Method for extracting manganese from calcium-process vanadium extraction circulating water by using ammonium bicarbonate
By adding ammonium bicarbonate to the circulating water in the calcium-based vanadium extraction process in stages and heating and stirring to control the reaction conditions, the problem of manganese enrichment in the circulating water in the calcium-based titanium extraction process was solved. This method produces manganese carbonate, achieving efficient manganese recovery and the preparation of high-purity manganese carbonate, thus reducing resource waste and simplifying operating costs.
Patent Information
- Application Number
- CN202511839111.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-08
- Publication Date
- 2026-02-17
AI Technical Summary
In the calcium-based vanadium extraction process, manganese continuously accumulates in the circulating water without being effectively recovered, leading to resource waste.
Manganese carbonate was prepared by adding ammonium bicarbonate in portions to the circulating water used in the calcium vanadium extraction process, and controlling the reaction conditions by combining heating and stirring, and then extracting manganese ions by precipitation.
It enables a simple and rapid recovery of high-purity manganese carbonate products, reducing resource waste and lowering operating costs.
Smart Images
Figure CN121538469A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of calcium method vanadium extraction circulating water treatment, and particularly relates to a method for extracting manganese from calcium method vanadium extraction circulating water by using ammonium bicarbonate. BACKGROUND
[0002] Currently, the vanadium extraction processes in the industry mainly include sodium method vanadium extraction and calcium method vanadium extraction. The calcium method vanadium extraction mainly utilizes calcium and vanadium in raw materials to generate calcium vanadate through roasting, and then separates vanadium through acid leaching and vanadium precipitation processes. In the production process of the calcium method vanadium extraction, after the vanadium hydrolysis and precipitation separation, the supernatant of vanadium precipitation is obtained, the pH of the supernatant is about 1, and lime needs to be added for neutralization treatment and impurity removal. The remaining water is recycled for use.
[0003] Because the vanadium extraction raw material of the calcium method vanadium extraction process usually contains a certain amount of manganese, the manganese is retained in the supernatant of vanadium precipitation after the roasting, acid leaching and vanadium precipitation processes, and part of the manganese is precipitated after the lime neutralization, but part of the manganese is still retained in the circulating water. Through continuous circulation enrichment, the manganese in the circulating water of the calcium method vanadium extraction process is continuously enriched, and the concentration gradually increases. When the concentration reaches a certain value, excessive lime is added to remove the manganese. At present, there is no mature technology for recycling and utilizing the manganese in the industry. Most of the manganese elements enter the tailings, and the manganese as a valuable element is not effectively recycled and utilized, resulting in resource waste.
[0004] In the prior art, there are some researches on the recovery and extraction of manganese in the calcium method vanadium extraction circulating water system. For example, there are researches on the separation of organic solvent extraction, and there are researches on the removal of vanadium by ferrous sulfate, impurity removal, electrolytic recovery of metallic manganese, adjustment of pH, and precipitation of calcium with oxalate to produce manganese carbonate. SUMMARY
[0005] In view of the above prior art, the application provides a method for extracting manganese from calcium method vanadium extraction circulating water by using ammonium bicarbonate, which solves the problem that the manganese in the circulating water of the calcium method vanadium extraction process is continuously enriched but not recycled, and realizes simple and rapid recovery of manganese carbonate products meeting the standards.
[0006] In order to achieve the above purpose, the technical scheme adopted by the application is as follows: a method for extracting manganese from calcium method vanadium extraction circulating water by using ammonium bicarbonate is provided, which comprises the following steps: S1: taking calcium method vanadium extraction circulating water and detecting its composition; S2: weighing ammonium bicarbonate according to 3-3.8 times of the molar multiple of manganese ions in the calcium method vanadium extraction circulating water; S3: adding ammonium bicarbonate into the calcium method vanadium extraction circulating water in several times, the amount of each addition is not more than 16.7% of the total amount, the total number of ammonium bicarbonate addition is not less than 6 times, and the ammonium bicarbonate is fully stirred after each addition; S4: after the ammonium bicarbonate is completely added, heating and stirring are performed, the heating temperature is 45-60 DEG C, and the time is 70-120 min; S5: Filter the product obtained in step S4 and collect the precipitate; S6: The precipitate obtained from washing step S5; S7: Dry the product obtained in step S6 to obtain manganese carbonate product.
[0007] The beneficial effects of the above-mentioned technical solution in this invention are as follows: It detects the concentrations of manganese, calcium, and magnesium ions in the circulating water of the calcium-based vanadium extraction process, and determines the dosage of ammonium bicarbonate based on the amount of manganese ions, thus precisely controlling the addition amount. Ammonium bicarbonate must be added slowly in small amounts multiple times to the circulating water of the calcium-based vanadium extraction process. After each addition, the mixture must be thoroughly stirred until bubbles are generated and released before adding more ammonium bicarbonate to prevent a large number of bubbles from being generated at once and causing the solution to overflow. Heating after adding ammonium bicarbonate can accelerate and facilitate the reaction between ammonium bicarbonate and related ions, especially controlling the different degrees of reaction between carbonate and the three cations.
[0008] Based on the above technical solution, the present invention can be further improved as follows.
[0009] Furthermore, the circulating water for vanadium extraction via the calcium process is the supernatant obtained by filtration after vanadium precipitation in the industrial production of vanadium extraction via the calcium process.
[0010] Furthermore, the pH of the circulating water for vanadium extraction via the calcium method is 0.8~1.5, with a manganese ion concentration of 9~15 g / L, a calcium ion concentration of 0.4~0.7 g / L, and a magnesium ion concentration of 4.5~7 g / L.
[0011] Furthermore, the ammonium bicarbonate is of industrial grade purity.
[0012] Furthermore, the washing method in step S6 is as follows: add water to the precipitate, stir for 30 minutes, filter, and repeat twice.
[0013] Furthermore, the drying method in step S7 is: drying at a temperature of 80~120℃.
[0014] Furthermore, manganese carbonate products were prepared by extracting manganese from the circulating water of the calcium-based vanadium extraction process using ammonium bicarbonate.
[0015] Furthermore, the manganese carbonate product is in powder form, with a manganese content of 41.5-42.5%.
[0016] The beneficial effects of this invention are as follows: The principle of this invention utilizes the reaction of carbonates with acids. After adjusting the pH of the circulating water in the calcium-based vanadium extraction process to a suitable range, the precipitates obtained from the reactions of carbonates with Ca, Mg, and Mn have different solubility products. By using an appropriate amount of ammonium bicarbonate, the precipitation rates of the three precipitates are controlled, ensuring that most of the Mn precipitates while only a small amount of Ca and Mg precipitates, resulting in a high-purity manganese carbonate product. Therefore, the technical method provided by this invention, which directly uses ammonium bicarbonate as a pH adjuster and precipitant to extract and prepare manganese carbonate, features a single raw material, fewer steps, simple operation, low cost, and high product yield, enabling simple and rapid recovery of standard-compliant manganese carbonate products. Attached Figure Description
[0017] Figure 1 This is a schematic diagram of the process for extracting manganese from the circulating water of the calcium-based vanadium extraction method using ammonium bicarbonate. Detailed Implementation
[0018] The specific embodiments of the present invention will be described in detail below with reference to examples.
[0019] Example 1 A method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate is illustrated in the following flowchart. Figure 1 As shown, the specific steps include: S1: The circulating water for vanadium extraction by calcium process is the supernatant of vanadium precipitation produced during the vanadium extraction process. It was sampled and tested, and the pH was 1.0. The main components are shown in Table 1. Table 1. Main components of circulating water for vanadium extraction via calcium process (unit: g / L)
[0020] S2: Take 200 L of circulating water for vanadium extraction using the calcium method, and weigh out 9.48 kg of ammonium bicarbonate based on 3.4 times the molar ratio of manganese ions in it. S3: Add 9.48 kg of ammonium bicarbonate to the vanadium extraction circulating water in 6 portions, each time adding 1.58 kg. Before each addition, confirm that no more bubbles are generated in the liquid. S4: After adding ammonium bicarbonate, heat and stir at 55 ℃ for 90 min. S5: After the reaction in step S4 is completed, the obtained product is filtered by plate and frame filter press or belt filter press. The main elements of the filtrate are shown in Table 2. Table 2. Main elements in the filtrate (unit: g / L)
[0021] S6: After filtration, rinse the filter cloth twice with clean water; then transfer the precipitate into a mixing tank, add an appropriate amount of clean water, stir for 30 minutes, and then filter. Repeat twice. S7: The precipitate obtained in step S6 is dried at 100°C to obtain a powdered manganese carbonate product, which is found to contain 41.9% Mn.
[0022] Although specific embodiments of the present invention have been described in detail with reference to examples, they should not be construed as limiting the scope of protection of this patent. Various modifications and variations that can be made by those skilled in the art without inventive effort within the scope described in the claims are still within the scope of protection of this patent.
Claims
1. A method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate, characterized in that, Includes the following steps: S1: Take vanadium-extracting circulating water using the calcium extraction method and analyze its composition; S2: Weigh ammonium bicarbonate at 3 to 3.8 times the molar ratio of manganese ions in the circulating water for vanadium extraction using the calcium method; S3: Add the ammonium bicarbonate to the vanadium extraction circulating water in the calcium process in several portions, with each addition not exceeding 16.7% of the total amount, and the total number of additions of ammonium bicarbonate is not less than 6. Stir thoroughly after each addition of ammonium bicarbonate. S4: After the ammonium bicarbonate is completely added, heat and stir. The heating temperature is 45~60℃ and the time is 70~120 min. S5: Filter the product obtained in step S4 and collect the precipitate; S6: The precipitate obtained from washing step S5; S7: Dry the product obtained in step S6 to obtain manganese carbonate product.
2. The method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate according to claim 1, characterized in that: The circulating water for vanadium extraction via the calcium process is the supernatant obtained by filtration after vanadium precipitation in the industrial production of vanadium extraction via the calcium process.
3. The method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate according to claim 1, characterized in that: The pH of the circulating water for vanadium extraction via the calcium method is 0.8-1.5, with a manganese ion concentration of 9-15 g / L, a calcium ion concentration of 0.4-0.7 g / L, and a magnesium ion concentration of 4.5-7 g / L.
4. The method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate according to claim 1, characterized in that: The ammonium bicarbonate is of industrial grade purity.
5. The method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate according to claim 1, characterized in that: The washing method in step S6 is as follows: add water to the precipitate, stir for 30 minutes, filter, and repeat twice.
6. The method for extracting manganese from vanadium extraction circulating water using ammonium bicarbonate according to claim 1, characterized in that, The drying method in step S7 is: drying at a temperature of 80~120℃.
7. The manganese carbonate product prepared by the method of extracting manganese from the circulating water of the calcium vanadium extraction process according to any one of claims 1 to 6.
8. The manganese carbonate product according to claim 7, characterized in that: The manganese carbonate product is in powder form, and the manganese content is 41.5-42.5%.