Method for removing manganese and recovering cobalt from cobalt-containing copper extraction raffinate
By employing two manganese precipitation processes and ultrasonic-assisted neutralization and cobalt precipitation, the problem of incomplete oxidation precipitation was solved, thereby improving the cobalt grade and reducing impurity manganese in the cobalt concentrate, thus enhancing the quality of the cobalt concentrate.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YUNNAN CHIHONG ZN & GE CO LTD
- Filing Date
- 2023-11-24
- Publication Date
- 2026-05-19
AI Technical Summary
In existing technologies, the oxidation precipitation process cannot completely remove manganese from the cobalt-containing copper extraction residue, resulting in a decrease in the cobalt grade in the cobalt-enriched material and affecting the overall quality of the cobalt-enriched material.
The process employs a two-stage manganese precipitation process. First, the manganese is oxidized and neutralized by an oxidant. Then, cobalt-manganese slag is used for leaching and further manganese precipitation. Finally, ultrasonic-assisted magnesium oxide is used to neutralize and precipitate cobalt, which significantly improves the mass ratio of cobalt and manganese in the leaching solution.
It significantly improved the cobalt grade of cobalt-enriched materials, reduced the content of impurity manganese, and improved the quality of cobalt-enriched materials.
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Figure CN117802317B_ABST
Abstract
Description
Technical Field
[0001] This invention application relates to the field of non-ferrous metallurgical technology, specifically to a method for removing manganese and recovering cobalt from copper extraction residue containing cobalt. Background Technology
[0002] Cobalt is an important national strategic resource, playing a key role in aerospace, defense industry, medical and health care, new energy and other fields. With the promotion of the national new energy strategy, the battery industry has ushered in rapid development. As a raw material for lithium batteries, the demand for cobalt materials has increased rapidly. my country's cobalt resources are of low grade, complex occurrence, and relatively scarce, and mainly rely on imports. Therefore, developing a low-cost, high-efficiency, and green method for recycling cobalt resources has high economic value and social benefits.
[0003] Cobalt-containing copper extraction residue typically comes from the leaching of copper-cobalt ore or from the copper-cadmium slag and cobalt slag produced during hydrometallurgical zinc refining. This residue usually contains high levels of cobalt and manganese. Both cobalt and manganese need to be recovered during production.
[0004] To improve the quality of cobalt-enriched materials, it is necessary to remove as much manganese as possible from the cobalt-containing copper extraction residue.
[0005] To address manganese ions in the residue of copper extraction containing cobalt, existing technologies typically employ oxidation precipitation, where manganese is removed along with iron ions from the solution, forming an iron-manganese slag. The problem with this method is that the oxidation precipitation process does not completely remove manganese, leaving a high manganese content in the solution. This high manganese content then enters the cobalt concentrate during the subsequent cobalt precipitation process, resulting in a lower cobalt grade and overall lower quality of the concentrate. Summary of the Invention
[0006] To address the problems existing in the background technology, this invention provides a method for recovering cobalt from manganese in copper extraction residue containing cobalt. Through two manganese precipitation processes, the mass ratio of cobalt to manganese in the leaching solution is significantly improved. Thus, when the leaching solution is neutralized and cobalt is precipitated, not only is cobalt more likely to settle into the cobalt concentrate, but the content of impurity manganese entering the cobalt concentrate is also relatively less. Ultimately, the cobalt grade in the cobalt concentrate is significantly improved, and the quality of the cobalt concentrate is higher.
[0007] This application provides a method for removing manganese and recovering cobalt from copper extraction residue containing cobalt, comprising the following steps:
[0008] S1. The cobalt-containing copper extraction residue is oxidized and a neutralizing agent is added to neutralize and precipitate cobalt and manganese. After liquid-solid separation, cobalt-manganese slag is obtained.
[0009] S2. Add the cobalt-manganese slag to the cobalt-containing copper extraction residue for leaching, leach out the cobalt and precipitate the manganese again, and obtain the leaching liquid and manganese concentrate after liquid-solid separation.
[0010] S3. Add magnesium oxide to the leaching solution to neutralize and precipitate cobalt. After liquid-solid separation, cobalt precipitate residue is obtained. After washing the cobalt precipitate residue with water, cobalt enrichment is obtained.
[0011] Specifically, in step S2, the mass of cobalt in the cobalt-manganese slag is 1.2 to 2.2 times the mass of manganese in the cobalt-containing copper extraction residue, the leaching reaction time is 4 to 8 hours, the leaching temperature is 30 to 80°C, and the final pH is 5.0 to 5.5.
[0012] Specifically, in step S3, when neutralizing and depositing cobalt, ultrasonic waves are used to assist in the neutralization and deposition process.
[0013] Specifically, in step S3, ultrasonic-assisted neutralization and cobalt precipitation are used, wherein the ultrasonic power is 200~1000W and the frequency is 10~25KHz.
[0014] Specifically, the final pH of the cobalt neutralization in step S3 is 8.0 to 9.0.
[0015] Specifically, in step S1, the oxidation of the cobalt-containing copper extraction residue involves continuously introducing SO2 into the cobalt-containing copper extraction residue while simultaneously introducing oxygen and / or air for oxidation. The oxidation temperature is controlled at 30–80°C, and the oxidation time is 2–8 hours.
[0016] Specifically, in step S1, the final pH of the neutralizing agent added to neutralize the cobalt-manganese precipitation is 4.5 to 5.5.
[0017] Specifically, the neutralizing agent in step S1 is limestone or quicklime.
[0018] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit the scope of this application.
[0019] Compared with the prior art, the beneficial technical effects of the present invention are:
[0020] In treating the cobalt-containing copper extraction residue, this invention, in addition to the initial demanganese removal by oxidizing and neutralizing with an oxidant to precipitate cobalt and manganese, then leaches the resulting cobalt-manganese slag using the cobalt-containing copper extraction residue. This leaching process simultaneously removes cobalt and precipitates manganese again. Through these two manganese precipitation processes, the mass ratio of cobalt to manganese in the leaching solution is significantly increased. Thus, when the leaching solution is neutralized and precipitated for cobalt, not only is cobalt more likely to settle into the cobalt concentrate, but the amount of impurity manganese entering the cobalt concentrate is also relatively less. Ultimately, this significantly improves the cobalt grade in the cobalt concentrate, resulting in a higher quality cobalt concentrate. Attached Figure Description
[0021] Figure 1 This is a process flow diagram for the present invention application. Detailed Implementation
[0022] The alternative embodiments of this application will now be described in more detail with reference to the accompanying drawings. While alternative embodiments of this application are shown in the drawings, it should be understood that this application can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided to make this application more thorough and complete, and to fully convey the scope of this application to those skilled in the art.
[0023] The terminology used in this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The singular forms “a,” “the,” and “the” used in this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any or all possible combinations of one or more of the associated listed items.
[0024] In this invention application, the liquid-to-solid ratio refers to the ratio of the mass of the solution to the mass of the solid material in the reaction system.
[0025] The following is a detailed description of a method for removing manganese and recovering cobalt from the residue of copper extraction containing cobalt, in conjunction with the accompanying drawings:
[0026] The method for recovering cobalt from manganese in the copper extraction residue of cobalt-containing copper extract in this invention application includes the following steps:
[0027] S1. The cobalt-containing copper extraction residue is oxidized with an oxidant, and a neutralizing agent is added to neutralize and precipitate cobalt and manganese. After liquid-solid separation, cobalt-manganese slag is obtained. The above operation is based on the fact that the manganese and cobalt ions in the cobalt-containing copper extraction residue are oxidized from low valence to high valence by an oxidant, and then neutralized with a neutralizing agent and hydrolyzed to precipitate, thereby achieving the co-precipitation of cobalt and manganese ions.
[0028] S2. Cobalt-manganese slag is added to the cobalt-containing copper extraction residue for leaching, cobalt is leached out and manganese is precipitated again, and after liquid-solid separation, the leaching solution and manganese-enriched material are obtained. The process of adding cobalt-manganese slag to the cobalt-containing copper extraction residue to leach cobalt and precipitate manganese utilizes the strong oxidizing properties of high-valence cobalt oxides under acidic conditions, which oxidizes and precipitates low-valence manganese ions. After the cobalt compounds in the cobalt-manganese slag are oxidized and precipitated, the concentration of manganese ions in the solution is reduced again. Meanwhile, the high-valence cobalt is reduced to low-valence cobalt ions and enters the solution, resulting in a significant increase in the cobalt-manganese mass ratio in the leaching solution.
[0029] S3. Add magnesium oxide to the manganese-removed liquid for neutralization and cobalt precipitation. After liquid-solid separation, cobalt-precipitated slag is obtained. After washing the cobalt-precipitated slag with water, cobalt-enriched material is obtained. The manganese sulfate produced by the neutralization and cobalt precipitation reaction using magnesium oxide is a soluble salt, which can reduce the entrainment of magnesium in the precipitate.
[0030] In one embodiment of this invention application, the magnesium oxide in step S3 is active magnesium oxide.
[0031] In one embodiment of this invention, step S3 employs ultrasonic-assisted neutralization with an ultrasonic power of 200-1000W and a frequency of 10-25KHz. The growth and collapse of cavitation nuclei during ultrasonic cavitation generate strong shear forces within the solution, separating the neutralizing agent from the cobalt-precipitated product. This exposes the active surface of the neutralizing agent, breaks down its encapsulation, and reduces the diffusion layer, thereby promoting the cobalt-precipitated neutralization reaction and reducing the amount of neutralizing agent required. Simultaneously, its stirring and stripping effect further reduces the entrainment of soluble compounds in the solution and improves the utilization rate of magnesium oxide, ensuring the production of higher-quality cobalt-enriched material.
[0032] In one embodiment of this invention application, the endpoint pH in step S3 is 8.0 to 9.0.
[0033] In one embodiment of this invention, the oxidation of the cobalt-containing copper extraction residue in step S1 involves continuously introducing SO2 into the residue while simultaneously introducing oxygen and / or air. The oxidation temperature is controlled at 30–80°C, and the oxidation time is 2–8 hours. Under higher pH conditions, the oxidation and neutralization of cobalt and manganese is rapid, and the proportion of cobalt precipitating as low-valence hydrolysis is very small below pH 5.5. Therefore, the cobalt in the residue is primarily in a high-valence state, which is beneficial for subsequent oxidation and precipitation of low-valence manganese ions. Cobalt-manganese ion co-precipitation is also easier to achieve in production.
[0034] In one embodiment of this invention application, the neutralizing agent in step S1 is limestone or quicklime.
[0035] In one embodiment of this invention application, in step S2, the mass of cobalt in the cobalt-manganese slag is 1.2 to 2.2 times the mass of manganese in the cobalt-containing copper extraction residue, the reaction time is 4 to 8 hours, the temperature is 30 to 80°C, and the final pH is 5.0 to 5.5.
[0036] Ultrasonic-assisted neutralization and precipitation of cobalt using activated magnesium oxide utilizes manganese sulfate, produced after the magnesium oxide neutralization reaction, as a soluble salt. This reduces the entrainment of magnesium in the slag. Ultrasonic assistance further reduces the entrainment of soluble compounds in the solution and improves the utilization rate of magnesium oxide by utilizing its stirring and stripping effect, thus ensuring the production of higher quality cobalt oxide products.
[0037] For clarity, the following examples will be used to provide a detailed description.
[0038] Example 1
[0039] The composition of the cobalt-containing copper extraction residue is shown in Table 1.
[0040] Table 1. Components of Cobalt-Containing Copper Extraction Residue
[0041]
[0042] like Figure 1 As shown in the flowchart, a method for removing manganese and recovering cobalt from the residue of copper extraction containing cobalt includes the following steps:
[0043] 1. Take 4000 mL of the above cobalt-containing copper extraction residue, oxidize it by passing SO2 and air through it, and neutralize it by adding limestone. The temperature is controlled at 40℃ throughout the process, and the oxidation and neutralization are carried out for 5 hours. The final pH is 5.0. After oxidation and neutralization to precipitate cobalt and manganese, the slurry is subjected to liquid-solid separation to obtain cobalt and manganese precipitated liquid and manganese-cobalt slag. The composition of the cobalt and manganese precipitated liquid is shown in Table 2.
[0044] Table 2. Components of the liquid after cobalt-manganese precipitation
[0045]
[0046] The table contains The unit is mg / L.
[0047] 2. The obtained cobalt-manganese slag was added to 1.2L of cobalt-containing copper extraction residue for cobalt leaching and manganese redeposition. The reaction temperature was controlled at 40℃ and the reaction time was 6h. The final pH of the reaction was 5.0. After the reaction, the slurry was subjected to liquid-solid separation to obtain manganese enrichment and leaching solution. The composition of the leaching solution is shown in Table 3.
[0048] Table 3 Components of the leaching solution
[0049]
[0050] 3. Take 1000 mL of the leachate and add active magnesium oxide under ultrasonic assistance to neutralize and precipitate cobalt. Control the final pH to 8.3. After liquid-solid separation, cobalt precipitated slag and cobalt precipitated liquid are obtained. The cobalt precipitated slag is washed with water to obtain cobalt enrichment. The chemical composition analysis of cobalt enrichment is shown in Table 4.
[0051] Table 4. Composition of Cobalt Accumulated Materials
[0052]
[0053] Example 2
[0054] The composition of the cobalt-containing copper extraction residue is shown in Table 5.
[0055] Table 5. Components of Cobalt-Containing Copper Extraction Residue
[0056]
[0057] like Figure 1 As shown in the flowchart, a method for removing manganese and recovering cobalt from the residue of copper extraction containing cobalt includes the following steps:
[0058] 1. Take 4000 mL of the above cobalt-containing copper extraction residue, oxidize it by passing SO2 and air, and neutralize it by adding limestone. The temperature is controlled at 40℃ throughout the process, and the oxidation and neutralization are carried out for 4.5 h. The final pH is 5.5. After oxidation and neutralization to precipitate cobalt and manganese, the slurry is subjected to liquid-solid separation to obtain cobalt and manganese precipitated liquid and manganese-cobalt slag. The composition of the cobalt and manganese precipitated liquid is shown in Table 6.
[0059] Table 6. Components of the liquid after cobalt and manganese precipitation
[0060]
[0061] The table contains The unit is mg / L.
[0062] 2. The obtained cobalt-manganese slag was added to 1.2L of cobalt-containing copper extraction residue for cobalt leaching and manganese redeposition. The reaction temperature was controlled at 40℃ throughout the process, and the reaction time was 6h. The final pH of the reaction was 5.5. After the reaction, the slurry was subjected to liquid-solid separation to obtain manganese enrichment and leaching solution. The composition of the leaching solution is shown in Table 7.
[0063] Table 7 Components of the leaching solution
[0064]
[0065] 3. Take 1000 mL of the leachate and add active magnesium oxide under ultrasonic assistance to neutralize and precipitate cobalt. Control the final pH to 8.5. After liquid-solid separation, cobalt precipitate residue and cobalt precipitate liquid are obtained. The cobalt precipitate residue is washed with water to obtain cobalt enrichment. The chemical composition analysis of cobalt enrichment is shown in Table 8.
[0066] Table 8. Composition of Cobalt-Enriched Materials
[0067]
[0068] Example 3
[0069] The composition of the cobalt-containing copper extraction residue is shown in Table 9.
[0070] Table 9. Components of Cobalt-Containing Copper Extraction Residue
[0071]
[0072] A method for removing manganese and recovering cobalt from copper extraction residue containing cobalt includes the following steps:
[0073] 1. Take 4000 mL of the above cobalt-containing copper extraction residue, oxidize it by passing SO2 and air through it, and add limestone for neutralization. The temperature is controlled at 40℃ throughout the process, and the oxidation and neutralization are carried out for 5 hours. The final pH is 5.0. After oxidation and neutralization to precipitate cobalt and manganese, the slurry is subjected to liquid-solid separation to obtain cobalt and manganese precipitated liquid and manganese-cobalt slag. The composition of the cobalt and manganese precipitated liquid is shown in Table 10.
[0074] Table 6. Components of the liquid after cobalt and manganese precipitation
[0075]
[0076] The table contains The unit is mg / L.
[0077] 2. The obtained cobalt-manganese slag was added to 1.2L of cobalt-containing copper extraction residue for cobalt leaching and manganese redeposition. The reaction temperature was controlled at 40℃ and the reaction time was 6h. The final pH of the reaction was 5.0. After the reaction, the slurry was subjected to liquid-solid separation to obtain manganese enrichment and leaching solution. The composition of the leaching solution is shown in Table 11.
[0078] Table 11 Components of the Leachate
[0079]
[0080] 3. Take 1000 mL of the leachate and add active magnesium oxide under ultrasonic assistance to neutralize and precipitate cobalt. Control the final pH to 8.3. After liquid-solid separation, cobalt precipitate residue and cobalt precipitate liquid are obtained. The cobalt precipitate residue is washed with water to obtain cobalt enrichment. The chemical composition analysis of cobalt enrichment is shown in Table 12.
[0081] Table 12 Composition of Cobalt-Enriched Specimens
[0082]
[0083] Comparative Example 1
[0084] The composition of the cobalt-containing copper extraction residue is shown in Table 13.
[0085] Table 13 Components of Cobalt-Containing Copper Extraction Residue
[0086]
[0087] The cobalt-containing copper extraction residue (with the same composition as in Example 1) was treated by using the existing technology of oxidation neutralization followed by the direct addition of magnesium oxide for cobalt precipitation neutralization.
[0088] Specifically, SO2 and air are first introduced for oxidation, followed by the addition of limestone for neutralization. The temperature is controlled at 40℃ throughout the process, and the oxidation and neutralization last for 5 hours. The final pH is 5.0.
[0089] Activated magnesium oxide was added to the above slurry to neutralize and precipitate cobalt. The slurry was oxidized and neutralized for 5 hours under ultrasonic assistance, and the final pH was controlled at 8.3. After liquid-solid separation, the slurry yielded cobalt-manganese precipitated liquid and filter residue. The composition of the cobalt-manganese precipitated liquid is shown in Table 14.
[0090] Table 14 Composition of the liquid after cobalt-manganese precipitation
[0091]
[0092] The table contains The unit is mg / L.
[0093] The composition of the water-washed residue obtained after rinsing the filter residue with water is shown in Table 15.
[0094] Table 15 Components of Washed Sludge
[0095]
[0096] As can be seen from Examples 1-3, the method of the present invention can be used to treat the cobalt-containing copper extraction residue to achieve efficient separation of manganese and cobalt. The manganese is separated as a manganese concentrate, which can be used as an oxidant in the wet zinc leaching process, while the cobalt is finally separated as a cobalt concentrate. In particular, the average cobalt grade of the cobalt concentrates obtained in Examples 1-3 is 47.01%, and the manganese content in the cobalt concentrates is only 0.94% on average. The above experimental data fully demonstrate that the method of the present invention can achieve efficient enrichment of cobalt and significantly improve the quality of the cobalt concentrates.
[0097] In contrast, in Comparative Example 1, since the two-step manganese precipitation was not performed, the cobalt content in the washed residue was only 25.39%, while the manganese content in the washed residue was as high as 14.73%. The above data fully demonstrate that the method in the comparative example cannot achieve efficient enrichment of cobalt, nor can it achieve effective separation of cobalt and manganese.
[0098] The various embodiments of this invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or improvement of the technology in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.
Claims
1. A method for removing manganese and recovering cobalt from copper extraction residue containing cobalt, characterized in that, Includes the following steps: S1. The cobalt-containing copper extraction residue is oxidized and a neutralizing agent is added to neutralize and precipitate cobalt and manganese. After liquid-solid separation, cobalt-manganese slag is obtained. S2. Add the cobalt-manganese slag to the cobalt-containing copper extraction residue for leaching, leach out the cobalt and precipitate the manganese again, and obtain the leaching liquid and manganese concentrate after liquid-solid separation. S3. Add magnesium oxide to the leaching solution to neutralize and precipitate cobalt. After liquid-solid separation, cobalt precipitate residue is obtained. After washing the cobalt precipitate residue with water, cobalt enrichment is obtained.
2. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt according to claim 1, characterized in that, In step S2, the mass of cobalt in the cobalt-manganese slag is 1.2 to 2.2 times the mass of manganese in the cobalt-containing copper extraction residue, the leaching reaction time is 4 to 8 hours, the leaching temperature is 30 to 80°C, and the final pH is 5.0 to 5.
5.
3. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt as described in claim 1 or 2, characterized in that, In step S3, when neutralizing and depositing cobalt, ultrasonic waves are used to assist in the neutralization and deposition process.
4. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt according to claim 3, characterized in that, In step S3, ultrasonic-assisted neutralization and cobalt precipitation are used, wherein the ultrasonic power is 200~1000W and the frequency is 10~25KHz.
5. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt according to claim 3, characterized in that, The final pH value for neutralizing and precipitating cobalt in step S3 is 8.0 to 9.
0.
6. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt according to claim 1, characterized in that, In step S1, the oxidation of the cobalt-containing copper extraction residue is carried out by continuously introducing SO2 into the cobalt-containing copper extraction residue, while simultaneously introducing oxygen and / or air for oxidation. The oxidation temperature is controlled at 30-80°C, and the oxidation time is 2-8 hours.
7. The method for removing manganese and recovering cobalt from the residual liquid of copper extraction containing cobalt according to claim 6, characterized in that, In step S1, the final pH of the neutralizing agent added to neutralize the cobalt-manganese precipitation is 4.5–5.
5.
8. The method for recovering cobalt from manganese in the residual liquid of copper extraction containing cobalt according to claim 7, characterized in that, The neutralizing agent mentioned in step S1 is limestone or quicklime.