, vanadium also has important applications in aerospace, nuclear power, large-scale energy storage, and the chemical industry.
[0003] In recent years, Panzhihua Iron and Steel Group has conducted research on vanadium extraction technology through vanadium slag calcination roasting and has applied it industrially. Domestic scientists and engineers have also launched research in the field of vanadium slag calcination roasting. Calcination roasting mainly utilizes the roasted vanadium slag phase and oxygen from the air to extract vanadium. 3+ Fe 2+ MFe and other compounds are oxidized to higher valence V. 5+ Fe 3+ The process involves the combination of pentavalent vanadium with calcium and manganese to form vanadates such as calcium vanadate, manganese vanadate, and calcium manganese vanadate, which are soluble in sulfuric acid. Manganese vanadate is a key vanadate and one of the key products of vanadium slag roasting. The study of the physical and chemical properties of manganese vanadate requires manganese vanadate reagents. Manganese vanadate also has good electrochemical and optical properties and can be used in batteries and optoelectronic materials.
[0004] Patent application CN112142113A discloses a method for preparing spherical manganese ammonium vanadate particles. In this method, calcined vanadium leaching solution is used, the pH is adjusted to 1.8–2.2, ammonium chloride is added and stirred until homogeneous, and then dried using a spray dryer to obtain spherical manganese ammonium vanadate particles. Since manganese ammonium vanadate is a precursor to vanadium pentoxide, this method differs from the preparation method of manganese vanadate. Furthermore, there are fewer methods for preparing manganese vanadate, making it difficult to meet practical needs. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention proposes a method for preparing manganese vanadate using vanadium pentoxide, thereby solving the problem that existing manganese vanadate preparation methods cannot meet practical needs.
[0006] A method for preparing manganese vanadate from vanadium pentoxide includes the following steps:
[0007] (1) Mix vanadium pentoxide powder with manganese carbonate or manganese oxide reagent;
[0008] (2) The raw materials after uniform mixing are heated to 600-1000℃ in an inert gas atmosphere and kept at this temperature for 2-5 hours. Then they are cooled to room temperature and pulverized in an inert gas atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder.
[0009] (3) Prepare a slurry by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water at a solid-liquid ratio of 1:2-5 g / m; control the pH of the slurry to be 8-11.2 at 40-80℃ and the reaction time to be 30-120 min; wash the slurry multiple times with distilled water to obtain a water-containing manganese vanadate filter cake.
[0010] (4) The water-containing manganese vanadate filter cake is dried at 150-500℃ for 3-48 hours under inert gas protection to obtain manganese vanadate powder.
[0011] Furthermore, in step (1), the ratio of vanadium pentoxide to manganese carbonate / manganese oxide is controlled to be 0.4 to 4:1 mol / mol.
[0012] Furthermore, the quality standard of vanadium pentoxide in step (1) must meet the requirements of YB / T5304-2017.
[0013] Furthermore, the quality standard of manganese carbonate in step (1) must meet the requirements of the first-class product standard of HG / T4203-2011.
[0014] Furthermore, the inert gas in step (2) includes at least one of carbon dioxide, nitrogen, and argon.
[0015] Furthermore, in step (3), the pH is controlled between 8.0 and 11.2 when preparing ammonia water.
[0016] Furthermore, the inert gas in step (4) includes at least one of carbon dioxide, nitrogen, and argon.
[0017] Furthermore, step (2) also includes: sieving to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide powder to -120 mesh.
[0018] Furthermore, step (3) also includes: after the slurry has completed the reaction, it is allowed to stand, and then filtered using a vacuum filter. During the filtration process, it is washed five times with distilled water.
[0019] Furthermore, step (3) also includes: using a constant temperature water bath to control the temperature of the slurry at 40-80℃; and using a magnetic stirrer to stir during the reaction.
[0020] The beneficial effects of this invention are as follows: This invention proposes an original method for preparing manganese vanadate by roasting vanadium pentoxide. Manganese vanadate is obtained by mixing vanadium pentoxide powder with manganese carbonate (or manganese oxide) reagent. As a ternary vanadate, manganese vanadate has good electrochemical and optical properties and can be used in batteries and optoelectronic materials. It is of great significance for the study of vanadium slag leaching mechanism and subsequent product development. Attached Figure Description
[0021] Figure 1 A schematic flowchart of a method for preparing manganese vanadate from vanadium pentoxide provided by the present invention is shown. Detailed Implementation
[0022] It should be understood that the embodiments of the invention shown in the exemplary embodiments are merely illustrative. Although only a few embodiments have been described in detail in this invention, those skilled in the art will readily recognize that various modifications are possible without substantially departing from the teachings of the invention. Accordingly, all such modifications should be included within the scope of the invention. Other substitutions, modifications, variations, and deletions can be made to the design, operating conditions, and parameters of the following exemplary embodiments without departing from the spirit of the invention.
[0023] like Figure 1 As shown, this embodiment of the invention provides a method for preparing manganese vanadate from vanadium pentoxide, comprising the following steps:
[0024] (1) Mix vanadium pentoxide powder with manganese carbonate or manganese oxide reagent;
[0025] (2) The raw materials after uniform mixing are heated to 600-1000℃ in an inert gas atmosphere and kept at this temperature for 2-5 hours. Then they are cooled to room temperature and pulverized in an inert gas atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder.
[0026] (3) Prepare a slurry by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water at a solid-liquid ratio of 1:2-5 (unit g / ml); control the pH of the slurry at 8-11.2 at 40-80℃ and the reaction time at 30-120 min; wash the slurry multiple times with distilled water to obtain a water-containing manganese vanadate filter cake.
[0027] (4) The water-containing manganese vanadate filter cake is dried at 150-500℃ for 3-48 hours under inert gas protection to obtain manganese vanadate powder.
[0028] This invention proposes an original method for preparing manganese vanadate by calcining vanadium pentoxide. The method involves mixing vanadium pentoxide powder with manganese carbonate (or manganese oxide) to obtain manganese vanadate. As a ternary vanadate, manganese vanadate has excellent electrochemical and optical properties and can be used in batteries and optoelectronic materials. It is of great significance for the study of vanadium slag leaching mechanism and subsequent product development.
[0029] In some embodiments, in step (1), the ratio of vanadium pentoxide to manganese carbonate / manganese oxide is controlled to be 0.4 to 4:1 mol / mol.
[0030] In some embodiments, the quality standard of vanadium pentoxide in step (1) needs to meet the requirements of YB / T5304-2017 to ensure the reliability and stability of the product.
[0031] In some embodiments, the quality standard of manganese carbonate in step (1) needs to meet the requirements of the first-class product standard of HG / T4203-2011, which also ensures the reliability and stability of the product. Specifically, the technical requirements for first-class products include: the content of manganese carbonate (calculated as Mn) should not be less than 42.5%, the content of chloride (calculated as Cl) should not be higher than 0.01%, the content of sulfate (calculated as SO4) should not be higher than 0.6%, and the fineness (45pm sieve residue) should be determined through negotiation.
[0032] In some embodiments, the inert gas in step (2) includes at least one of carbon dioxide, nitrogen, and argon, and its function is to expel oxygen and moisture during the reaction process and prevent the reactants from being oxidized by oxygen in the air.
[0033] In some embodiments, the pH is controlled to be 8.0 to 11.2 when preparing ammonia water in step (3).
[0034] In some embodiments, the inert gas in step (4) includes at least one of carbon dioxide, nitrogen, and argon, and its function is to expel oxygen and moisture during the reaction process and prevent the reactants from being oxidized by oxygen in the air.
[0035] In some embodiments, step (2) further includes: sieving to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide powder to -120 mesh in order to improve reaction efficiency.
[0036] In some embodiments, step (3) further includes: after the slurry has completed the reaction, it is allowed to stand, and then filtered using a vacuum filter. During the filtration process, it is washed five times with distilled water.
[0037] In some embodiments, step (3) further includes: using a constant temperature water bath to control the temperature of the slurry at 40-80°C; and using a magnetic stirrer to stir during the reaction to further improve the reaction efficiency.
[0038] To further illustrate this, the following embodiments are provided for reference, but the scope of protection of this invention is not limited thereto:
[0039] Example 1:
[0040] Take 1.1 mol of vanadium pentoxide (purchased V2O599.5-P) and 1 mol of manganese carbonate, mix them evenly and put them into a crucible. Heat the crucible in a tube furnace under a nitrogen atmosphere to 800°C and maintain the temperature at 800°C for 4 hours. Then cool the material to room temperature and pulverize it under a nitrogen atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder. Sieve the powder to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide to -120 mesh.
[0041] A slurry was prepared by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water with a pH of approximately 11.0 at a solid-liquid ratio of 1:5 g / ml. The slurry temperature was controlled at 60±5℃ using a constant temperature water bath. A magnetic stirrer was used to stir the mixture at approximately 450 rpm. During this process, the pH was monitored using a pH meter. When the solution pH was less than 8, the pH was adjusted using ammonia water with a pH of 11.0 to control the slurry pH to ≥8. The reaction time was 60 min. After settling, the mixture was filtered using a vacuum filter. During the filtration process, 500 ml of distilled water with a pH of 6.5–7.5 was used to wash the mixture five times to obtain a manganese vanadate filter cake containing water.
[0042] The manganese vanadate filter cake was dried in a tube furnace under a nitrogen atmosphere, heated to 300°C, and maintained at 300°C for 6 hours. The material was then cooled to room temperature and packaged to obtain manganese vanadate reagent.
[0043] Example 2:
[0044] Take 1.1 mol of vanadium pentoxide (purchased V2O599.5-P) and 1 mol of manganese carbonate, mix them evenly and put them into a crucible. Heat the crucible in an argon atmosphere using a tube furnace to 800°C and maintain the temperature at 800°C for 4 hours. Then cool the material to room temperature and pulverize it in a nitrogen atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder. Sieve the powder to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide to -120 mesh.
[0045] A slurry was prepared by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water with a pH of approximately 11.2 at a solid-liquid ratio of 1:4 g / ml. The slurry temperature was controlled at 60±5℃ using a constant temperature water bath. A magnetic stirrer was used at a stirring speed of approximately 400 rpm. During the process, the pH was monitored using a pH meter. When the solution pH was less than 8, the pH was adjusted using ammonia water with a pH of 11.2 to control the slurry pH ≥ 8. The reaction time was 60 min. After standing, the mixture was filtered using a vacuum filter. During the filtration process, 500 ml of distilled water with a pH of approximately 7.0 was used to wash the mixture 5 times to obtain a manganese vanadate filter cake containing water.
[0046] The manganese vanadate filter cake was dried in a tube furnace under a nitrogen atmosphere, heated to 350°C, and maintained at 350°C for 6 hours. The material was then cooled to room temperature and packaged to obtain manganese vanadate reagent.
[0047] Example 3:
[0048] Take 1.1 mol of vanadium pentoxide (purchased V2O599.5-P) and 1 mol of manganese carbonate, mix them evenly and put them into a crucible. Heat the crucible in a tube furnace under a nitrogen atmosphere to 870°C and maintain the temperature at 870°C for 4 hours. Then cool the material to room temperature and pulverize it under a nitrogen atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder. Sieve the powder to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide to -120 mesh.
[0049] A slurry was prepared by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water with a pH of approximately 11.2 at a solid-liquid ratio of 1:4 g / ml. The slurry temperature was controlled at approximately 60℃ using a constant temperature water bath. A magnetic stirrer was used at a stirring speed of approximately 400 rpm. During the process, the pH was monitored using a pH meter. When the solution pH was less than 8, the pH was adjusted using ammonia water with a pH of 11.2 to control the slurry pH ≥ 8. The reaction time was 60 min. After standing, the mixture was filtered using a vacuum filter. During the filtration process, 500 ml of distilled water with a pH of approximately 7.0 was used to wash the mixture five times to obtain a manganese vanadate filter cake containing water.
[0050] The manganese vanadate filter cake was dried in a tube furnace under a nitrogen atmosphere, heated to 350°C, and maintained at 350°C for 6 hours. The material was then cooled to room temperature and packaged to obtain manganese vanadate reagent.
[0051] Example 4:
[0052] Take 1.1 mol of vanadium pentoxide (purchased V2O599.5-P) and 1 mol of manganese monoxide, mix them evenly and put them into a crucible. Heat the crucible in a tube furnace under a nitrogen atmosphere to 870°C and maintain the temperature at 870°C for 4 hours. Then cool the material to room temperature and pulverize it under a nitrogen atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder. Sieve the powder to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide to -120 mesh.
[0053] A slurry was prepared by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water with a pH of approximately 11.2 at a solid-liquid ratio of 1:4 g / ml. The slurry temperature was controlled at approximately 60℃ using a constant temperature water bath. A magnetic stirrer was used at a stirring speed of approximately 400 rpm. During the process, the pH was monitored using a pH meter. When the solution pH was less than 8, the pH was adjusted using ammonia water with a pH of 11.2 to control the slurry pH ≥ 8. The reaction time was 60 min. After standing, the mixture was filtered using a vacuum filter. During the filtration process, 500 ml of distilled water with a pH of approximately 7.0 was used to wash the mixture five times to obtain a manganese vanadate filter cake containing water.
[0054] The manganese vanadate filter cake was dried in a tube furnace under a nitrogen atmosphere, heated to 350°C, and maintained at 350°C for 6 hours. The material was then cooled to room temperature and packaged to obtain manganese vanadate reagent.
[0055] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Any modifications or equivalent substitutions made to the present invention without departing from the spirit and scope thereof should be covered within the protection scope of the claims of the present invention.
Claims
1. A method for preparing manganese vanadate from vanadium pentoxide, characterized in that, Includes the following steps: (1) Mix vanadium pentoxide powder with manganese carbonate or manganese oxide reagent, and control the ratio of vanadium pentoxide to manganese carbonate or manganese oxide to be 0.4~4:1 mol / mol; (2) The raw materials after uniform mixing are heated to 600~1000℃ in an inert gas atmosphere and kept at this temperature for 2~5 hours. Then they are cooled to room temperature and pulverized in an inert gas atmosphere to obtain a mixture of manganese vanadate and unreacted vanadium pentoxide powder. (3) Prepare a slurry by mixing manganese vanadate powder with unreacted vanadium pentoxide powder and ammonia water at a solid-liquid ratio of 1:2~5 g / ml; control the pH of the slurry at 8~11.2 at 40~80℃ and the reaction time at 30~120 min; wash the slurry multiple times with distilled water to obtain a water-containing manganese vanadate filter cake. (4) Dry the water-containing manganese vanadate filter cake at 150~500℃ for 3~48 hours under inert gas protection to obtain manganese vanadate powder.
2. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, In step (2), the inert gas includes at least one of carbon dioxide, nitrogen, and argon.
3. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, In step (3), the pH of the ammonia solution is controlled to be 8.0~11.
2.
4. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, The inert gas in step (4) includes at least one of carbon dioxide, nitrogen, and argon.
5. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, Step (2) further includes: sieving to control the particle size of the mixture of manganese vanadate and unreacted vanadium pentoxide powder to -120 mesh.
6. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, The step (3) also includes: after the slurry has completed the reaction, it is allowed to stand, and then it is filtered using a vacuum filter. During the filtration process, it is washed 5 times with distilled water.
7. The method for preparing manganese vanadate from vanadium pentoxide according to claim 1, characterized in that, The step (3) also includes: using a constant temperature water bath to control the temperature of the slurry at 40~80℃; and using a magnetic stirrer to stir during the reaction.