Multi-element extraction method for polymetallic manganese ore

Abstract

The present application relates to the technical field of metal smelting extraction, and specifically to a multi-element extraction method for polymetallic manganese ore. The method comprises: ball-milling polymetallic manganese ore; reduction roasting and protectively cooling same; then performing sulfuric acid leaching to obtain a plurality of valuable metals; using an alkaline substance to adjust the pH to remove iron; then adding a precipitant to recover nickel and cobalt; finally transferring a finished manganese sulfate solution to an electrolysis system to prepare electrolytic manganese; subjecting a nickel-cobalt intermediate product to leaching, impurity removal, and extraction for further purification; and then performing evaporative crystallization to obtain a final product, wherein copper can be precipitated by the precipitant to be recovered and to be subjected to electrowinning and purification, or can be recovered by means of replacement after acid leaching, and the leaching efficiency of nickel, cobalt, manganese and copper can all reach 99% or more. The hydrometallurgical process used in the present method can efficiently extract valuable metals such as nickel, cobalt, manganese and copper from the polymetallic manganese ore, is simple and environmentally friendly, has a high rate of recovering nickel, cobalt, manganese and copper from the polymetallic manganese ore, recovers high-purity nickel, cobalt, manganese and copper, can achieve full utilization of resources.

Description

A method for multi-element extraction from polymetallic manganese ore

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese Patent Application No. 202411618279.X, filed on November 13, 2024, entitled "A Multi-element Extraction Method for Polymetallic Manganese Ore", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of metal smelting and extraction technology, specifically to a multi-element extraction method for polymetallic manganese ore. Background Technology

[0004] Polymetallic manganese ore is a mineral resource containing multiple valuable metals (such as manganese, nickel, cobalt, and copper). It is widely found in deep-sea basins at depths of 4000-6000 meters in the Pacific, Indian, and Atlantic Oceans. Due to its high content of nickel, cobalt, copper, and manganese, it is considered an important source of future metal resources. The main processing technology for polymetallic manganese ore is the pyrometallurgical FFC Cambridge process to obtain ferromanganese alloys. This process suffers from low metal recovery rates, high energy consumption, and environmental pollution. Furthermore, most ore processing methods focus on the recovery or treatment of a single metal, neglecting the complexity of multi-metal coexistence and the significant economic potential of other valuable metals. Hydrometallurgical processes typically employ reduction roasting-ammonia leaching. For example, US Patent 3983017 discloses a process using cuprous ions as a catalyst and carbon monoxide as a reducing agent to reduce polymetallic manganese nodules in an ammonia-ammonium carbonate solution. Nickel, cobalt, and copper dissociate from the manganese mineral lattice and complex with ammonia into the solution. However, the recovery rate of cobalt is usually low, below 90%, and manganese exists in the slag as manganese carbonate along with iron. Ammonia leaching typically uses Cu as a catalyst and CO gas as a reducing agent. While it can selectively leach nickel, cobalt, and copper, and separate them from nickel, cobalt, and copper by leaving manganese in the leaching residue, Cu is highly susceptible to oxidation in air. Improper operation can significantly impact the separation effect, and the process requires a high-quality operating environment. Chinese patent CN113528815A discloses a method and application for recovering valuable metals from cobalt-manganese polymetallic oxide ores. This method improves upon conventional ammonia leaching by using a combination of sulfite and ammonium salts, or ammonium sulfite, as the leaching agent and carbonaceous reducing agent to efficiently separate nickel, cobalt, and copper from manganese and iron. The leaching residue, rich in manganese and iron, is then roasted and followed by water leaching to achieve iron-manganese separation. However, this method primarily targets the recovery of nickel, cobalt, and copper, resulting in low manganese recovery. Furthermore, ammonia leaching can easily generate toxic gases, and the separation effect between manganese and iron is not ideal. In addition, manganese can be extracted from manganese ore using sulfation roasting. For example, Chinese patent CN118813953A proposes a method for selective leaching of manganese, nickel, cobalt, and copper from deep-sea polymetallic nodules using ammonium sulfate-activated roasting. This method uses ammonium sulfate or ammonium bisulfate as an activator or sulfating agent to perform solid-state activation roasting on the polymetallic nodules. After the pellets are crushed, they can be directly leached in water without grinding, reducing processing costs. However, this method generates a large amount of corrosive gas during roasting, placing high demands on the roasting equipment.

[0005] Therefore, the traditional processing technology for polymetallic manganese ore is complex, involving the recovery and separation of multiple metals. Thus, it is necessary to develop a low-cost, environmentally friendly, and efficient method for separating manganese, nickel, cobalt, and other metal elements to achieve effective extraction of multiple elements and full utilization of resources. Summary of the Invention

[0006] This application proposes a method for multi-element extraction from polymetallic manganese ore, the specific scheme of which is as follows:

[0007] A method for multi-element extraction from polymetallic manganese ore includes the following steps:

[0008] Step 1: Ball mill the polymetallic manganese ore to obtain ball-milled ore powder, wherein the particle size of the ball-milled ore powder is not greater than 0.074 mm;

[0009] Step 2: The ball-milled mineral powder is subjected to reduction roasting at a temperature of 600-900℃ for 0.5-6 hours. The material after reduction roasting is then subjected to protective cooling, which can be done by one of the following two methods: water cooling or cooling with inert gas, to obtain the cooled material.

[0010] Step 3: Add sulfuric acid to the cooled material from Step 2 to maintain the pH at 0.5-1.5 for acid leaching. The acid leaching temperature is 20-90℃ and the acid leaching time is 2-8 hours. Then perform solid-liquid separation to obtain an acidic leachate.

[0011] Step 4: Add an oxidizing agent to the acidic leachate to oxidize it, and obtain an oxidized solution, wherein the ferrous content in the oxidized solution is not greater than 0.001 g / L;

[0012] Step 5: Mix the oxidized liquid and alkaline substance in a reaction vessel by convection, control the pH of the mixed solution system to 3.0-4.5 to remove iron, mix for 0.5-6 hours, mix at 25-60℃, and then perform solid-liquid separation to obtain the iron-removed liquid, wherein the iron content in the iron-removed liquid is not greater than 100ppm.

[0013] Step 6: Add sulfide precipitant to the iron-removed liquid and allow it to settle for 0.5-2 hours. Perform solid-liquid separation and allow the filtrate to stand for 8-24 hours. Perform a second solid-liquid separation. The second filtrate is the finished manganese sulfate solution. Combine the two filter residues to form nickel-cobalt sulfide intermediate. The finished manganese sulfate solution contains not less than 38 g / L of manganese and not more than 1 ppm of nickel, cobalt, and copper.

[0014] Step 7: Electrolyze the finished manganese sulfate solution to obtain electrolytic manganese product; leach, remove impurities and extract the nickel-cobalt sulfide intermediate to obtain battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution, and evaporate and crystallize the battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution to obtain battery-grade nickel sulfate crystals and battery-grade cobalt sulfate crystals.

[0015] Furthermore, in step 6, the combined filter residues from the two steps also yield copper sulfide intermediate. In step 7, the copper sulfide intermediate is leached, impurity removed, and extracted to obtain a high-purity copper sulfate solution. The high-purity copper sulfate solution is then electrowinning to obtain a cathode copper product.

[0016] Alternatively, after step 3 and before step 4, iron powder is added to the acidic leaching solution to carry out a displacement reaction. The amount of iron powder added is 0.91-0.96 times the copper content in the acidic leaching solution. During the displacement process, the system temperature is 65-80℃ and the reaction time is 0.5-1h. Copper powder and copper-free acidic leaching solution are obtained by filtration and separation. In step 4, an oxidant is added to the copper-free acidic leaching solution for oxidation.

[0017] Further, in step 1, the polymetallic manganese ore contains: Mn: 15%-40%; Ni+Co+Cu: 2%-3%; Fe: 5%-15%; Mn / Fe: 1-6. The composition and proportions described are those of the dried polymetallic manganese ore, i.e., the composition and proportions of the water-free polymetallic manganese ore.

[0018] Furthermore, in step 2, the reducing agent in the reduction roasting process is carbon monoxide, hydrogen, sulfur dioxide, or reducing coal powder. The reducing coal powder includes anthracite, semi-coke, bituminous coal, and lignite. The amount of reducing coal powder added is 20-30% of the mass of the mineral powder.

[0019] Furthermore, when the cooling method in step 2 is water cooling, the amount of water added for water cooling is 4-7 times the mass of the material after reduction roasting.

[0020] Furthermore, when the cooling method in step 2 is to introduce inert gas, in step 3, before adding sulfuric acid to the cooled material, water is first added to the cooled material to slurry it, and the amount of water added is 4-7 times the mass of the cooled material.

[0021] Further, the oxidant in step 4 is hydrogen peroxide or the ball-milled mineral powder obtained in step 1: when the oxidant is hydrogen peroxide, the amount of hydrogen peroxide added is 1.05-2.0 times the theoretical amount required for complete reaction, the reaction time is 0.5-1 h, and the temperature is 20-60℃; when the oxidant is ball-milled mineral powder, the amount of mineral powder added is 1.0-1.5 times the theoretical amount required for complete reaction, the reaction time is 0.5-2 h, the temperature is 20-90℃, and the pH of the reaction system is maintained at 0.5-1.5.

[0022] Furthermore, in step 5, the oxidized liquid and alkaline substance are mixed in a convection manner in a reactor equipped with a stirrer and baffles, while stirring is performed to increase turbulence and ensure thorough mixing.

[0023] Furthermore, the alkaline substance mentioned in step 5 is one or more of ammonia, calcium carbonate, calcium oxide, and liquid alkali.

[0024] Further, the precipitant in step 6 is one or more of sodium sulfide, sodium sulfide nonahydrate, and sodium thiram. The amount of precipitant used is 1.0-2.5 times the theoretical amount required for complete reaction, and the precipitation endpoint is controlled at 5.6. <pH<7.0。

[0025] Furthermore, in step 7, ammonium sulfate and selenium dioxide additives are added to the finished manganese sulfate solution before electrowinning, controlling the concentration of ammonium sulfate in the solution before electrowinning to be 50-130 g / L and the amount of selenium dioxide added to be 10-100 g / L. 3 The electrolysis temperature during the electrowinning process is 35-45℃, and the electrolysis current density is 350-450 A / m. 2 The electrode plate spacing is 70-80mm; the nickel-cobalt sulfide intermediate is subjected to deep purification by sulfuric acid leaching, alkali removal, P204 extraction, and P507 extraction in sequence. Attached Figure Description

[0026] The embodiments of this application will be further described below with reference to the accompanying drawings, wherein:

[0027] Figure 1 shows the process flow diagrams of embodiments 1-4 of this method;

[0028] Figure 2 shows a process flow diagram of Embodiment 5 of this method. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description, in conjunction with the accompanying drawings, provides specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0030] A method for multi-element extraction from polymetallic manganese ore includes the following steps:

[0031] Step 1: Ball mill the polymetallic manganese ore to obtain ball-milled ore powder with a particle size not exceeding 0.074 mm. The polymetallic manganese ore contains: Mn 15%-40%; Ni+Co+Cu 2%-3%; Fe 5%-15%; Mn / Fe ratio 1-6; and the balance being other trace elements and non-metallic elements. This composition and content are based on the composition and content after drying to remove moisture.

[0032] Step 2: The ball-milled mineral powder is subjected to reduction roasting at a temperature of 600-900℃ for 0.5-6 hours. The roasted material is then subjected to protective cooling, either by water cooling or by introducing inert gas, to obtain the cooled material. The reducing agent is carbon monoxide, hydrogen, sulfur dioxide, or reducing coal powder, including anthracite, semi-coke, bituminous coal, and lignite. The amount of reducing coal powder added is 20-30% of the mass of the ball-milled mineral powder. This application focuses on reducing and roasting polymetallic manganese ore to reduce various elements within it. Protective cooling, achieved by introducing inert gas or water cooling, prevents MnO from being re-oxidized by air, significantly improving the reduction effect of manganese.

[0033] Step 3: Add sulfuric acid to the cooled material from Step 2, maintaining the pH at 0.5-1.5, for acid leaching. The leaching temperature is 20-90℃, and the leaching time is 2-8 hours. Then, perform solid-liquid separation to obtain an acidic leachate. When the cooling method is water cooling, the amount of water added is 4-7 times the mass of the material after reduction roasting. When the cooling method is inert gas, before adding sulfuric acid to the cooled material in Step 3, add water to slurry the material, with the amount of water being 4-7 times the mass of the cooled material. This application utilizes sulfuric acid leaching, which can achieve efficient leaching of multiple elements in polymetallic manganese ore, avoiding incomplete leaching of useful elements. Compared with ammonia leaching, it significantly improves the cobalt leaching rate. Compared with the stringent equipment requirements of sulfation roasting, it can reduce equipment costs and equipment wear.

[0034] Step 4: Add an oxidizing agent to the acidic leachate for oxidation to obtain an oxidized solution. The ferrous content in the oxidized solution is not greater than 0.001 g / L. The oxidizing agent is hydrogen peroxide or the ball-milled mineral powder obtained in Step 1. When the oxidizing agent is hydrogen peroxide, the amount of hydrogen peroxide added is 1.05-2.0 times the theoretical amount required for complete reaction, the reaction time is 0.5-1 h, and the temperature is 20-60℃. When the oxidizing agent is ball-milled mineral powder, the amount of mineral powder added is 1.0-1.0 times the theoretical amount required for complete reaction. The reaction time is 0.5-2 hours, the temperature is 20-90℃, and the pH of the reaction system is maintained at 0.5-1.5. After the leaching of multiple elements is completed, the solution is oxidized to completely oxidize ferrous iron to ferric iron, so that the multiple elements can be fully recovered in subsequent extraction processes such as precipitation and sulfidation. At the same time, the oxidant can be ball-milled mineral powder. By utilizing the oxidizing property of MnO2 in the ball-milled mineral powder, the oxidation of ferrous iron can be completed without introducing additional impurities.

[0035] Step 5: The oxidized liquid and alkaline substance are mixed and stirred in a reaction vessel equipped with a stirrer and baffles in a convective manner. The strong stirring and baffles make the mixing system highly turbulent, which can efficiently mix and transfer mass. The pH of the mixed solution system is controlled at 3.0-4.5 to remove iron and aluminum. The mixing time is 0.5-6 hours and the mixing temperature is 25-60℃. Then, solid-liquid separation is performed to obtain the iron-removed liquid. The iron content in the iron-removed liquid is not greater than 100ppm. The alkaline substance is one or more of ammonia, calcium carbonate, calcium oxide, and liquid alkali. When the alkaline substance is calcium carbonate or calcium oxide, it is prepared into a slurry with a mass content of 10-30% for convective mixing.

[0036] Step 6: Add a sulfide precipitant to the iron-removed liquid, allowing it to settle for 0.5-2 hours for solid-liquid separation. After the filtrate has stood for 8-24 hours, perform a second solid-liquid separation. The second filtrate is the finished manganese sulfate solution. Combine the residues from both filtrates to form a nickel-cobalt-copper sulfide intermediate. The finished manganese sulfate solution contains no less than 38 g / L of manganese and no more than 1 ppm of nickel, cobalt, and copper. The precipitant is one or more of sodium sulfide, sodium sulfide nonahydrate, and sodium formaldehyde sulfide. The amount of precipitant used is 1.0-2.5 times the theoretical amount required for complete reaction, and the precipitation endpoint is controlled at 5.6. <pH<7.0。

[0037] Step 7: Electrolyze the finished manganese sulfate solution to obtain electrolytic manganese product. Before electrowinning, add ammonium sulfate and selenium dioxide additives to the finished manganese sulfate solution to ensure that the concentration of ammonium sulfate in the system before the electrowinning reaction is 50-130 g / L and the concentration of selenium dioxide is 10-100 g / L. 3 To improve the conductivity of the electrolyte in the system, thereby enhancing the effect and efficiency of electrodeposition; the electrolysis temperature during electrodeposition is 35-45℃, and the electrolysis current density is 350-450 A / m. 2 The electrode plate spacing is 70-80mm. The intermediate nickel-cobalt-sulfide product is leached with sulfuric acid, purified by adding alkali, extracted with P204 and P507 to obtain battery-grade nickel sulfate solution, battery-grade cobalt sulfate solution and high-purity copper sulfate solution. The battery-grade nickel sulfate and battery-grade cobalt sulfate solutions are evaporated and crystallized to obtain battery-grade nickel sulfate crystals and battery-grade cobalt sulfate crystals. The high-purity copper sulfate solution is electrowinning to obtain cathode copper product.

[0038] Alternatively, following the same steps, after step 3 and before step 4, iron powder is added to the acidic leaching solution to initiate a displacement reaction. The amount of iron powder added is 0.91-0.96 times the copper content in the acidic leaching solution. During the displacement process, the system temperature is 65-80℃, and the reaction time is 0.5-1 hour. Copper powder and copper-free acidic leaching solution are obtained by filtration. In step 4, an oxidant is added to the copper-free acidic leaching solution for oxidation. Adding a sulfide precipitant prevents the formation of copper sulfide.

[0039] This application further improves the separation and recovery of multi-metal elements by adjusting and controlling parameters such as pH range, mixing method, and reaction temperature in each step. The leaching rates of nickel, cobalt, manganese, and copper are all greater than 99%, and the recovery rates are all greater than 90%. Among them, the recovery rates of manganese, nickel, and cobalt can reach more than 96%.

[0040] The specific implementation method is as follows:

[0041] Example 1:

[0042] Step 1: Weigh 150 g of polymetallic manganese ore. After drying the polymetallic manganese ore, it is detected that the content of Mn is 31.71%, Ni is 1.44%, Co is 0.13%, Cu is 1.19%, and Fe is 6.16%. The original ore powder contains about 20% water. The undried polymetallic manganese ore is ball-milled and crushed to obtain the ball-milled ore powder with a particle size not greater than 0.074 mm.

[0043] Step 2: The ball-milled ore powder is subjected to reduction roasting. The reducing agent is anthracite, with an addition amount of 35 g. The reduction roasting temperature is 700 °C, and the roasting time is 2 h. Subsequently, the material after reduction roasting is water-cooled with 0.7 L of water added to obtain the cooled material.

[0044] Step 3: The cooled material in Step 2 is acid-leached with sulfuric acid to maintain a pH of 1. The acid-leaching temperature is 40 °C, and the acid-leaching time is 2 h. Then, solid-liquid separation is carried out to obtain the acidic leachate. The leaching rates of nickel, cobalt, manganese, and copper are 99.21%, 99.69%, 99.65%, and 99.42% respectively.

[0045] Step 4: After detection, the content of ferrous iron in the acidic leachate is 0.5 g / L. 0.42 g of 30% hydrogen peroxide is added to the acidic leachate for oxidation. The reaction time is 1 h, and the temperature is 40 °C to obtain the oxidized solution with a ferrous iron content of 0 g / L in the oxidized solution.

[0046] Step 5: The oxidized solution and ammonia water are mixed in a reaction kettle with strong stirring and baffles in a countercurrent manner. The pH of the mixed solution system is controlled at 4.0 to remove iron. The mixing time is 2 h, and the mixing temperature is 60 °C. Then, solid-liquid separation is carried out to obtain the iron-removed solution with an iron content not greater than 100 ppm in the iron-removed solution.

[0047] Step 6: Sodium sulfide precipitant is added to the iron-removed solution with a dosage of 1.0 - 1.5 times the theoretical dosage for complete reaction. The precipitation time is 1 h, and the precipitation end point is controlled at 5.6 < pH < 7.0. Solid-liquid separation is carried out. The filtrate is allowed to stand for 8 hours and then undergoes secondary solid-liquid separation. The second filtrate is the finished product of manganese sulfate solution. The manganese content in the finished product of manganese sulfate solution is 42 g / L, and the contents of nickel, cobalt, and copper are all 1 ppm, and the contents of iron and aluminum are < 1 ppm. The two filter residues are combined into the nickel-cobalt-copper intermediate product.

[0048] Step 7: Ammonium sulfate is added to the finished product of manganese sulfate solution to adjust ammonia, with a concentration of ammonium sulfate of 120 g / L, and selenium dioxide is added to make the concentration of selenium dioxide 70 g / m 3 , and then electrowinning is carried out to obtain electrolytic manganese products. The electrolysis temperature is 40 °C, and the current density is 400 A / m 2The electrode plate spacing is 70 mm, the manganese recovery rate is 97.78%, and the electrolytic manganese purity is 99.7%. The nickel-cobalt-sulfide intermediate is subjected to sulfuric acid leaching, alkali removal, P204 extraction, and P507 extraction to obtain battery-grade nickel sulfate solution, battery-grade cobalt sulfate solution, and high-purity copper sulfate solution. The battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution are evaporated and crystallized to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate. The copper sulfate solution is electrowinning to obtain cathode copper product. The recovery rates of nickel, cobalt, and copper are 96.6%, 97.0%, and 92.5%, respectively.

[0049] Example 2:

[0050] Step 1: Weigh 150g of polymetallic manganese ore. After drying, the polymetallic manganese ore is tested and found to contain Mn: 37.07%, Ni: 1.38%, Co: 0.13%, Cu: 1.19%, Fe: 12.84%. The original ore powder contains about 21% water. The undried polymetallic manganese ore is ball-milled to obtain ball-milled ore powder with a particle size not greater than 0.074mm.

[0051] Step 2: The ball-milled mineral powder is subjected to reduction roasting. The reducing agent is anthracite, the amount of anthracite added is 30g, the reduction roasting temperature is 800℃, and the roasting time is 3h. Then the reduced roasted material is cooled under a nitrogen atmosphere to obtain the cooled material.

[0052] Step 3: Add 0.7L of water to the cooled material from Step 2, then add sulfuric acid to maintain the pH at 1.2 for acid leaching. The acid leaching temperature is 60℃ and the acid leaching time is 3 hours. Then perform solid-liquid separation to obtain an acidic leachate. The leaching rates of nickel, cobalt, manganese, and copper are 99.5%, 99.3%, 98.9%, and 99.1%, respectively.

[0053] Step 4: The ferrous content in the acidic leachate is 3 g / L. Add 3.6 g of ball-milled mineral powder to the acidic leachate for oxidation. The reaction time is 0.5 h and the temperature is 60 °C. Sulfate is added to maintain the pH of the reaction system at 0.5-1.5 to obtain the oxidized solution, in which the ferrous content is 0 g / L.

[0054] Step 5: Mix the oxidized liquid and 30% calcium carbonate slurry in a reaction vessel equipped with a strong stirrer and baffles in a convection manner, control the pH of the mixed solution system to 3.5 to remove iron, mix for 5 hours, mix at 50°C, and then perform solid-liquid separation to obtain the iron-removed liquid, wherein the iron content in the iron-removed liquid is not greater than 100 ppm.

[0055] Step 6: Add sodium sulfide precipitant to the iron-removed liquid, the amount of which is 2.0 times the theoretical amount for complete reaction, the precipitation time is 1.0 h, the endpoint pH is 6.8, and solid-liquid separation is performed. After the filtrate has been allowed to stand for 8 hours, a second solid-liquid separation is performed. The second filtrate is the finished manganese sulfate solution. The two filter residues are combined to form nickel-cobalt-copper sulfide intermediate. The finished manganese sulfate solution has a manganese content of 40 g / L, a nickel, cobalt, and copper content of 1 ppm, and an iron and aluminum content of <1 ppm.

[0056] Step 7: Add ammonium sulfate to the finished manganese sulfate solution to adjust the ammonia concentration, wherein the ammonium sulfate concentration is 50 g / L, and add selenium dioxide to make the selenium dioxide concentration 90 g / L. 3 Subsequently, electrowinning was performed to obtain electrolytic manganese product. The electrolysis temperature was 45℃ and the current density was 380A / m³. 2 The electrode plate spacing is 80 mm, the manganese recovery rate is 97.20%, and the electrolytic manganese purity is 99.7%. The nickel-cobalt-sulfide intermediate is subjected to sulfuric acid leaching, alkali removal, P204 extraction, and P507 extraction to obtain battery-grade nickel sulfate solution, battery-grade cobalt sulfate solution, and high-purity copper sulfate solution. The battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution are evaporated and crystallized to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate. The copper sulfate solution is electrowinning to obtain cathode copper product. The recovery rates of nickel, cobalt, and copper are 97.1%, 97.2%, and 92.1%, respectively.

[0057] Example 3:

[0058] Step 1: Weigh 150g of polymetallic manganese ore. After drying, the polymetallic manganese ore is tested and found to contain Mn: 32.61%, Ni: 1.42%, Co: 0.14%, Cu: 1.10%, Fe: 5.80%. The original ore powder contains about 20% water. The undried polymetallic manganese ore is ball-milled to obtain ball-milled ore powder with a particle size not greater than 0.074mm.

[0059] Step 2: The ball-milled mineral powder is subjected to reduction roasting with hydrogen as the reducing agent. The reduction roasting temperature is 900℃ and the roasting time is 2h. The material after reduction roasting is then cooled in a helium atmosphere to obtain the cooled material.

[0060] Step 3: Add 0.8L of water to the cooled material from Step 2, then add sulfuric acid to maintain the pH at 0.5 for acid leaching. The acid leaching temperature is room temperature (20℃), and the acid leaching time is 8 hours. Then perform solid-liquid separation to obtain an acidic leachate. The leaching rates of nickel, cobalt, manganese, and copper are 99.6%, 99.5%, 99.1%, and 99.8%, respectively.

[0061] Step 4: The content of ferrous iron in the acidic leaching solution is 0.8 g / L. Add 1.7 g of polymetallic manganese ore powder to the acidic leaching solution for oxidation. The reaction time is 2 h and the temperature is 40 °C to obtain the oxidized solution. Sulfuric acid is added to maintain the pH of the reaction system at 0.5 - 1.5. The content of ferrous iron in the oxidized solution is 0 g / L;

[0062] Step 5: Mix the oxidized solution and calcium oxide slurry (mass content of 20%) in a reaction kettle equipped with strong stirring and baffles in a countercurrent manner. Control the pH of the mixed solution system to 4.5 to remove iron. The mixing time is 6 h and the mixing temperature is 30 °C. Then, solid-liquid separation is carried out to obtain the solution after iron removal. The iron content in the solution after iron removal is not more than 100 ppm;

[0063] Step 6: Add sodium dimethyldithiocarbamate precipitant to the solution after iron removal. The dosage is 1.0 times the theoretical dosage for complete reaction. The precipitation time is 2 h. Control the precipitation end point at 5.6 < pH < 7.0. Solid-liquid separation is carried out. The filtrate is allowed to stand for 8 hours and then secondary solid-liquid separation is carried out. The second filtrate is the finished manganese sulfate solution. The manganese content in the finished manganese sulfate solution is 41 g / L, and the contents of nickel, cobalt, and copper are all 1 ppm. The contents of iron and aluminum are < 1 ppm;

[0064] Step 7: Add ammonium sulfate to the finished manganese sulfate solution to adjust ammonia. The concentration of ammonium sulfate is 80 g / L, and add selenium dioxide to make the concentration of selenium dioxide 100 g / m 3 , and then electrolytic deposition is carried out to obtain electrolytic manganese products. The electrolytic temperature is 35 °C, the current density is 420 A / m 2 , the electrode plate spacing is 80 mm, the recovery rate of manganese is 96.91%, and the purity of electrolytic manganese is 99.7%. The sulfide nickel-cobalt-copper intermediate product is obtained through sulfuric acid leaching, alkali addition for impurity removal, P204 extraction, and P507 extraction to obtain battery-grade nickel sulfate solution, battery-grade cobalt sulfate solution, and high-purity copper sulfate solution. The battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution are obtained through evaporation crystallization to obtain battery-grade nickel sulfate and battery-grade cobalt. The copper sulfate solution is obtained through electrolytic deposition to obtain cathode copper products. The recovery rate of nickel is 96.5%, the recovery rate of cobalt is 97.2%, and the recovery rate of copper is 90.6%.

[0065] Example 4:

[0066] Weigh 150 g of polymetallic manganese ore. After drying the polymetallic manganese ore, detect that Mn: 28%, Ni: 1.2%, Co: 0.3%, Cu: 1.5%, Fe: 8.2%. The original ore powder contains about 20% water. Grind and crush the undried polymetallic manganese ore to obtain the milled ore powder. The particle size of the ore powder is not more than 0.074 mm;

[0067] Step 2: The ball-milled ore powder is subjected to reduction roasting. The reducing agent is anthracite, the addition amount of anthracite is 40 g, the reduction roasting temperature is 700 °C, and the roasting time is 5 h. Subsequently, the materials after reduction roasting are added with 0.65 L of water for cooling to obtain the cooled materials.

[0068] Step 3: The cooled materials in Step 2 are acid-leached with sulfuric acid to maintain the pH at 1.0. The acid-leaching temperature is 90 °C, and the acid-leaching time is 1 h. Then, solid-liquid separation is carried out to obtain an acidic leachate. The leaching rates of nickel, cobalt, manganese, and copper are 99.7%, 99.5%, 99.3%, and 99.8% respectively.

[0069] Step 4: The content of ferrous iron in the acidic leachate is 10.6 g / L. 21 g of ball-milled ore powder is added to the acidic leachate for oxidation. The reaction time is 1 h, and the temperature is 80 °C. Sulfuric acid is added to maintain the pH of the reaction system at 1.0 to obtain the oxidized solution. The content of ferrous iron in the oxidized solution is 0 g / L.

[0070] Step 5: The oxidized solution and ammonia water are mixed in a reaction kettle equipped with strong stirring and baffles in a countercurrent manner. The pH of the mixed solution system is controlled at 3.0 to remove iron. The mixing time is 0.5 h, and the mixing temperature is 60 °C. Then, solid-liquid separation is carried out to obtain the solution after iron removal. The iron content in the solution after iron removal is not more than 100 ppm.

[0071] Step 6: A sodium sulfide precipitant is added to the solution after iron removal, and the dosage is 2.5 times the theoretical dosage for complete reaction. The precipitation time is 0.5 h. The pH at the precipitation end point is controlled at 5.6 < pH < 7.0. Solid-liquid separation is carried out. The filtrate is allowed to stand for 8 hours and then subjected to secondary solid-liquid separation. The second filtrate is the finished manganese sulfate solution. The manganese content in the finished manganese sulfate solution is 40 g / L, and the contents of nickel, cobalt, and copper are all 1 ppm, and the contents of iron and aluminum are < 1 ppm.

[0072] Step 7: Ammonium sulfate is added to the finished manganese sulfate solution to adjust ammonia, where the concentration of ammonium sulfate is 100 g / L, and selenium dioxide is added to make the concentration of selenium dioxide 60 g / m 3 , and then electrowinning is carried out to obtain an electrolytic manganese product. The electrolysis temperature is 45 °C, and the current density is 350 A / m 2The electrode plate spacing is 80 mm, the manganese recovery rate is 97.4%, and the electrolytic manganese purity is 99.7%. The nickel-cobalt-sulfide intermediate is subjected to sulfuric acid leaching, alkali removal, P204 extraction, and P507 extraction to obtain battery-grade nickel sulfate solution, battery-grade cobalt sulfate solution, and high-purity copper sulfate solution. The battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution are evaporated and crystallized to obtain battery-grade nickel sulfate and battery-grade cobalt sulfate. The copper sulfate solution is electrowinning to obtain cathode copper product. The recovery rates of nickel, cobalt, and copper are 97.8%, 96.8%, and 93.9%, respectively.

[0073] Example 5:

[0074] The process conditions were the same as in Example 4. After step 3 and before step 4, iron powder was added to the acidic leaching solution to initiate a displacement reaction. The amount of iron powder added was 1.70 g, the displacement temperature was 70°C, and the reaction time was 0.5 h. Copper powder and a copper-free acidic leaching solution were obtained by filtration. Subsequently, the subsequent steps, such as adding an oxidant to the copper-free acidic leaching solution in step 4, were continued. The final recovery rates were 96.6% for nickel, 97.0% for cobalt, and 98.8% for copper.

[0075] Comparative Example 1:

[0076] Step 1: Weigh 150g of polymetallic manganese ore. After drying, the polymetallic manganese ore is tested to determine its content: Mn: 31.71%, Ni: 1.44%, Co: 0.13%, Cu: 1.19%, Fe: 6.16%. The undried polymetallic manganese ore is ball-milled to obtain ball-milled mineral powder with a particle size not greater than 0.074mm.

[0077] Step 2: The ball-milled mineral powder is subjected to reduction roasting. The reducing agent is anthracite, and the amount of anthracite added is 30g. The reduction roasting temperature is 700℃ and the roasting time is 3h. Then the material after reduction roasting is naturally cooled.

[0078] Step 3: Add sulfuric acid to the cooled material from Step 2 to maintain the pH at 1 for acid leaching for 2 hours, then perform solid-liquid separation to obtain an acidic leachate; the leaching rates of nickel, cobalt, manganese, and copper are 84.15%, 88.1%, 75.07%, and 94.12%, respectively.

[0079] The process conditions and raw materials used in steps 4-7 were the same as in Example 1. The final recovery rates were 73.66% for manganese, 81.94% for nickel, 85.72% for cobalt, and 87.57% for copper.

[0080] Comparative Example 2:

[0081] The ammonia leaching method described in Chinese patent CN113528815A involves mixing cobalt-manganese polymetallic oxide ore, ammonia water, a leaching agent, and a carbonaceous reducing agent, followed by stirring and leaching to obtain a leaching slurry. The main components of the cobalt-manganese polymetallic oxide ore are Mn 21.57%, Fe 15.46%, Ni 0.38%, Co 0.41%, and Cu 0.076%. The leaching agent includes ammonium sulfite, and the carbonaceous reducing agent includes anthracite. The mass of the anthracite is three times the Mn content in the cobalt-rich crust. The ammonia water concentration in the slurry is 3 mol / L, the ammonium sulfite concentration is 1.5 mol / L, and the liquid-to-solid ratio is 10:1. The leaching temperature is 80℃, the leaching time is 2 hours, and after filtration, a leaching residue rich in manganese and iron and a leaching solution rich in nickel, cobalt, and copper are obtained. The leaching rates of nickel, cobalt, and copper in the nickel-cobalt-rich leachate were 78.52%, 93.51%, and 91.01%, respectively, while the leaching rates of manganese and iron in the manganese-iron-rich leachate were 6.74% and 5.98%, respectively.

[0082] The foregoing description of some exemplary embodiments of this application is intended to explain this application only and does not constitute a limitation on the scope of protection of this application. Features in these embodiments can be recombined in a suitable manner, and the resulting solutions are still within the scope of protection claimed by this application. All other embodiments obtained by those skilled in the art based on the above embodiments without inventive effort, that is, all modifications, equivalent substitutions, and improvements made within the spirit and principles of this application, fall within the scope of protection claimed by this application.

Claims

1. A method for multi-element extraction from polymetallic manganese ore, comprising the following steps: Step 1: Ball mill the polymetallic manganese ore to obtain ball-milled ore powder, wherein the particle size of the ball-milled ore powder is not greater than 0.074 mm; Step 2: The ball-milled mineral powder is subjected to reduction roasting at a temperature of 600-900℃ for 0.5-6 hours. The material after reduction roasting is then subjected to protective cooling, which can be done by one of the following two methods: water cooling or cooling with inert gas, to obtain the cooled material. Step 3: Add sulfuric acid to the cooled material from Step 2 to maintain the pH at 0.5-1.5 for acid leaching. The acid leaching temperature is 20-90℃ and the acid leaching time is 2-8 hours. Then perform solid-liquid separation to obtain an acidic leachate. Step 4: Add an oxidizing agent to the acidic leachate to oxidize it, and obtain an oxidized solution, wherein the ferrous content in the oxidized solution is not greater than 0.001 g / L; Step 5: Mix the oxidized liquid and alkaline substance in a reaction vessel by convection, control the pH of the mixed solution system to 3.0-4.5 to remove iron, mix for 0.5-6 hours, mix at 25-60℃, and then perform solid-liquid separation to obtain the iron-removed liquid, wherein the iron content in the iron-removed liquid is not greater than 100ppm. Step 6: Add sulfide precipitant to the iron-removed liquid and allow it to settle for 0.5-2 hours. Perform solid-liquid separation and allow the filtrate to stand for 8-24 hours. Perform a second solid-liquid separation. The second filtrate is the finished manganese sulfate solution. Combine the two filter residues to form nickel-cobalt sulfide intermediate. The finished manganese sulfate solution contains not less than 38 g / L of manganese and not more than 1 ppm of nickel, cobalt, and copper. Step 7: Electrolyze the finished manganese sulfate solution to obtain electrolytic manganese product; leach, remove impurities and extract the nickel-cobalt sulfide intermediate to obtain battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution, and evaporate and crystallize the battery-grade nickel sulfate solution and battery-grade cobalt sulfate solution to obtain battery-grade nickel sulfate crystals and battery-grade cobalt sulfate crystals.

2. A method of multi-element extraction of a polymetallic manganese ore according to claim 1, wherein, In step 6, the filter residues from both steps are combined to obtain copper sulfide intermediate. In step 7, the copper sulfide intermediate is leached, impurity removed, and extracted to obtain a high-purity copper sulfate solution. The high-purity copper sulfate solution is then electrowinning to obtain a cathode copper product.

3. A method of multi-element extraction of polymetallic manganese ores according to claim 1, wherein, After step 3 and before step 4, iron powder is added to the acidic leaching solution to carry out a displacement reaction. The amount of iron powder added is 0.91-0.96 times the copper content in the acidic leaching solution. The system temperature during the displacement process is 65-80℃, and the reaction time is 0.5-1h. Copper powder and copper-removed acidic leaching solution are obtained by filtration and separation. In step 4, an oxidant is added to the copper-removed acidic leaching solution for oxidation.

4. The method for multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, The composition of the polymetallic manganese ore after drying in step 1 is as follows: Mn: 15%-40%; Ni+Co+Cu: 2%-3%; Fe: 5%-15%; Mn / Fe: 1-6.

5. The method for multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, In step 2, the reducing agent in the reduction roasting process is carbon monoxide, hydrogen, sulfur dioxide, or reducing coal powder. The reducing coal powder includes anthracite, semi-coke, bituminous coal, and lignite. The amount of reducing coal powder added is 20-30% of the mass of the mineral powder.

6. The method for multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, When the cooling method in step 2 is water cooling, the amount of water added for water cooling is 4-7 times the mass of the material after reduction roasting.

7. The method of multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, In step 2, when the cooling method is to introduce inert gas, in step 3, before adding sulfuric acid to the cooled material, water is added to the cooled material to slurry it, and the amount of water added is 4-7 times the mass of the cooled material.

8. The method for multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, The oxidant in step 4 is hydrogen peroxide or the ball-milled mineral powder obtained in step 1: When the oxidant is hydrogen peroxide, the amount of hydrogen peroxide added is 1.05-2.0 times the theoretical amount required for complete reaction, the reaction time is 0.5-1 h, and the temperature is 20-60℃; when the oxidant is ball-milled mineral powder, the amount of mineral powder added is 1.0-1.5 times the theoretical amount required for complete reaction, the reaction time is 0.5-2 h, the temperature is 20-90℃, and the pH of the reaction system is maintained at 0.5-1.

5.

9. The method of multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, In step 5, the oxidized liquid and alkaline substance are mixed in a convection manner in a reaction vessel equipped with a stirrer and baffles, while stirring is performed simultaneously.

10. The method for multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, The alkaline substance mentioned in step 5 is one or more of ammonia, calcium carbonate, calcium oxide, and liquid alkali.

11. The method of multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, The precipitant mentioned in step 6 is one or more of sodium sulfide, sodium sulfide nonahydrate, and sodium thiram. The amount of precipitant used is 1.0-2.5 times the theoretical amount required for complete reaction, and the precipitation endpoint is controlled at 5.

6. <pH<7.0。 12. The method of multi-element extraction of a polymetallic manganese ore according to any one of claims 1 to 3, wherein, The finished manganese sulfate solution in step 7 is added with ammonium sulfate and selenium dioxide additives before electrodeposition, the ammonium sulfate concentration in the solution before electrodeposition is controlled to be 50-130 g / L, the selenium dioxide addition amount is 10-100 g / m 3 , the electrolysis temperature during electrodeposition is 35-45℃, the electrolysis current density is 350-450 A / m 2 , the electrode plate spacing is 70-80 mm; the nickel-cobalt sulfide intermediate product is sequentially subjected to deep purification by using sulfuric acid leaching, alkali removal, P204 extraction and P507 extraction.

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