Methods and apparatus for extracting copper, manganese, and cobalt from copper-containing, manganese-containing, and cobalt-containing materials.

Abstract

This invention discloses a method and apparatus for extracting copper, manganese, and cobalt from copper-containing materials. The method includes: sulfuric acid reduction leaching; iron removal from the leaching solution; copper extraction from the iron-removed solution; electrowinning of the copper solution obtained after organic reverse extraction to obtain electrowinning copper; open-circuiting the leaching residue for manganese and cobalt separation to obtain manganese slag and cobalt products that can be used as manganese products; and returning the cobalt precipitate and copper slag produced during the separation process to the sulfuric acid reduction leaching process. Using this invention for copper, manganese, and cobalt extraction avoids the introduction of impurities, achieves good separation results, yields high-purity products, and high yields of each metal. It avoids the complex pretreatment processing steps for cobalt products, ensures stable operation of the copper extraction and electrowinning processes, and reduces extractant consumption and electrowinning energy consumption.

Description

Technical Field

[0001] This invention relates to the field of wet processing technology for copper-containing materials, and in particular to a method and apparatus for extracting copper, manganese and cobalt from copper-, manganese and cobalt-containing materials. Background Technology

[0002] Currently, copper-containing materials are typically treated using a wet process, where the leachate is used for copper extraction, and the extracted liquid is then subjected to a copper electrowinning process to produce copper products.

[0003] During implementation, the inventors of this application discovered that when the raw material also contains manganese, the manganese enters the solution during the leaching process. After the extraction system has been running for a period of time, the manganese will continuously accumulate in the extraction system, easily causing emulsification of the extractant, which in turn increases the consumption of the extractant and affects the extraction process. In addition, when the manganese content in the back-extraction solution is too high, it will lead to a decrease in the electrical efficiency of the electrowinning process after entering the electrowinning system, increasing energy consumption and also affecting the stability of the electrowinning system.

[0004] Based on this, through research and practice on how to remove manganese during the processing of copper-containing materials, it was further discovered that: using conventional oxidants to remove manganese has problems such as high processing costs, introduction of impurities, and corrosion of equipment. Moreover, the precipitation pH varies greatly depending on the valence state of manganese; low-valence manganese only begins to precipitate at a pH of 8. In the presence of low-valence manganese, even a small amount of oxygen from the air entering the solution will slowly oxidize the manganese, while the resulting high-valence manganese begins to precipitate at around a pH of 3, making comprehensive utilization of manganese quite difficult. In addition, the inventors of this application also discovered that divalent cobalt begins to precipitate at around a pH of 7, and that using the sulfide precipitation method for cobalt requires complex pretreatment methods such as oxygen pressure leaching after obtaining the intermediate cobalt product before it can be processed into the final product. Summary of the Invention

[0005] In view of the above problems, according to one embodiment of the present invention, the object is to provide a method and apparatus for extracting copper, manganese and cobalt from copper-containing materials.

[0006] The above objective can be achieved through the following technical solutions:

[0007] According to one aspect of the present invention, a method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials is provided, comprising:

[0008] Materials containing copper, manganese, and cobalt were leached by sulfuric acid reduction; iron was removed from the reduction leaching solution; the iron-removed solution was extracted with a copper extractant; the extract was back-extracted and then electrowinning was performed to obtain electrowinning copper.

[0009] The raffinate is opened for manganese and cobalt separation to obtain manganese and cobalt products. This includes: using sodium persulfate or SO2 / O2 system as oxidant and MgO as neutralizing agent, controlling the pH to 3.5-4.2, removing manganese from the raffinate to obtain manganese-removed solution and manganese slag as manganese product; precipitating copper in the manganese-removed solution and returning the copper slag after copper precipitation to reduction leaching; using MgO or sodium carbonate as neutralizing agent, precipitating cobalt in the copper precipitation solution to directly obtain cobalt product, and returning the cobalt precipitation solution after cobalt precipitation to reduction leaching.

[0010] Optionally, when sodium persulfate is used as the oxidant, the excess coefficient is 3 to 8, the temperature is 30 to 90°C, and the reaction time is 1 to 3 hours.

[0011] Optionally, when using an SO2 / O2 system as the oxidant, the SO2 flow rate is 0.1–1.0 L / (L 溶液 O2 flow rate is 0.8–100 L / (L·h). 溶液 The reaction time is 1 to 6 hours, with a temperature of 0 to 90°C.

[0012] Optionally, the raffinate is demanganese to ensure that the manganese concentration in the demanganese-removed solution does not exceed 0.5 g / L. And / or, optionally, when sodium persulfate is used as the oxidant, the temperature is 50–90 °C; when an SO2 / O2 system is used as the oxidant, the temperature is 20–60 °C.

[0013] Optionally, when the cobalt content in the manganese slag is ≥1.5%, the manganese slag is leached to extract cobalt to obtain manganese products. The leaching acid is sulfuric acid, and a reduction leaching method is used. The cobalt-containing solution after leaching is mixed with the copper precipitation solution to jointly precipitate cobalt.

[0014] Optionally, the reducing agent used in the leaching of cobalt and the sulfuric acid reduction leaching is selected from at least one of hydrogen peroxide, sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium sulfite, sodium metabisulfite, potassium sulfite, or ammonium sulfite.

[0015] Optionally, during sulfuric acid reduction leaching, the leaching temperature is 0–95℃, the reaction time is 2–8 h, and the final pH value is 0.9–2.0. And / or, optionally, during cobalt extraction leaching, the pH value is 1.5–4.0, the leaching temperature is 0–90℃, and the reaction time is 1–6 h.

[0016] Optionally, during sulfuric acid reduction leaching, the leaching temperature is 20–60°C and the liquid-to-solid ratio is 3:1.

[0017] And / or, optionally, when leaching cobalt, the leaching temperature is 20–60°C and the liquid-to-solid ratio is 5:1.

[0018] Optionally, the leachate is subjected to iron removal so that the iron concentration in the solution after iron removal is not higher than 0.5 g / L.

[0019] Optionally, an oxidation precipitation method is used to remove iron, using at least one of hydrogen peroxide, air, and oxygen as the oxidant, and one or more of NaOH, MgO, CaCO3, or Ca(OH)2 as the neutralizing agent, controlling the pH to be 2.0–4.8. Optionally, when precipitating copper, MgO is used as the neutralizing agent, controlling the pH to be 4.4–6.5. And / or, optionally, when precipitating cobalt, MgO or sodium carbonate is used as the neutralizing agent, controlling the pH to be 7.5–8.5.

[0020] Optionally, the manganese product obtained by leaching cobalt has a cobalt content of ≤0.2%.

[0021] Optionally, the copper leaching rate in the leachate obtained by sulfuric acid reduction leaching is ≥93%; the leachate is extracted using a copper extractant composed of an amine extractant and a neutral oxygen-containing extractant; the copper content in the raffinate is ≤0.2g / L.

[0022] Optionally, the leaching rate of cobalt in the leachate obtained by sulfuric acid reduction leaching is ≥81%; the cobalt product obtained directly by cobalt precipitation is cobalt hydroxide, and the cobalt concentration in the cobalt precipitation solution after cobalt precipitation is ≤0.02g / L.

[0023] According to another aspect of the present invention, an apparatus for extracting copper, manganese, and cobalt is provided, comprising:

[0024] The acid leaching unit is used to receive materials containing copper, manganese, and cobalt, as well as copper slag and cobalt precipitation solution, and to perform sulfuric acid reduction leaching treatment to obtain leachate;

[0025] The iron removal unit is used to receive the leachate and remove iron, resulting in an iron-removed solution.

[0026] An extraction system is used to receive the leachate, extract the leachate using a copper extractant, and back-extract the extract.

[0027] An electrowinning system for receiving the back-extraction solution and performing electrowinning to obtain electrowinning copper; and

[0028] The manganese-cobalt open-circuit separation system is used to receive the raffinate generated by the extraction system and separate manganese and cobalt to obtain manganese and cobalt products;

[0029] The manganese-cobalt open-circuit separation system includes:

[0030] The manganese removal unit is used to remove manganese by using sodium persulfate or SO2 / O2 system as oxidant, MgO as neutralizing agent, and controlling the pH to 3.5-4.2, to obtain manganese removal liquid and manganese slag as manganese product;

[0031] The copper plating unit is used to receive manganese removal solution and plating copper to obtain copper plating solution and copper slag. The copper plating unit is also connected to the acid leaching unit to return the copper slag to the acid leaching unit.

[0032] The cobalt immersion unit is used to receive the copper immersion solution and use MgO or sodium carbonate as a neutralizing agent to perform cobalt immersion, directly obtaining cobalt products. The copper immersion unit is also connected to the acid leaching unit to return the cobalt immersion solution after cobalt immersion to the acid leaching unit.

[0033] Optionally, the manganese-cobalt open-circuit separation system further includes: a manganese slag cobalt extraction unit, used to receive manganese slag and leach cobalt to obtain manganese products, and to produce cobalt-containing liquid and send it to the cobalt precipitation unit to mix with copper precipitation liquid for cobalt precipitation.

[0034] Beneficial effects: According to one embodiment of the present invention, sulfuric acid reduction leaching is used to extract materials containing copper, manganese, and cobalt. Iron is removed from the leaching solution, and the iron-removed solution is extracted. After extraction, back-extraction is performed for electrowinning to obtain copper-enriched products. At the same time, the raffinate is treated by open-circuiting, and manganese and cobalt are separated after open-circuiting, so manganese and cobalt products can be obtained directly. The cobalt-precipitated solution and copper slag produced are returned to the sulfuric acid reduction leaching process for further extraction. No impurities are introduced during the entire extraction process, the separation effect is good, the purity of the obtained products is high, and the yield of each metal is high. It also avoids the complex pretreatment process of cobalt products, ensures the stable operation of copper extraction and electrowinning processes, and reduces the consumption of extractant and the energy consumption of electrowinning. Attached Figure Description

[0035] Figure 1 This is a schematic flowchart of a method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to an embodiment of the present invention. Detailed Implementation

[0036] The technical solution of the present invention will be clearly and completely described below with reference to embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0037] Figure 1This illustration schematically depicts the process flow of a method for extracting copper, manganese, and cobalt from copper-containing materials according to an embodiment of the present invention. The apparatus used in this embodiment includes an acid leaching unit, an iron removal unit, an extraction system, and an electrowinning system arranged sequentially, as well as a manganese-cobalt open-circuit separation system. The manganese-cobalt open-circuit separation system includes a manganese removal unit, a copper precipitation unit, and a cobalt precipitation unit arranged sequentially. It may also include a manganese slag cobalt extraction unit and an iron removal unit. The copper precipitation unit and the cobalt precipitation unit are both connected to the acid leaching unit. This apparatus performs sulfuric acid reduction leaching, iron removal, extraction, and electrowinning through the sequentially arranged leaching unit, extraction system, and electrowinning system. By using the open-circuit raffinate of the manganese-cobalt open-circuit separation system for manganese-cobalt separation, copper, manganese, and cobalt are extracted and fully separated, directly yielding copper-enriched products, high-purity manganese products, and cobalt products. Furthermore, the extraction system and electrowinning system operate stably throughout the entire extraction process.

[0038] like Figure 1 As shown in this embodiment, the method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials specifically includes the following steps:

[0039] Step S10: Leaching-Iron Removal-Extraction-Electrowinning. Copper-, manganese-, and cobalt-containing materials are leached using sulfuric acid and a reducing agent. The leaching slurry undergoes liquid-solid separation. Iron is removed from the leachate obtained after liquid-solid separation. Copper is extracted from the iron-removed leachate. The extract is then back-extracted and electrowinning is performed to obtain electrowinning copper. Furthermore, the raffinate is sent to a manganese-cobalt open-circuit separation system for open-circuit treatment. The resulting copper slag and cobalt-containing solution are then returned to the leaching process described above.

[0040] In sulfuric acid reduction leaching, the reducing agent used is selected from at least one of hydrogen peroxide, sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium sulfite, sodium metabisulfite, potassium sulfite, or ammonium sulfite. Using these reducing agents promotes cobalt leaching and ensures a high cobalt leaching rate.

[0041] Furthermore, when using sulfuric acid reduction leaching, the leaching temperature is controlled at 0–95°C, preferably 20–60°C, the reaction time is 2–8 hours, and the final pH value is 0.9–2.0. The leached slurry is then separated into solid and liquid components to obtain the leachate. Further, during sulfuric acid reduction leaching, the liquid-to-solid ratio is controlled at 3:1. The inventors of this application have discovered that during sulfuric acid reduction leaching, a liquid-to-solid ratio of 3:1 results in a relatively high leaching rate for all metals. Within the aforementioned temperature, reaction time, and pH range, the leaching rate can be increased. However, excessively high temperatures lead to increased energy consumption and water evaporation, while excessively low temperatures result in a decreased reaction rate.

[0042] In this step, by using sulfuric acid and the reducing agent described above, and by carrying out sulfuric acid reduction leaching under the conditions described above, the leaching rate of metals such as copper and cobalt is improved; wherein, the leaching rate of copper is ≥93% and the leaching rate of cobalt is ≥81%.

[0043] In addition, an oxidation precipitation method is used to remove iron from the leachate. The reagents used include oxidants and neutralizing agents. O2, air, or H2O2 is used as the oxidant, and NaOH, MgO, CaCO3, or Ca(OH)2 is used as the neutralizing agent. After controlling the pH to 2.0–4.8, iron precipitates out. After liquid-solid separation, an iron-removed solution is obtained, and the iron ion concentration in this solution does not exceed 0.5 g / L.

[0044] The iron-removed liquid is extracted, wherein the organic phase used in the copper extraction process comprises an extractant and a diluent solvent. The copper extractant consists of an amine extractant and a neutral oxygen-containing extractant, with an alcohol reagent as a phase modifier and aviation kerosene, 260# solvent oil, or Escaid 100 as a diluent. After extraction, the copper-rich organic phase is washed with an aqueous phase and then back-extracted using copper electrodeposition anolyte. The back-extracted anolyte, i.e., the back-extracted solution, enters the electrodeposition system for electrodeposition to obtain electrodeposited copper, while the raffinate enters the manganese-cobalt open-circuit separation system for manganese-cobalt separation.

[0045] In this step, the copper extraction efficiency is improved by using the copper extractant to extract and back-extract the leachate obtained from sulfuric acid reduction leaching. This concentrates the copper, with only a small amount entering the raffinate. Furthermore, this small amount of copper is returned to the sulfuric acid leaching reduction step after copper precipitation in the open-circuit treatment, thereby further improving the copper yield.

[0046] Step S20: Open-circuit separation of manganese and cobalt in the raffinate. By sequentially removing manganese, precipitating copper, and precipitating cobalt in the raffinate, cobalt products can be obtained directly. The copper slag after copper precipitation and the cobalt precipitation solution after cobalt precipitation are returned to the sulfuric acid reduction leaching process for reuse. Among them, the manganese slag obtained from manganese removal is leached to extract cobalt to obtain manganese products, while the cobalt-containing solution produced from leaching to extract cobalt is precipitated together with the copper precipitation solution.

[0047] By promptly removing manganese with the raffinate, manganese and cobalt products can be directly obtained through manganese-cobalt separation, ensuring that the manganese concentration in the system is within a safe range. This, in turn, ensures the stable operation of the copper extraction system and the electrowinning system, reducing extractant consumption and electrowinning energy consumption.

[0048] In addition, in this embodiment, the manganese and cobalt are separated by removing manganese and leaching cobalt-copper precipitation-cobalt precipitation in the open-circuit raffinate. This method can directly obtain manganese and cobalt products without introducing impurities. The separation effect is good, and the obtained cobalt product is almost entirely cobalt hydroxide with high purity.

[0049] In manganese removal, sodium persulfate or an SO2 / O2 system is used as the oxidant, and MgO is used as the neutralizing agent. The pH is controlled at 3.5–4.2 to reduce the manganese concentration to no more than 0.5 g / L. The resulting solution and slag are obtained through filtration. The slag is then leached to extract cobalt, and the resulting residue is the manganese product. By using sodium persulfate or an SO2 / O2 system as the oxidant and MgO to adjust the pH, the reaction is rapid and cost-effective. This also avoids introducing impurities, thereby improving separation efficiency and product purity.

[0050] Furthermore, when sodium persulfate is used as the oxidant, the excess coefficient is 3–8, the temperature is 30–90°C, and the reaction time is 1–3 hours. More preferably, the temperature is 50–90°C. Under these conditions, sodium persulfate can achieve better manganese removal effect and efficiency.

[0051] When using an SO2 / O2 system as the oxidant, the SO2 flow rate is 0.1–1.0 L / (L). 溶液 O2 flow rate is 0.8–100 L / (L·h). 溶液 The reaction conditions are 0–90℃ and 1–6 h. Under these conditions, the SO2 / O2 system can achieve good manganese removal effect and efficiency.

[0052] Preferably, when sodium persulfate is used as the oxidant, the preferred temperature is 50–90°C; when an SO2 / O2 system is used as the oxidant, the preferred temperature is 20–60°C. The above preferred temperature range can achieve the best manganese removal effect and better separation effect.

[0053] When extracting cobalt from manganese slag, sulfuric acid is used as the leaching acid, and a reducing leaching method is employed. The reducing agent is selected from at least one of hydrogen peroxide, sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium sulfite, sodium metabisulfite, potassium sulfite, or ammonium sulfite. By using sulfuric acid reducing leaching to extract cobalt from manganese slag, cobalt can be recovered from the slag, avoiding cobalt loss. It should be noted that when the cobalt content in the manganese slag is below 1.5%, it can be directly used as a manganese product. When the solid content is high, such as above 1.5%, cobalt extraction from the manganese slag requires leaching.

[0054] Furthermore, during cobalt leaching, sulfuric acid is used as the leaching acid, the pH is adjusted to 1.5–4.0, the leaching temperature is 0–90℃, and the reaction time is 1–6 hours. Under these conditions, sulfuric acid reduction leaching can recover the vast majority of cobalt, and the manganese product has high purity.

[0055] More preferably, during cobalt leaching, the leaching temperature is controlled at 20–60°C, and the liquid-to-solid ratio is controlled at 5:1. By adopting this temperature and liquid-to-solid ratio, the leaching efficiency can be further improved, resulting in a further reduction in the cobalt content of the manganese product to no more than 0.2%.

[0056] When precipitating copper in the manganese removal solution, MgO is used as a neutralizing agent, and the pH value is controlled at 4.4–6.5, preferably 5.0–6.5. The copper precipitation is then filtered to obtain the copper precipitation solution and copper slag. The copper slag is returned to the sulfuric acid reduction leaching process for further leaching treatment. The copper slag is returned to the system and finally opened at the electrodeposition terminal.

[0057] The copper leaching solution obtained from copper leaching and the cobalt-containing solution obtained from manganese slag leaching are jointly subjected to cobalt precipitation treatment. During cobalt precipitation, MgO or sodium carbonate is used as a neutralizing agent, and the pH is controlled at 7.5–8.5 to reduce the cobalt concentration to no more than 0.02 g / L. The precipitate is the cobalt product, specifically cobalt carbonate or cobalt hydroxide. The cobalt leaching solution is then returned to the sulfuric acid reduction leaching process for further leaching treatment. The cobalt leaching solution is returned to a recyclable solution, which mainly contains water; it is recycled without discharge.

[0058] Furthermore, the neutralizing agent used in each step of this application is MgO, which will not affect the system and the product.

[0059] The present invention will be further described below with reference to specific embodiments:

[0060] The composition of the copper, manganese and cobalt raw materials used in the examples is shown in Table 1 below, and the particle size of the raw materials is -200 mesh 75%.

[0061] Table 1 Raw Material Composition

[0062] Element Cu Co Mn Fe Al2O3 SiO2 MgO content,% 2.03 0.16 0.56 6.35 0.0280 49.32 8.76

[0063] Example 1

[0064] Leaching was carried out under a liquid-to-solid ratio of 3:1, with an excess sodium metabisulfite coefficient of 1.5, a reaction time of 3 hours, a reaction temperature of 40℃, and an acid-to-ore ratio of 160 kg / t. The leaching rates of Cu and Co were 95% and 81%, respectively. The leachate was then subjected to iron removal, extraction, and electrowinning to obtain electrowinning copper.

[0065] The raffinate in the system contains Cu 0.2 g / L, Co 2.2 g / L, Mn 2.3 g / L, and Fe 0.6 g / L.

[0066] Manganese removal was performed using sodium persulfate as the oxidant and MgO as the neutralizing agent. The excess sodium persulfate was 6 times the concentration of Fe, the reaction temperature was 90℃, the pH was 4.0, and the reaction time was 2 hours. After the reaction, the concentrations of Mn, Fe, and Co in the solution decreased to 0.2 g / L, Fe to 0.02 g / L, and Co to 2.1 g / L. The pH of the filtrate after manganese removal was adjusted to 5.5 using MgO, at which point the concentration of Cu in the solution decreased to 0.01 g / L. After copper precipitation, the pH of the solution was adjusted to 8.5, and the cobalt concentration decreased to 0.01 g / L. The precipitate was cobalt hydroxide.

[0067] The manganese slag contained 1.67% Co, 35.47% Mn, and 14.76% Fe. It was leached with sodium metabisulfite as a reducing agent at a dosage of 5 g / L, a liquid-to-solid ratio of 5:1, and a reaction time of 4 h at 30 °C. The leached residue contained 0.1% Co.

[0068] Example 2

[0069] Leaching was carried out under a liquid-to-solid ratio of 3:1, an SO2 excess coefficient of 2.5, a reaction time of 4 hours, a reaction temperature of 30℃, and an acid-to-ore ratio of 140 kg / t. The leaching rates of Cu and Co were 93% and 85%, respectively. The leachate was then subjected to iron removal, extraction, and electrowinning to obtain electrowinning copper.

[0070] The raffinate in the system contains Cu 0.2 g / L, Co 2.4 g / L, Mn 3.0 g / L, and Fe 1.2 g / L.

[0071] Manganese was removed using SO2 / O2 as the oxidant and MgO as the neutralizing agent. The SO2 flow rate was 0.2 L / (L). 溶液 ·h), O2 flow rate is 10L / (L) 溶液 The reaction was carried out at 60℃ and pH 3.5 for 3 hours. After the reaction, the Mn concentration in the solution decreased to 0.1 g / L, and the Co concentration was 2.0 g / L. The pH of the filtrate after manganese removal was adjusted to 6.0 with MgO, at which point the Cu concentration in the solution decreased to 5 mg / L. After copper precipitation, the pH of the solution was adjusted to 8.0, and the cobalt concentration decreased to 0.02 g / L. The precipitate was cobalt hydroxide.

[0072] The manganese-removing slag contained 4.47% Co, 19.47% Mn, and 3.26% Fe. Leaching was performed using SO2 as a reducing agent at a flow rate of 0.4 L / (L). 溶液 The reaction was carried out at 40℃ for 3 hours with a liquid-to-solid ratio of 5:1. The leaching residue contained 0.2% Co.

[0073] The description of this invention is given for illustrative and descriptive purposes only and is not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials, characterized in that, include: Materials containing copper, manganese, and cobalt were leached using sulfuric acid reduction at a temperature of 0–95°C for 2–8 hours, with a final pH of 0.9–2.

0. The leachate was then subjected to iron removal. The iron-removed solution was extracted using a copper extractant, and the extract was back-extracted and electrowinning was performed to obtain electrowinning copper. The raffinate is opened for manganese and cobalt separation to obtain manganese and cobalt products; including: Sodium persulfate or SO2 / O2 system is used as oxidant, MgO is used as neutralizer, and pH is controlled at 3.5-4.2 to remove manganese from the raffinate, resulting in manganese-removed liquid and manganese slag as manganese product; The manganese removal solution is subjected to copper precipitation, and the copper slag after copper precipitation is returned to the reduction leaching process. Using MgO or sodium carbonate as a neutralizing agent, cobalt is precipitated in the copper precipitating solution to directly obtain cobalt products, and the cobalt precipitating solution is then returned to reduction leaching.

2. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 1, characterized in that, When sodium persulfate is used as the oxidant, the excess coefficient is 3-8, the temperature is 30-90℃, and the reaction time is 1-3h. When using an SO2 / O2 system as the oxidant, the SO2 flow rate is 0.1–1.0 L / (L). 溶液 O2 flow rate is 0.8–100 L / (L·h). 溶液 The reaction time is 1 to 6 hours, with a temperature of 0 to 90°C.

3. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 2, characterized in that, Remove manganese from the raffinate to ensure that the manganese concentration in the de-manganese solution does not exceed 0.5 g / L; And / or, when sodium persulfate is used as the oxidant, the temperature is 50–90°C; when the SO2 / O2 system is used as the oxidant, the temperature is 20–60°C.

4. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to any one of claims 1-3, characterized in that, When the cobalt content in the manganese slag is ≥1.5%, the manganese slag is leached to extract cobalt to obtain manganese products. The leaching acid is sulfuric acid, and a reduction leaching method is used. The cobalt-containing solution after leaching is mixed with the copper precipitation solution to jointly precipitate cobalt. During the leaching of cobalt and the sulfuric acid reduction leaching, the reducing agent used is selected from at least one of hydrogen peroxide, sulfur dioxide, flue gas containing sulfur dioxide, sodium thiosulfate, calcium sulfite, sodium sulfite, sodium metabisulfite, potassium sulfite, or ammonium sulfite.

5. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 4, characterized in that, When leaching cobalt, the pH value is 1.5 to 4.0, the leaching temperature is 0 to 90℃, and the reaction time is 1 to 6 hours.

6. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 5, characterized in that, During sulfuric acid reduction leaching, the leaching temperature is 20–60℃, and the liquid-to-solid ratio is 3:

1. And / or, when leaching cobalt, the leaching temperature is 20–60°C and the liquid-to-solid ratio is 5:

1.

7. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 1, characterized in that, The leachate is subjected to iron removal so that the iron concentration in the solution after iron removal is not higher than 0.5 g / L; Among them, the iron removal method is adopted by oxidation precipitation. The oxidant used is at least one of hydrogen peroxide, air and oxygen, and the neutralizing agent is one or more of NaOH, MgO, CaCO3 or Ca(OH)2. The pH is controlled at 2.0 to 4.

8.

8. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 1, characterized in that, During copper plating, MgO is used as a neutralizing agent, and the pH is controlled at 4.4–6.

5. And / or, when precipitating cobalt, use MgO or sodium carbonate as a neutralizing agent and control the pH to 7.5–8.

5.

9. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 1, characterized in that, The copper leaching rate in the leachate obtained by sulfuric acid reduction leaching is ≥93%; the leachate is extracted using a copper extractant composed of an amine extractant and a neutral oxygen-containing extractant; the copper content in the raffinate is ≤0.2g / L.

10. The method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials according to claim 4, characterized in that, The manganese product obtained by leaching cobalt contains ≤0.2% cobalt. The leaching rate of cobalt in the leachate obtained by sulfuric acid reduction leaching is ≥81%; the cobalt product obtained directly by cobalt precipitation is cobalt hydroxide, and the cobalt concentration in the cobalt precipitation solution after cobalt precipitation is ≤0.02g / L.

11. An apparatus for extracting copper, manganese, and cobalt, characterized in that, The apparatus for implementing the method for extracting copper, manganese, and cobalt from copper-, manganese-, and cobalt-containing materials as described in any one of claims 1-6 and 8-10 comprises: The acid leaching unit is used to receive materials containing copper, manganese, and cobalt, as well as copper slag and cobalt precipitation solution, and to perform sulfuric acid reduction leaching treatment to obtain leachate; The iron removal unit is used to receive the leachate and remove iron, resulting in an iron-removed solution. An extraction system is used to receive the iron-removed liquid, extract the iron-removed liquid with a copper extractant, and back-extract the extract. An electrowinning system for receiving the back-extraction solution and performing electrowinning to obtain electrowinning copper; and The manganese-cobalt open-circuit separation system is used to receive the raffinate generated by the extraction system and separate manganese and cobalt to obtain manganese and cobalt products; The manganese-cobalt open-circuit separation system includes: The manganese removal unit is used to remove manganese by using sodium persulfate or SO2 / O2 system as oxidant, MgO as neutralizing agent, and controlling the pH to 3.5-4.2, to obtain manganese removal liquid and manganese slag as manganese product; The copper plating unit is used to receive manganese removal solution and plating copper to obtain copper plating solution and copper slag. The copper plating unit is also connected to the acid leaching unit to return the copper slag to the acid leaching unit. The cobalt immersion unit is used to receive the copper immersion solution and use MgO or sodium carbonate as a neutralizing agent to perform cobalt immersion, directly obtaining cobalt products. The copper immersion unit is also connected to the acid leaching unit to return the cobalt immersion solution after cobalt immersion to the acid leaching unit.

12. The apparatus for extracting copper, manganese, and cobalt according to claim 11, characterized in that, The manganese-cobalt open-circuit separation system further includes: The manganese slag cobalt extraction unit is used to receive manganese slag and leach it to extract cobalt, obtain manganese products, and produce cobalt-containing liquid, which is sent to the cobalt precipitation unit to be mixed with copper precipitation liquid for cobalt precipitation.

Images