Method for recovering manganese from post-MHP-precipitation solution

Abstract

The present application discloses a method for recovering manganese from a post-MHP-precipitation solution. The method comprises the following steps: (1) subjecting manganese in a post-MHP-precipitation solution to resin adsorption, followed by elution to obtain a manganese-rich solution; (2) extracting the manganese-rich solution to obtain a manganese-rich organic phase and a raffinate, wherein the extractant used in the extraction treatment is one or more of HBL110 and HBL116; and (3) stripping the manganese-rich organic phase to obtain a battery-grade stripped manganese solution, which can be directly compounded and used for synthesizing a ternary NCM battery material. In the present application, manganese is recovered from the filtrate in the stage of preparing MHP from laterite nickel ore via resin adsorption combined with a continuous extraction process. The resulting manganese solution can meet the standards for battery-grade manganese solutions, which not only reduces resource waste and environmental pollution caused by manganese slag landfill, but also alleviates the shortage of manganese ore resources in China.

Description

Method for recovering manganese from MHP post-precipitation liquid TECHNICAL FIELD

[0001] The application belongs to the technical field of laterite nickel ore metallurgy, and particularly relates to a method for recovering manganese from MHP post-precipitation liquid. BACKGROUND

[0002] The current processing method of laterite nickel ore is mainly a hydrometallurgical process. After acid leaching, cyclic leaching, CDD washing, neutralization iron and aluminum removal, and nickel-cobalt precipitation, nickel-cobalt hydroxide (MHP) is obtained. At present, the target elements recovered in the field of hydrometallurgy are nickel and cobalt. During the preparation of MHP, about 80% of manganese in the waste liquid is precipitated by alkali and then treated as waste slag for landfill, and about 0.3-0.65 tons of manganese slag is generated per ton of MHP produced, which not only causes waste of manganese resources, but also pollutes the environment.

[0003] SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the application is to provide a method for recovering manganese from MHP post-precipitation liquid, which solves the problems of environmental pollution and waste of manganese resources in the current laterite nickel ore metallurgical process.

[0005] To achieve the above-mentioned purpose, the application realizes the following technical scheme:

[0006] The application provides a method for recovering manganese from MHP post-precipitation liquid, comprising the following steps:

[0007] (1) Resin adsorption of manganese in MHP post-precipitation liquid, and obtaining a manganese-rich solution after elution;

[0008] (2) Extracting the manganese-rich solution to obtain a manganese-rich organic phase and a raffinate; the extractant used in the extraction treatment is one or more of HBL110 and HBL116;

[0009] (3) Stripping the manganese-rich organic phase to obtain a battery-grade manganese solution.

[0010] Preferably, in step (1), the resin used in the resin adsorption process is one or more of LSC-495, HP606, D854, HP4080, and CH27.

[0011] Preferably, in step (1), the resin adsorption process comprises:

[0012] Manganese adsorption: passing the MHP post-precipitation liquid through the column at a flow rate of 0.5-6 BV / h for adsorption;

[0013] Resin elution: eluting the manganese-adsorbed resin with a desorption solution to obtain a manganese-rich solution.

[0014] Preferably, the stripping solution comprises one or more of nitric acid, sulfuric acid, and hydrochloric acid solution; the concentration of the stripping solution is 1-25%, and the flow rate of the stripping solution is 0.5-5 BV / h.

[0015] Preferably, in step (2), the extraction treatment comprises:

[0016] The extractant is mixed with the diluent to obtain an extraction organic phase;

[0017] The extraction organic phase is mixed with a manganese-rich solution to perform manganese extraction, to obtain a loaded organic phase and a raffinate;

[0018] The loaded organic phase is washed with a washing solution to obtain a manganese-rich organic phase and washing water.

[0019] Preferably, the diluent comprises one or more of sulfonated kerosene, aviation kerosene, and No. 260 solvent oil, and the dilution rate of the extractant is 5-50%.

[0020] Preferably, the volume ratio of the extraction organic phase to the manganese-rich solution is 1:0.1-10, and the extraction stage number is 1-15.

[0021] Preferably, the volume ratio of the loaded organic phase to the washing solution is 1-40:1, the washing stage number is 1-15, and the washing solution comprises one or more of nitric acid, sulfuric acid, and hydrochloric acid solution.

[0022] Preferably, in step (3), the stripping treatment step comprises: mixing a stripping solution with the manganese-rich organic phase to perform stripping, to obtain a manganese stripping solution and a stripped organic phase; the concentration of the stripping solution is 0.5-3.0 mol / L, the volume ratio of the manganese-rich organic phase to the stripping solution is 5-40:1, and the stripping stage number is 1-15; the stripping solution comprises one or more of nitric acid, sulfuric acid, and hydrochloric acid solution.

[0023] The application has the following beneficial effects:

[0024] The application recovers manganese from the filtrate in the MHP section prepared from laterite nickel ore by using a low-cost resin adsorption method combined with a continuous extraction process. The recovered manganese solution can meet the standard of a battery-grade manganese solution, and the manganese recovery rate is 95% or higher. This not only reduces resource waste and environmental pollution caused by manganese residue landfill, but also alleviates the problem of tight manganese resources in China. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the application, the drawings of the embodiments will be briefly introduced below.

[0026] FIG. 1 is a flowchart of a method for recovering manganese from a post-MHP liquid according to the application. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort belong to the scope of the present application.

[0028] As shown in FIG. 1, the present application provides a method for recovering manganese from MHP precipitation liquid, comprising the following steps:

[0029] (1) Resin adsorption of manganese in MHP precipitation liquid, and obtaining a manganese-rich solution after elution;

[0030] The resin adsorption process specifically comprises:

[0031] Manganese adsorption: The MHP precipitation liquid is passed through the column at a flow rate of 0.5-6 BV / h for adsorption. The type of resin used in the present application is not limited, and can be any resin capable of adsorbing manganese ions, including but not limited to one or more of LSC-495, HP606, D854, HP4080, and CH27.

[0032] Resin elution: The manganese-adsorbed resin is eluted with a desorption solution having a concentration of 1-25% to obtain a manganese-rich solution. The desorption solution includes one or more of nitric acid, sulfuric acid, and hydrochloric acid solution. The flow rate of the desorption solution is 0.5-5 BV / h.

[0033] (2) The manganese-rich solution is subjected to extraction treatment to obtain a manganese-rich organic phase and a raffinate;

[0034] Specifically, the extraction treatment comprises:

[0035] The extractant is mixed with a diluent to obtain an extraction organic phase. The extractant is one or more of HBL110 and HBL116. The diluent includes one or more of sulfonated kerosene, aviation kerosene, and No. 260 solvent oil. The dilution rate of the extractant is 5-50%. The present application uses HBL110 and / or HBL116 as the extractant, which does not need to be subjected to saponification treatment. Compared with the prior art, the present application greatly reduces the process cost and can obtain good manganese extraction effect.

[0036] The extraction organic phase is mixed with the manganese-rich solution at a volume ratio of 1:0.1-10 for manganese extraction. The extraction stage is 1-15 stages to obtain a loaded organic phase and a raffinate.

[0037] The loaded organic phase is washed with a washing liquid at a volume ratio of 1-40:1. The washing stage is 1-15 stages to obtain a manganese-rich organic phase and washing water. The washing liquid includes one or more of nitric acid, sulfuric acid, and hydrochloric acid solution.

[0038] (3) stripping treatment of the manganese-rich organic phase to obtain a battery-grade manganese solution;

[0039] The stripping treatment step specifically comprises: mixing the manganese-rich organic phase with a stripping solution having a concentration of 0.5-3.0 mol / L at a volume ratio of 5-40:1, performing stripping, and obtaining a stripping manganese solution and a stripping organic phase; the stripping solution comprises one or more of nitric acid, sulfuric acid, and hydrochloric acid solution.

[0040] To make the objectives, technical solutions, and advantages of the present application clearer, the embodiments of the present application will be described in further detail below.

[0041] The main components of the post-sink MHP solution used in the following examples and comparative examples are as follows: nickel ions 0.002 g / L, cobalt ions 0.004 mg / L, manganese ions 1.65 g / L, calcium ions 0.59 g / L, and magnesium ions 5.67 g / L.

[0042] Example 1

[0043] A method for recovering manganese from a post-sink MHP solution, comprising the following steps:

[0044] (1) resin adsorption

[0045] The post-sink MHP solution is passed through the column at a flow rate of 2.5 BV / h for adsorption, and the filtration liquid is stopped when the Mn in the adsorption tail liquid is >0.005 g / L; wherein the resin is D854, and the series number of the resin is 6;

[0046] Then, a 15% sulfuric acid solution is used as a desorption solution to desorb the manganese adsorption resin at a flow rate of 2.5 BV / h, and a manganese-rich solution is obtained;

[0047] Table 1 Composition of the manganese-rich solution

[0048] (2) extraction

[0049] The extractant HBL110 is mixed with a diluent sulfonated kerosene to obtain an extraction organic phase; the dilution rate of the extractant is 40%. The extraction organic phase is mixed with the manganese-rich solution at a volume ratio of 1:0.4 to extract manganese, the extraction series number is 8, and a loaded organic phase and a raffinate are obtained; a washing liquid 0.15 mol / L sulfuric acid solution is mixed with the loaded organic phase at a volume ratio of 1:20 for washing, the washing series number is 6, and a manganese-rich organic phase and washing water are obtained.

[0050] (3) stripping

[0051] The manganese-rich organic phase is mixed with a back-extraction solution of sulfuric acid with a concentration of 2.0 mol / L at a volume ratio of 20:1, back-extraction is performed, and the back-extraction is performed for 7 stages to obtain a back-extraction manganese solution and a back-extraction organic phase.

[0052] Table 2 Composition of the back-extraction manganese solution

[0053] As can be seen from Table 2, the back-extraction manganese solution, i.e., the manganese sulfate solution, obtained by the resin adsorption combined continuous extraction process provided in the application has high purity and meets the battery grade standard, and can be directly used for compounding into ternary NCM battery materials.

[0054] Example 2

[0055] The difference from Example 1 is that the extractant used in the extraction process of step (2) is HBL116.

[0056] Table 3 Composition of the manganese solution after back-extraction treatment

[0057] As can be seen from Table 3, the battery-grade manganese sulfate solution can also be obtained by using the extractant HBL116, and similar to the extractant HBL110, no saponification treatment is required, and the cost of recovering and preparing the battery-grade manganese solution is very low.

[0058] Example 3

[0059] The difference from Example 1 is that the resin used in the adsorption process of step (1) is LSC-495

[0060] Table 4 Composition of the manganese-rich solution

[0061] The O / A ratio needs to be adjusted to 1:0.58 during extraction, and other extraction process parameters remain unchanged.

[0062] Table 5 Composition of the back-extraction manganese solution

[0063] It can be found that the adsorption selectivity of LSC-495 resin for nickel, cobalt and manganese is different from that of D854, and therefore the ratio of nickel, cobalt and manganese in the battery-grade manganese solution obtained by the final back-extraction changes.

[0064] Comparative Example 1

[0065] The difference from Example 1 is that only extraction is performed, and no adsorption is performed, i.e., the resin adsorption step of step (1) is not performed.

[0066] Table 6 Composition of the back-extraction manganese solution

[0067] It can be found that the calcium and magnesium impurities in the manganese solution obtained by extraction only, no adsorption and back extraction are easy to exceed the standard. In addition, it must be noted that if the low concentration manganese solution directly enters the extraction line, not only will it result in too large amount of raffinate and high cost of raffinate treatment, but also will reduce the effective utilization rate of equipment and production efficiency.

[0068] Comparative Example 2

[0069] The difference from Example 1 is only that adsorption is performed only, no extraction, i.e. no extraction and back extraction steps of steps (2) and (3) are performed. As shown in Table 1, it can be found that the calcium and magnesium impurities in the manganese solution obtained by direct elution of the resin are unstable and often exceed the standard, which does not meet the standard of battery-grade manganese solution, and the concentration of manganese in the manganese solution is low.

[0070] Comparative Example 3

[0071] The difference from Example 1 is only that P507 extractant is used in the extraction process of step (2).

[0072] Table 7 Composition of back-extracted manganese solution

[0073] The extraction order of P507 extractant for nickel, cobalt, manganese, calcium and magnesium is calcium > manganese > cobalt > magnesium > nickel, and the separation coefficient of the extractant for Mn / Mg is small. As can be seen from Table 7, the contents of calcium and magnesium in the manganese sulfate solution obtained by back extraction all exceed the standard.

[0074] Comparative Example 4

[0075] The difference from Example 1 is only that DY319 extractant is used in the extraction process of step (2).

[0076] Table 8 Composition of back-extracted manganese solution

[0077] As can be seen from the above table, the extraction effect of DY319 extractant without saponification treatment is poor, while the application uses HBL110 and / or HBL116 as extractant, which can obtain good manganese extraction effect without saponification treatment, and has lower cost advantage.

[0078] It should be noted that each of the above examples belongs to the same application concept, and the description of each example has its own emphasis. If the description is not exhaustive in individual examples, the description in other examples can be referred to.

[0079] The above embodiments only express the implementation of the present application, and the description is more specific and detailed, but it cannot be understood as a limitation on the scope of the application. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method of recovering manganese from a post-MHP settling liquor, characterized in that, The method comprises the following steps: (1) resin adsorption of manganese in the MHP precipitation solution, and obtaining a manganese-rich solution after desorption; (2) extraction treatment of the manganese-rich solution to obtain a manganese-rich organic phase and a raffinate; the extractant used in the extraction treatment is one or more of HBL110 and HBL116; (3) stripping treatment of the manganese-rich organic phase to obtain a battery-grade manganese solution.

2. The method of recovering manganese from post-sink MHP liquor according to claim 1, wherein, In step (1), the resin used in the resin adsorption process is one or more of LSC-495, HP606, D854, HP4080 and CH27.

3. The method of recovering manganese from post-sink MHP liquor of claim 1, wherein, In step (1), the resin adsorption process comprises: Manganese adsorption: passing the MHP precipitation solution through the column at a flow rate of 0.5-6 BV / h for adsorption; Resin desorption: desorption of the manganese adsorption resin with a desorption solution to obtain a manganese-rich solution.

4. The method of recovering manganese from post-sink MHP liquor according to claim 3, wherein, The desorption solution comprises one or more of nitric acid, sulfuric acid and hydrochloric acid solutions with a concentration of 1-25%; the flow rate of the desorption solution is 0.5-5 BV / h.

5. The method of recovering manganese from post-sink MHP liquor of claim 1, wherein, In step (2), the extraction treatment comprises: Mixing the extractant with a diluent to obtain an extraction organic phase; Mixing the extraction organic phase with the manganese-rich solution to extract manganese, thereby obtaining a loaded organic phase and a raffinate; Washing the loaded organic phase with a washing solution to obtain a manganese-rich organic phase and washing water.

6. The method of recovering manganese from post-sink MHP liquor according to claim 5, wherein, The diluent comprises one or more of sulfonated kerosene, aviation kerosene and No. 260 solvent oil; the dilution rate of the extractant is 5-50%.

7. The method of recovering manganese from post-sink MHP liquor according to claim 5, wherein, The volume ratio of the extraction organic phase to the manganese-rich solution is 1:0.1-10, and the extraction stage number is 1-15.

8. The method of recovering manganese from post-sink MHP liquor of claim 5, wherein, The volume ratio of the loaded organic phase to the washing solution is 1-40:1, the washing stage number is 1-15, and the washing solution comprises one or more of nitric acid, sulfuric acid and hydrochloric acid solutions.

9. The method of recovering manganese from post-sink MHP liquor of claim 1, wherein, In step (3), the stripping treatment step comprises: mixing a stripping solution with the manganese-rich organic phase to perform stripping, thereby obtaining a battery-grade manganese solution and a stripping organic phase; The concentration of the stripping solution is 0.5-3.0 mol / L, the volume ratio of the manganese-rich organic phase to the stripping solution is 5-40:1, and the stripping stage number is 1-15; the stripping solution comprises one or more of nitric acid, sulfuric acid and hydrochloric acid solutions.

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