A method for leaching manganese carbonate ore using low-temperature ammonium sulfate in a wet process

Abstract

The present invention discloses a method for leaching manganese carbonate ore with low-temperature ammonium sulfate by wet process, comprising the following steps: S1: obtaining manganese ore powder to be leached, and mixing it with ammonium sulfate to obtain a mixture; S2: mixing the mixture with water, and then reacting 4-8h under heating and stirring conditions to obtain a reactant; S3: separating the reactant to obtain a leachate one and a solid one; S4: mixing the solid one with sulfuric acid, stirring continuously, continuously monitoring the pH value of the mixed solution during stirring, and maintaining the pH value of the mixed solution at 2-3 by dripping sulfuric acid; S5: when the pH value of the mixed solution is stably maintained at 2-3, stopping stirring, filtering to obtain a leachate two; S6: mixing the leachate one with the leachate two to obtain a total leachate. The present invention can efficiently leach manganese under low temperature conditions, and compared with traditional hydrometallurgy, the acid consumption is less, and the calcium leaching amount is also greatly reduced.

Description

Technical Field

[0001] The invention relates to the technical field of leaching ore, and in particular to a method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate. Background Art

[0002] Manganese (Mn) is a grayish white, hard, brittle, and shiny transition metal element. It is an important industrial raw material and is widely used in industrial fields such as steel, magnetic materials, and batteries. There are seven kinds of manganese minerals in nature, namely pyrolusite, psilomelane, manganese ore, ferromanganese ore, rochusite, rhodochrosite, and pyrolusite. They are important mineral raw materials for extracting manganese. In these minerals, manganese exists in the form of tetravalent and trivalent manganese oxides and divalent manganese carbonate. Among them, high-valent manganese oxides need to be reduced to divalent by various methods in order to achieve efficient extraction and recovery. At present, high-grade manganese ore in China is gradually becoming exhausted, but there are still abundant low-grade manganese ores that have not been fully utilized. Therefore, in order to meet the demand for manganese resources, an efficient technology should be developed to extract manganese from low-grade manganese carbonate ores.

[0003] At present, the methods for treating manganese ore mainly include direct acid leaching, pre-roasting leaching and bio-leaching. Among them, direct acid leaching is widely used in industry because of its simple process and easy operation. However, due to the large number of poor manganese ores and impurities in my country, the direct acid leaching method consumes a lot of acid and produces a large amount of acid leaching manganese ore tailings. The pre-roasting leaching method is mainly suitable for treating imported pyrolusite with high manganese content, and is not applicable to domestic manganese oxide ore with low grade and high impurity content. The bio-leaching method has problems such as low leaching efficiency, long time consumption, and strain preservation, and there are still certain difficulties in application. Therefore, it is very important to develop an efficient, green and environmentally friendly method to obtain manganese resources from low-grade manganese carbonate ore. Summary of the invention

[0004] In view of the above problems, the present invention aims to provide a method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate.

[0005] The technical solution of the present invention is as follows:

[0006] A method for leaching manganese carbonate ore with low-temperature ammonium sulfate by wet process, comprising the following steps:

[0007] S1: obtaining manganese ore powder to be leached, and mixing it with ammonium sulfate to obtain a mixture;

[0008] S2: mixing the mixture with water, and then reacting for 4-8 hours under heating and stirring conditions to obtain a reactant;

[0009] S3: separating the reactants to obtain a leachate and a solid;

[0010] S4: mixing the solid 1 with sulfuric acid, stirring continuously, continuously monitoring the pH value of the mixed solution during the stirring process, and maintaining the pH value of the mixed solution at 2-3 by dropping sulfuric acid;

[0011] S5: When the pH value of the mixed solution is stably maintained at 2-3, the stirring is stopped, and the mixture is filtered to obtain the second leaching solution;

[0012] S6: Mix the leachate 1 and the leachate 2 to obtain a total leachate.

[0013] Preferably, the more ammonium sulfate is used in step S1, the less sulfuric acid is used in step S4.

[0014] Preferably, in step S1, the mass ratio of manganese ore to ammonium sulfate is 1:0.35-5.

[0015] Preferably, in step S2, the water is deionized water.

[0016] Preferably, in step S2, the temperature of the heating condition is less than or equal to 100°C.

[0017] Preferably, the heating condition has a temperature of 60-98°C.

[0018] Preferably, the heating condition is at a temperature of 98°C.

[0019] Preferably, during the stirring in step S2 and step S4, the stirring rate adopted is 200-500 r / min.

[0020] The beneficial effects of the present invention are:

[0021] The present invention can efficiently leach manganese under low temperature conditions, and compared with traditional hydrometallurgy, the acid consumption is less and the calcium leaching amount is greatly reduced; in addition, the present invention does not require complex pretreatment equipment, occupies a relatively small area, and has low investment costs for manganese ore leaching projects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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 described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0023] Figure 1 The present invention is a schematic flow chart of the method for leaching manganese carbonate ore with low-temperature ammonium sulfate using the wet method. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with the accompanying drawings and embodiments. It should be noted that, in the absence of conflict, the embodiments in this application and the technical features in the embodiments can be combined with each other. It should be noted that, unless otherwise specified, all technical and scientific terms used in this application have the same meanings as those generally understood by those of ordinary skill in the art to which this application belongs. The words "including" or "comprising" and the like used in the disclosure of the present invention mean that the elements or objects appearing before the word cover the elements or objects listed after the word and their equivalents, without excluding other elements or objects.

[0025] like Figure 1 As shown, the present invention provides a method for leaching manganese carbonate ore using low-temperature ammonium sulfate in a wet process, comprising the following steps:

[0026] S1: obtaining manganese ore powder to be leached, and mixing it with ammonium sulfate to obtain a mixture.

[0027] S2: mixing the mixture with water, and then reacting for 4-8 hours under heating and stirring conditions to obtain a reactant.

[0028] S3: Separating the reactants to obtain a leachate and a solid.

[0029] S4: mixing the solid 1 with sulfuric acid, stirring continuously, continuously monitoring the pH value of the mixed solution during stirring, and maintaining the pH value of the mixed solution at 2-3 by dropping sulfuric acid.

[0030] S5: When the pH value of the mixed solution is stably maintained at 2-3, the stirring is stopped and the leaching solution 2 is obtained by filtering.

[0031] S6: Mix the leachate 1 and the leachate 2 to obtain a total leachate.

[0032] In a specific embodiment, the more ammonium sulfate is used in step S1, the less sulfuric acid is used in step S4. Optionally, the mass ratio of manganese ore to ammonium sulfate is 1:0.35-5.

[0033] In a specific embodiment, in step S2, the water is deionized water.

[0034] In a specific embodiment, the temperature of the heating condition is less than or equal to 100°C; optionally, the temperature of the heating condition is 60-98°C; optionally, the temperature of the heating condition is 98°C.

[0035] In a specific embodiment, during the stirring in step S2 and step S4, the stirring rate adopted is 200-500 r / min.

[0036] Example 1

[0037] A method for leaching manganese carbonate ore with low-temperature ammonium sulfate by wet process, comprising the following steps:

[0038] (1) obtaining a manganese ore powder to be leached, and mixing it with 35 g / L of ammonium sulfate at a mass ratio of 1:0.35 to obtain a mixture;

[0039] (2) mixing the mixture with 100 mL of water, and then reacting at 98° C. under stirring for 4-8 hours to obtain a reactant;

[0040] (3) separating the reactants to obtain a leachate and a solid;

[0041] (4) mixing the solid 1 with sulfuric acid, stirring continuously, continuously monitoring the pH value of the mixed solution during the stirring process, and maintaining the pH value of the mixed solution at 2-3 by adding sulfuric acid dropwise;

[0042] (5) When the pH value of the mixed solution is stably maintained at 2-3, stirring is stopped and filtering is performed to obtain a second leaching solution;

[0043] (6) Mixing the leachate 1 and the leachate 2 to obtain a total leachate.

[0044] Example 2

[0045] Different from Example 1, the ammonium sulfate used in step (1) of this embodiment is 52 g / L ammonium sulfate, and the mass ratio of manganese ore to ammonium sulfate is 1:0.52.

[0046] Example 3

[0047] Different from Example 1, the ammonium sulfate used in step (1) of this embodiment is 70 g / L ammonium sulfate, and the mass ratio of manganese ore to ammonium sulfate is 1:0.7.

[0048] Example 4

[0049] Different from Example 1, the ammonium sulfate used in step (1) of this embodiment is 173 g / L ammonium sulfate, and the mass ratio of manganese ore to ammonium sulfate is 1:1.73.

[0050] Example 5

[0051] Different from Example 1, the ammonium sulfate used in step (1) of this embodiment is 350 g / L ammonium sulfate, and the mass ratio of manganese ore to ammonium sulfate is 1:3.5.

[0052] Example 6

[0053] Different from Example 1, the ammonium sulfate used in step (1) of this embodiment is 500 g / L ammonium sulfate, and the mass ratio of manganese ore to ammonium sulfate is 1:5.

[0054] Example 7

[0055] Different from Example 1, the heating temperature in step (2) of this example is 60°C.

[0056] Example 8

[0057] Different from Example 1, the heating temperature in step (2) of this example is 70°C.

[0058] Example 9

[0059] Different from Example 1, the heating temperature in step (2) of this example is 80°C.

[0060] Example 10

[0061] Different from Example 1, the heating temperature in step (2) of this example is 90°C.

[0062] Comparative Example 1

[0063] Different from Example 1, the acid added in step (4) of this comparative example is hydrochloric acid.

[0064] Comparative Example 2

[0065] Different from Example 1, the acid added in step (4) of this comparative example is nitric acid.

[0066] The amount of sulfuric acid consumed by different ammonium sulfate concentrations and the corresponding leaching rate results are shown in Table 1:

[0067] Table 1 Effect of ammonium sulfate concentration on sulfuric acid consumption and leaching rate

[0068]

[0069] As can be seen from Table 1, the higher the amount of ammonium sulfate used in step (1) of the present invention, the less sulfuric acid is consumed in step (4). Compared with traditional hydrometallurgy, the acid consumption of the present invention can be reduced by more than 70%; the manganese leaching rate of the present invention is relatively high, all above 85%. When the ammonium sulfate concentration is 500 g / L and the mass ratio of manganese ore to ammonium sulfate is 1:5, the manganese leaching rate can reach 98.74% (it should be noted that the present invention has conducted multiple experiments under the same conditions. When the ammonium sulfate concentration is 500 g / L and the mass ratio of manganese ore to ammonium sulfate is 1:5, the manganese leaching rate fluctuates between 98% and 100%, and sometimes a manganese leaching rate of 100% can be achieved); the calcium leaching amount of the present invention is relatively small, below 35%. If a lower concentration of ammonium sulfate is used, the manganese leaching rate can be guaranteed to be above 85%, but the calcium leaching rate can be guaranteed to be below 15%.

[0070] The amount of sulfuric acid consumed at different heating temperatures and the corresponding leaching rate results are shown in Table 2:

[0071] Table 2 Effect of heating temperature on sulfuric acid consumption and leaching rate

[0072]

[0073] As can be seen from Table 2, the present invention can react at a temperature below 100° C., and the temperature is greatly reduced compared to the traditional ammonium sulfate baking method.

[0074] The results of the effects of different acids on the leaching rate in Example 6 and Comparative Examples 1-2 are shown in Table 3:

[0075] Table 3 Effect of acid on leaching rate

[0076]

[0077] It can be seen from Table 3 that the present invention can achieve a higher manganese leaching rate by using sulfuric acid.

[0078] The above description is only a representative embodiment of the present invention and does not limit the present invention in any form. Any technician familiar with the profession, without departing from the scope of the technical solution of the present invention, uses the above-disclosed technical contents to make some changes or modifications to the embodiments are equivalent embodiments of the present invention. However, any simple modification, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for leaching manganese carbonate ore with low-temperature ammonium sulfate by wet process, characterized in that: The following steps are involved: S1: obtaining manganese ore powder to be leached, and mixing it with ammonium sulfate to obtain a mixture; S2: mixing the mixture with water, and then reacting for 4-8 hours under heating and stirring conditions to obtain a reactant; the temperature of the heating conditions is less than or equal to 100° C.; S3: separating the reactants to obtain a leachate and a solid; S4: mixing the solid 1 with sulfuric acid, stirring continuously, continuously monitoring the pH value of the mixed solution during the stirring process, and maintaining the pH value of the mixed solution at 2-3 by dropping sulfuric acid; S5: When the pH value of the mixed solution is stably maintained at 2-3, the stirring is stopped, and the mixture is filtered to obtain the second leaching solution; S6: Mix the leachate 1 and the leachate 2 to obtain a total leachate.

2. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 1, characterized in that: The more ammonium sulfate is used in step S1, the less sulfuric acid is used in step S4.

3. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 2, characterized in that: In step S1, the mass ratio of manganese ore to ammonium sulfate is 1:0.35-5.

4. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 1, characterized in that: In step S2, the water is deionized water.

5. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 1, characterized in that: The temperature of the heating condition is 60-98°C.

6. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 5, characterized in that: The temperature of the heating condition was 98°C.

7. The method for leaching manganese carbonate ore with wet low-temperature ammonium sulfate according to claim 1, characterized in that: When stirring in step S2 and step S4, the stirring rate adopted is 200-500 r / min.

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