Process for recovering metallic strontium from manganese leaching residue

Abstract

The application belongs to the technical field of non-ferrous metal smelting, and discloses a process method for recovering metallic strontium by using manganese leaching residue, which comprises the following steps: mixing the manganese leaching residue and water, and then feeding the mixture into a ball mill for wet ball milling to obtain manganese leaching residue slurry; adding the manganese leaching residue slurry into a mixed acid solution, and then performing heating and stirring reaction, filtering the strontium leaching slurry after the reaction to obtain leaching liquid and leaching residue; repeatedly leaching the leaching residue by using the mixed acid solution for 3-5 times, mixing the leaching liquid obtained in each time of leaching; cooling the mixed leaching liquid to a greenhouse, precipitating crystals, filtering to obtain the crystals and a crystallization mother liquor, and dissolving the crystals by adding water and heating to obtain a strontium precipitation precursor liquid; adding a carbonate into the strontium precipitation precursor liquid to obtain a strontium precipitation post-liquid and strontium carbonate precipitation, and performing filtration and drying on the strontium carbonate precipitation to obtain strontium carbonate products. The application adopts the method of first leaching and then strontium precipitation, has a short process flow, low cost, high strontium direct yield, and realizes efficient recovery and utilization of valuable metals in the manganese leaching residue.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of non-ferrous metal smelting, and relates to a process method for recovering metallic strontium by using manganese leaching residue, in particular to a process method for recovering metallic strontium by using manganese leaching residue after zinc electrowinning anode mud manganese leaching. BACKGROUND

[0002] Strontium carbonate is a white powder or particle without odor and taste, and is an extremely important strontium salt compound and an intermediate product for preparing many other important silver salt compounds. Due to its strong X-ray adsorption function and unique physical and chemical properties, it is widely used in the manufacture of industrial products such as color picture tube glass, cathode ray tube, electronic ceramics, magnetic materials, fuel, paint and the like, and is related to more than ten industries such as electronics, chemical industry, military industry, building materials, non-ferrous metals, aerospace, light industry, medicine and food. At present, the research on strontium extraction technology mainly focuses on extracting strontium from strontium minerals, and celestite (strontium sulfate) is the most important mineral for extracting strontium. Based on the differences in chemical properties such as solubility and reducibility of strontium compounds, chemical beneficiation method is the main method for extracting strontium, mainly including carbon thermal reduction method and double decomposition method.

[0003] Zinc anode mud is produced in the electrowinning process of the zinc hydrometallurgy system. In the electrowinning process, strontium carbonate is often added to the electrolytic cell to improve the quality of the cathode zinc. The strontium carbonate is first converted into strontium sulfate in the electrolyte, and then co-precipitates with lead sulfate. About 40-50 kg of anode mud is produced per ton of zinc. The anode mud contains strontium, lead, manganese, zinc, calcium and other valuable metals. Therefore, recovering metallic strontium from zinc anode mud can solve the problems of insufficient resource utilization and serious pollution caused by the accumulation of waste anode mud. However, due to the low strontium content in the zinc smelting system of the non-ferrous metal smelting industry, the existing strontium recovery process has the problems of high cost and difficulty in industrialization. Therefore, it is necessary to develop a low-cost process for recovering metallic strontium from low-grade strontium-containing materials. SUMMARY

[0004] The present application provides a process method for recovering metallic strontium by using manganese leaching residue, which has a short process flow, low cost, high strontium direct recovery rate and realizes efficient recovery and utilization of valuable metals in the manganese leaching residue.

[0005] To achieve the above-mentioned purposes, the following technical solutions are adopted in the present application:

[0006] The present application provides a process method for recovering metallic strontium by using manganese leaching residue, which has a short process flow, low cost, high strontium direct recovery rate and realizes efficient recovery and utilization of valuable metals in the manganese leaching residue.

[0007] a. Wet ball milling process: mix the manganese leaching residue and water in a ratio of 1:1-3 and then send them into a ball mill for wet ball milling to obtain manganese leaching residue slurry after ball milling;

[0008] b. leaching step: the manganese leaching residue slurry obtained in step a is added into a mixed acid solution for heating and stirring reaction, the leaching residue slurry after reaction is filtered to obtain leaching liquid and leaching residue;

[0009] c. repeated leaching: the leaching residue obtained in step b is repeatedly leached 3-5 times by using a mixed acid solution, and the leaching liquid obtained in each leaching is mixed;

[0010] d. cooling and dissolving: the mixed leaching liquid obtained in step c is cooled to a warm room to precipitate crystals, and the crystals and the crystallization mother liquor are obtained by filtration, the crystallization mother liquor is returned to the leaching step and mixed into the mixed acid solution, and the crystals are dissolved by adding water to obtain a strontium precipitation precursor liquid;

[0011] e. strontium precipitation step: a carbonate is added to the strontium precipitation precursor liquid obtained in step d to obtain a strontium precipitation post-liquid and strontium carbonate precipitate, the strontium carbonate precipitate is filtered and dried to obtain strontium carbonate product.

[0012] In one technical solution, in step a, when wet ball milling, the mass ratio of steel balls in the ball mill to manganese leaching residue is 10-15:1, the rotation speed of the ball mill is 200-240 rpm, and the ball milling time is 60-80 min.

[0013] In one technical solution, in step b, the mixed acid solution is prepared from oxalic acid and one of nitric acid, phosphoric acid or sulfuric acid, wherein the molar ratio of oxalic acid to strontium in the manganese leaching residue is 2-6:1, the concentration of nitric acid, phosphoric acid and sulfuric acid is 2 mol / L, and the molar ratio of nitric acid, phosphoric acid or sulfuric acid to oxalic acid is 2.5-5:1.

[0014] In one technical solution, in step d, the temperature of the heating and dissolving is 80-92℃.

[0015] In one technical solution, in step e, the carbonate is selected from one of sodium carbonate, sodium bicarbonate or ammonium carbonate.

[0016] The technical solution of the present application takes the manganese leaching residue after manganese leaching of zinc electrowinning anode slime as raw material, first the raw material is wet ball milled, under water bath heating conditions, the raw material is repeatedly leached by a mixed acid solution, and the leaching liquid and leaching residue are obtained after hot filtration; the leaching liquid is cooled to obtain crystals, and the crystallization mother liquor can be returned to the leaching step; the crystals are heated and dissolved, a carbonate is added for strontium precipitation, and the precipitate is filtered and dried to obtain strontium carbonate, the yield of strontium is 92.1-93.1%, and the purity of strontium carbonate product reaches more than 89%, which can meet the requirements of zinc electrowinning process.

[0017] Compared with the prior art, the beneficial effects of the present application are:

[0018] Compared to the costly conversion and acid leaching process (CN 116200610 A), this invention adopts a process of leaching followed by strontium precipitation, which has a shorter process flow, lower cost, higher direct strontium recovery rate, and does not introduce impurities that affect system stability, thus achieving efficient recovery and utilization of valuable metals in manganese leaching residue; in addition, the mixed acid solution can be recycled, saving costs and resulting in significant economic benefits. Attached Figure Description

[0019] Figure 1 This is a flowchart of the process for recovering metallic strontium using manganese leaching residue according to the present invention. Detailed Implementation

[0020] The following examples are used to illustrate the present invention, but are not intended to limit the scope of protection of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Unless otherwise specified, the experimental methods in the following examples are all conventional methods. The concentrations of nitric acid, phosphoric acid, and sulfuric acid used in the following examples are all 2 mol / L.

[0021] Example 1

[0022] like Figure 1 The flowchart shown illustrates the specific steps of the process for recovering metallic strontium using manganese leaching residue according to the present invention:

[0023] a. Wet ball milling process: Mix 100g of manganese leaching residue containing 4.4% strontium with an equal amount of water, and then feed the mixture into a ball mill for wet ball milling. The mass ratio of steel balls to manganese leaching residue inside the ball mill is 10:1. The ball mill speed is 200 rpm and the ball milling time is 60 min. After ball milling, manganese leaching residue slurry is obtained.

[0024] b. Leaching process: Prepare a mixed acid solution with a nitric acid to oxalic acid ratio of 3:1, with the oxalic acid being twice the molar amount of strontium in the manganese leaching residue. Add 400 ml of the mixed acid solution to the manganese leaching residue slurry and heat and stir at 92°C for 90 min. Filter the strontium leaching slurry after the reaction to obtain the leachate and leaching residue.

[0025] c. Repeated leaching: The leaching residue obtained in step b is leached again with mixed acid solution 5 times, and the leaching solutions obtained from each leaching are mixed.

[0026] d. Cooling and dissolving: Cool the mixed leachate obtained in step c to a warm temperature to precipitate crystals. Filter to obtain crystals and crystallization mother liquor. Return the crystallization mother liquor to the leaching process and mix it with the mixed acid solution to improve the utilization rate of the mixed acid solution. Add water to the crystals and heat to dissolve them to obtain the pre-precipitation solution for strontium.

[0027] e, strontium precipitation process: 7.85 g of ammonium carbonate is added to the strontium precipitation solution obtained in step d to obtain a strontium precipitation solution and strontium carbonate precipitate, and the strontium carbonate precipitate is filtered and dried to obtain 6.73 g of strontium carbonate product.

[0028] The strontium recovery rate of the manganese leaching residue in this example reaches 92.1%, and the strontium carbonate content of the obtained product reaches 90.91%.

[0029] Example 2

[0030] As shown in the flowchart, the specific steps of the process method for recovering metallic strontium from manganese leaching residue according to the present application are as follows: Figure 1

[0031] a, wet ball milling process: 100 g of manganese leaching residue containing 4.4% strontium is mixed with an equal amount of water, and then fed into a ball mill for wet ball milling. The mass ratio of steel balls to manganese leaching residue in the ball mill is 12:1, the rotation speed of the ball mill is 200 rpm, and the ball milling time is 60 min. After ball milling, a manganese leaching residue slurry is obtained.

[0032] b, leaching process: a mixed acid solution is prepared by mixing phosphoric acid and oxalic acid at a ratio of 4:1, and the amount of oxalic acid is 4 times the molar amount of strontium in the manganese leaching residue. 400 ml of the mixed acid solution is added to the manganese leaching residue slurry, and the mixture is heated and stirred at 92°C for 120 min. After the reaction, the strontium leaching slurry is filtered to obtain a leaching solution and a leaching residue.

[0033] c, repeated leaching: the leaching residue obtained in step b is repeatedly leached with the mixed acid solution for 5 times, and the leaching solutions obtained in each leaching are mixed.

[0034] d, cooling and dissolution: the mixed leaching solution obtained in step c is cooled to room temperature to precipitate crystals, which are filtered to obtain crystals and a crystallization mother liquor. The crystallization mother liquor is returned to the leaching process and mixed with the mixed acid solution to improve the utilization rate of the mixed acid solution. The crystals are dissolved by adding water to obtain a strontium precipitation solution.

[0035] e, strontium precipitation process: 7.85 g of ammonium carbonate is added to the strontium precipitation solution obtained in step d to obtain a strontium precipitation solution and strontium carbonate precipitate, and the strontium carbonate precipitate is filtered and dried to obtain 6.73 g of strontium carbonate product.

[0036] The strontium recovery rate of the manganese leaching residue in this example reaches 93.0%, and the strontium carbonate content of the obtained product reaches 89.01%.

[0037] Example 3

[0038] As shown in the flowchart, the specific steps of the process method for recovering metallic strontium from manganese leaching residue according to the present application are as follows: Figure 1

[0039] ​​a. Wet ball milling process: Mix 100g of manganese leaching residue containing 4.4% strontium with an equal amount of water, and then feed the mixture into a ball mill for wet ball milling. The mass ratio of steel balls to manganese leaching residue inside the ball mill is 15:1. The ball mill speed is 240 rpm and the ball milling time is 80 min. After ball milling, manganese leaching residue slurry is obtained.

[0040] b. Leaching process: Prepare a mixed acid solution with sulfuric acid and oxalic acid in a ratio of 5:1. The oxalic acid is 6 times the molar amount of strontium in the manganese leaching residue. Add 400 ml of the mixed acid solution to the manganese leaching residue slurry and heat and stir at 92°C for 120 min. Filter the strontium leaching slurry after the reaction to obtain the leachate and leaching residue.

[0041] c. Repeated leaching: The leaching residue obtained in step b is leached again with mixed acid solution 5 times, and the leaching solutions obtained from each leaching are mixed.

[0042] d. Cooling and dissolving: Cool the mixed leachate obtained in step c to a warm temperature to precipitate crystals. Filter to obtain crystals and crystallization mother liquor. Return the crystallization mother liquor to the leaching process and mix it with the mixed acid solution to improve the utilization rate of the mixed acid solution. Add water to the crystals and heat to dissolve them to obtain the pre-precipitation solution for strontium.

[0043] e. Strontium precipitation process: Add 8.04g of ammonium carbonate to the pre-strontium precipitation liquid obtained in step d to obtain the post-strontium precipitation liquid and strontium carbonate precipitate. Filter and dry the obtained strontium carbonate precipitate to obtain 7.63g of strontium carbonate product.

[0044] In this embodiment, the recovery rate of strontium from the manganese leaching residue reached 93.1%, and the strontium carbonate content in the obtained product reached 90.26%.

[0045] The embodiments described above are merely preferred embodiments of the present invention and are only used to explain the present invention. They are not intended to limit the scope of the present invention. For those skilled in the art, other implementation methods can be easily made by substitution or modification based on the technical content disclosed in this specification. Therefore, all changes and improvements made on the principle of the present invention should be included within the scope of the patent application of the present invention.

Claims

1. A process for the recovery of metallic strontium from manganese leach residue, characterized in that, The method comprises the following steps: a. A wet ball milling process: manganese leaching residue and water are mixed at a ratio of 1:1-3 and then fed into a ball mill for wet ball milling. After ball milling, a manganese leaching residue slurry is obtained; b. A leaching process: the manganese leaching residue slurry obtained in step a is added to a mixed acid solution for heating and stirring reaction. After reaction, the strontium leaching slurry is filtered to obtain a leaching solution and a leaching residue. The mixed acid solution is prepared from oxalic acid and one of nitric acid, phosphoric acid or sulfuric acid. The molar ratio of oxalic acid to strontium in the manganese leaching residue is 2-6:

1. The concentration of nitric acid, phosphoric acid and sulfuric acid is 2 mol / L. The molar ratio of nitric acid, phosphoric acid or sulfuric acid to oxalic acid is 2.5-5:1; c. Repeated leaching: the leaching residue obtained in step b is repeatedly leached with a mixed acid solution for 3-5 times. The leaching solutions obtained in each leaching are mixed; d. Cooling and dissolving: the mixed leaching solution obtained in step c is cooled to a warm room to precipitate crystals. The crystals are filtered to obtain a crystal and a crystallization mother liquor. The crystallization mother liquor is returned to the leaching process and mixed with the mixed acid solution. The crystals are dissolved by adding water and heating to obtain a strontium precipitation precursor solution; e. A strontium precipitation process: a carbonate is added to the strontium precipitation precursor solution obtained in step d to obtain a strontium precipitation solution and strontium carbonate precipitate. The strontium carbonate precipitate is filtered and dried to obtain a strontium carbonate product.

2. The process of claim 1, wherein, In step a, the mass ratio of steel balls in the ball mill to manganese leaching residue is 10-15:

1. The rotation speed of the ball mill is 200-240 rpm. The ball milling time is 60-80 min.

3. The process of claim 1, wherein, In step d, the temperature for dissolving by heating is 80-92℃.

4. The process of claim 1, wherein, In step e, the carbonate is selected from one of sodium carbonate, sodium bicarbonate or ammonium carbonate.

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