Method for recovering manganese in laterite-nickel ore

Abstract

The invention provides a method for recovering manganese from laterite-nickel ore. The method comprises the following steps: sequentially carrying out precipitation reaction and liquid-solid separation on substances comprising an alkaline precipitator, an oxidant and a nickel-cobalt-manganese-containing heavy metal solution to obtain a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution. According to the principle, an oxidizing agent is added in the precipitation process, the redox environment in the nickel-cobalt-manganese containing heavy metal solution is changed, and manganese can be precipitated together with nickel and cobalt under the alkaline condition. Specifically, after a proper oxidant is added into the solution, divalent manganese can be oxidized into a high valence state, so that the divalent manganese can form stable and insoluble precipitates more easily under an alkaline condition, and the stable and insoluble precipitates and nickel and cobalt hydroxides are separated out together, thereby realizing high-efficiency recovery of manganese.

Description

Technical Field

[0001] The present invention relates to the technical field of laterite nickel ore, and in particular, to a method for recovering manganese from laterite nickel ore. Background Art

[0002] After the laterite nickel ore is leached and iron and aluminum are removed, a solution containing nickel, cobalt, manganese, and magnesium is obtained. Industrially, a precipitant is generally used to precipitate nickel and cobalt. During the precipitation process, a reducing atmosphere is controlled to discharge manganese out of the precipitate as much as possible. Part of the manganese precipitates in the product, and part enters the tailings and is discharged in the liquid phase. Such a situation results in the non-recovery of manganese and a great waste of resources. Summary of the Invention

[0003] The main object of the present invention is to provide a method for recovering manganese from laterite nickel ore to solve the problem of resource waste caused by the ineffective recovery of manganese elements in the hydrometallurgy process of laterite nickel ore in the prior art.

[0004] To achieve the above object, according to one aspect of the present invention, a method for recovering manganese from laterite nickel ore is provided. The method includes: sequentially performing a precipitation reaction and a liquid-solid separation on substances including an alkaline precipitant, an oxidant, and a heavy metal solution containing nickel, cobalt, and manganese to obtain a nickel cobalt manganese hydroxide product and a magnesium-containing solution.

[0005] Further, the concentration of nickel ions in the heavy metal solution containing nickel, cobalt, and manganese is 0.1 to 100 g / L, the concentration of cobalt ions is 0.1 to 100 g / L, and the concentration of manganese ions is 0.1 to 100 g / L.

[0006] Further, the concentration of nickel ions in the heavy metal solution containing nickel, cobalt, and manganese is 1 to 8 g / L, the concentration of cobalt ions is 0.1 to 8 g / L, and the concentration of manganese ions is 0.5 to 6 g / L.

[0007] Further, the alkaline precipitant is selected from any one or more of hydroxides, alkali metal oxides, alkaline earth metal oxides, carbonates, bicarbonates, and basic carbonates; and / or the alkaline precipitant is selected from any one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, lithium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and basic magnesium carbonate.

[0008] Further, the oxidant is selected from any one or more of a mixture of oxygen and sulfur dioxide, air, oxygen, oxygen-enriched, ozone, hydrogen peroxide, persulfate, hypochlorite, and perchlorate.

[0009] Further, the dosage of the alkaline precipitant is 0.9 to 5 times the molar ratio of manganese in the heavy metal solution containing nickel, cobalt, and manganese.

[0010] Further, the dosage of the above-mentioned alkaline precipitant is 0.8 to 2 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0011] Further, the above-mentioned alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the mass ratio of sodium hydroxide to magnesium oxide is 10-90:10-90. The oxidant is ozone and / or hydrogen peroxide.

[0012] Further, the above-mentioned alkaline precipitant is a mixture of calcium hydroxide and magnesium oxide, and the mass ratio of calcium hydroxide to magnesium oxide is 10-90:10-90. The oxidant is hypochlorite and / or perchlorate.

[0013] Further, the above-mentioned alkaline precipitant is a mixture of sodium hydroxide, magnesium oxide and basic magnesium carbonate, and the mass ratio of sodium hydroxide, magnesium oxide and basic magnesium carbonate is 10-30:20-50:20-70. The oxidant is air, and the total molar amount of oxygen in the oxidant is 1 to 20 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0014] Further, the dosage of the above-mentioned oxidant is 0.5 to 10 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0015] Further, the dosage of the above-mentioned oxidant is 0.8 to 3 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0016] Further, the temperature of the above-mentioned precipitation reaction is 25°C to 200°C, and the time of the precipitation reaction is 1 to 300 min.

[0017] Further, the temperature of the above-mentioned precipitation reaction is 30°C to 150°C, and the time of the precipitation reaction is 30 to 120 min.

[0018] Further, the above-mentioned nickel-cobalt-manganese heavy metal solution is selected from any one or more of the post-iron-aluminum liquid in the field of laterite nickel ore hydrometallurgy, the battery material black powder leaching solution in the field of lithium battery recycling, and the copper-cobalt solution in copper-cobalt hydrometallurgy.

[0019] The technical solution of the present application is applied. The principle on which the present application is based is to add an oxidant during the precipitation process to change the redox environment in the nickel-cobalt-manganese heavy metal solution so that manganese can be precipitated together with nickel and cobalt under alkaline conditions. Specifically, when a suitable oxidant is added to the solution, divalent manganese can be oxidized to a high-valent state, making it easier to form a stable, insoluble precipitate under alkaline conditions, and precipitate together with the hydroxides of nickel and cobalt, thereby achieving efficient recovery of manganese. The above treatment has the following technical effects: First, manganese can be recovered from the liquid phase at one time, avoiding the loss of manganese, significantly improving the recovery rate of manganese and reducing resource waste; Second, by using a specific alkali as a precipitant, the composition and structure of the precipitate can be controlled to obtain an intermediate product (MHP) enriched in manganese, so that the intermediate product enriched in manganese provides a raw material for the subsequent preparation of high-value nickel-cobalt-manganese alloys or battery materials; Third, the method recovers manganese simultaneously during the nickel-cobalt precipitation process, avoiding additional manganese recovery steps, simplifying the entire hydrometallurgical process, reducing production costs and improving production efficiency; Fourth, by optimizing the process, the generation of tailings is reduced, the pollution to the environment is reduced, and a greener metal recovery process is achieved; Fifth, the method is not only suitable for the iron-aluminum-removed liquid in the hydrometallurgical process of laterite nickel ore, but also suitable for the treatment of heavy metal-containing solutions in multiple fields such as lithium battery recovery and copper-cobalt hydrometallurgy, and has broad industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0021] Figure 1 A process flow chart of a method for recovering manganese from laterite nickel ore according to Example 1 of the present invention is shown. DETAILED DESCRIPTION

[0022] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0023] As described in the background technology section, in the hydrometallurgical process of laterite nickel ore, manganese is not effectively recovered, resulting in a waste of resources. When precipitating nickel and cobalt, the traditional method is often operated under reducing conditions, which causes part of manganese to be precipitated in the product, while most of it is discharged in the form of tailings, and the comprehensive recovery of manganese is not achieved. That is, in the prior art, manganese is not effectively recovered in the hydrometallurgical process of laterite nickel ore, resulting in a waste of resources. In order to solve the above problem, the present invention provides a method for recovering manganese in laterite nickel ore.

[0024] In a typical embodiment of the present application, a method for recovering manganese from laterite nickel ore is provided. The method includes: sequentially performing precipitation reaction and liquid-solid separation on substances including an alkaline precipitant, an oxidant, and a heavy metal solution containing nickel, cobalt, and manganese to obtain nickel-cobalt-manganese hydroxide product and a magnesium-containing solution.

[0025] The principle relied on by the present application is to change the redox environment in the heavy metal solution containing nickel, cobalt, and manganese by adding an oxidant during the precipitation process, so that manganese can precipitate together with nickel and cobalt under alkaline conditions. Specifically, when an appropriate oxidant is added to the solution, divalent manganese can be oxidized to a higher valence state, making it easier to form a stable and insoluble precipitate under alkaline conditions and precipitate out together with the hydroxides of nickel and cobalt, thereby realizing the efficient recovery of manganese. The above treatment has the following technical effects: First, manganese can be recovered from the liquid phase at one time, avoiding the loss of manganese, significantly improving the recovery rate of manganese, and reducing resource waste; Second, by using a specific alkali as the precipitant, the composition and structure of the precipitate can be controlled to obtain an intermediate product (MHP) enriched in manganese, and such an intermediate product enriched in manganese provides raw materials for the subsequent preparation of high-value nickel-cobalt-manganese alloys or battery materials; Third, this method recovers manganese simultaneously during the precipitation of nickel and cobalt, avoiding additional manganese recovery steps, simplifying the entire hydrometallurgical process flow, reducing production costs, and improving production efficiency; Fourth, by optimizing the process, the generation of tailings is reduced, environmental pollution is reduced, and a more environmentally friendly metal recovery and treatment process is realized; Fifth, this method is not only applicable to the solution after iron and aluminum removal in the hydrometallurgy process of laterite nickel ore, but also applicable to the treatment of heavy metal-containing solutions in multiple fields such as lithium-ion battery recycling and copper-cobalt hydrometallurgy, and has broad industrial application prospects.

[0026] In an embodiment of the present application, the concentration of nickel ions in the heavy metal solution containing nickel, cobalt, and manganese is 0.1 - 100 g / L, the concentration of cobalt ions is 0.1 - 100 g / L, and the concentration of manganese ions is 0.1 - 100 g / L.

[0027] When the concentrations of various metal ions in the nickel-cobalt-manganese heavy metal solution are at relatively low levels, such as 0.1 g / L, it can promote the uniform distribution of metal ions in the solution, facilitate the uniform progress of the precipitation reaction, and reduce the risk of increased side reactions or incomplete precipitation caused by excessive local concentration. At a higher concentration of 100 g / L, it means that the amount of recoverable metals per unit volume increases significantly, improving the efficiency of single treatment, which is particularly important for large-scale industrial production. Controlling the concentrations of various metal ions in the nickel-cobalt-manganese heavy metal solution within the above range can, on the one hand, regulate the particle size, morphology, and component ratio of the obtained precipitate (MHP). Smaller or moderate-sized particles are beneficial for subsequent filtration and washing, while an appropriate component ratio is the basis for preparing high-performance alloys or battery materials. On the other hand, reasonable control of the metal ion concentration in the solution can reduce the energy consumption during the dilution and concentration processes. At the same time, since the precipitation reaction is carried out at an appropriate concentration, there is no need to excessively consume the precipitant, which helps to save raw material costs.

[0028] In an embodiment of the present application, the concentration of nickel ions in the above nickel-cobalt-manganese heavy metal solution is 1-8 g / L, the concentration of cobalt ions is 0.1-8 g / L, and the concentration of manganese ions is 0.5-6 g / L.

[0029] Preferably, the concentrations of various metal ions in the above nickel-cobalt-manganese heavy metal solution will not cause difficulty in forming precipitates due to excessive concentration, nor will they lead to low recovery efficiency due to too low concentration. On the one hand, the preferably above concentrations of various metal ions are more conducive to forming uniform and stable precipitates, thereby improving the precipitation efficiency and purity. On the other hand, the preferably above concentrations of various metal ions can more effectively control the recovery of metal ions. This enables nickel, cobalt, and manganese to be fully recovered, reduces the residue of metals in the solution, and improves the overall metal recovery rate. On the other hand, controlling within a specific concentration range helps to obtain precipitates with good structure and easy separation. Such precipitates not only have high purity but also perform better in subsequent processing (such as washing, drying, and sintering, etc.), and the final product quality is better.

[0030] In an embodiment of the present application, the above basic precipitant is selected from any one or more of hydroxides, alkali metal oxides, alkaline earth metal oxides, carbonates, bicarbonates, and basic carbonates; and / or the basic precipitant is selected from any one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, lithium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and basic magnesium carbonate.

[0031] Different alkaline precipitants have different effects and speeds when changing the pH value of the solution. By selecting an appropriate alkaline precipitant, the pH value of the solution can be precisely controlled, enabling the precipitation of nickel, cobalt, and manganese under specific conditions and improving the selectivity and efficiency of metal precipitation. The use of different alkaline precipitants can affect the composition, structure, and properties of the final precipitate. The choice of alkaline precipitant directly affects the cost. Some alkaline precipitants such as sodium hydroxide and sodium carbonate have relatively low costs, while lithium hydroxide has a higher cost. Based on actual requirements and cost considerations, selecting a suitable alkaline precipitant can maximize cost-effectiveness.

[0032] In one embodiment of the present application, the above-mentioned oxidant is selected from any one or more of a mixture of oxygen and sulfur dioxide, air, oxygen, enriched oxygen, ozone, hydrogen peroxide, persulfate, hypochlorite, and perchlorate.

[0033] Different oxidants have different oxidation capabilities for manganese (Mn). On the one hand, by selecting an appropriate oxidant, the rate and conditions of the oxidation reaction can be controlled; on the other hand, providing a variety of oxidant options enables the method to adapt to different production environments and requirements.

[0034] In one embodiment of the present application, the dosage of the above-mentioned alkaline precipitant is 0.9 to 5 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution, preferably 1 to 1.2 times.

[0035] Different dosages of alkaline precipitants will affect the composition, structure, and physicochemical properties of the precipitate. Within the above dosage range, on the one hand, the metal ratio, particle size, and morphology of the precipitate can be regulated to obtain a precipitate with a stable structure and easy separation, which is beneficial for subsequent treatment and applications, such as preparing battery materials or metal alloys; on the other hand, the preferred above dosage range can ensure that manganese and other metal ions in the solution fully react to form a precipitate. This not only improves the recovery rate of manganese but also promotes the precipitation of nickel and cobalt, thereby improving the overall efficiency of metal recovery.

[0036] In one embodiment of the present application, the dosage of the above-mentioned alkaline precipitant is 0.8 to 2 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0037] Control the dosage of the alkaline precipitant so that the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution is within the above range. On the one hand, overuse of the alkaline precipitant is avoided, which helps reduce reagent consumption and thus lower production costs. At the same time, excessive alkaline precipitant may bring additional washing and neutralization steps, increasing costs and energy consumption. On the other hand, in the precipitation reaction, the pH value is a key factor affecting the precipitation of metal ions. Controlling the dosage of the alkaline precipitant within the range of 0.8 to 2 times the molar ratio of manganese can ensure an effective increase in the solution pH value, promote the precipitation of manganese and co-existing metal ions such as nickel and cobalt, and at the same time avoid the redissolution of metal precipitates or the formation of unstable precipitation phases due to too high pH value. On the other hand, by reasonably controlling the dosage of the alkaline precipitant, the generation of wastewater can be reduced, the difficulty and cost of subsequent treatment can be lowered, and the potential impact on the environment can be reduced.

[0038] In one embodiment of the present application, the above-mentioned alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the mass ratio of sodium hydroxide to magnesium oxide is 10-90:10-90, and the oxidant is ozone and / or hydrogen peroxide.

[0039] Sodium hydroxide can obtain finer precipitates. The presence of magnesium oxide can increase the stability and structural strength of the precipitates, and avoid the decomposition or reconstruction of the precipitates during subsequent treatment processes (such as washing, filtering and drying). At the same time, the addition of magnesium oxide may also improve the particle size distribution of the precipitates, making the precipitates easier to separate and process. Using carbonates may form a more stable precipitation structure. Combining with hydrogen peroxide and / or ozone with stronger oxidation ability is beneficial to more quickly and thus more thoroughly recover manganese in the solution. Compared with other oxidants, ozone and hydrogen peroxide will not introduce additional ions or impurities during the treatment process, which helps to maintain the purity of the precipitates. The mixed use of sodium hydroxide and magnesium oxide can provide a relatively stable alkaline environment and promote the precipitation of nickel, cobalt and manganese. Different mixing ratios can adjust the pH value and precipitation environment to adapt to metal ion solutions with different concentrations and achieve the best precipitation effect.

[0040] In one embodiment of the present application, the above-mentioned alkaline precipitant is a mixture of calcium hydroxide and magnesium oxide, and the mass ratio of calcium hydroxide to magnesium oxide is 10-90:10-90, and the oxidant is hypochlorite and / or perchlorate.

[0041] Calcium hydroxide can reduce potential environmental pollution and meet the requirements of green production. The combined use of calcium hydroxide and magnesium oxide can provide a stable and controllable alkaline environment, which is crucial for the precipitation of metal ions. Within the mass ratio range of 10 - 90:10 - 90, the pH value of the solution can be finely adjusted, optimizing the precipitation conditions to ensure the effective precipitation of nickel, cobalt, and manganese without interference from other factors. Hypochlorites and perchlorates, as oxidants, have strong oxidation capabilities and can efficiently oxidize divalent manganese ions to higher valence states, making them more easily precipitated. This not only improves the recovery rate of manganese but also can be carried out under relatively mild operating conditions, reducing the stringent requirements for equipment and the operating environment. The combined use of calcium hydroxide and magnesium oxide, as well as the selection of hypochlorites and perchlorates, helps to reduce the generation of by-products and waste during the precipitation process. The precipitates or residues formed after the reaction of these substances are often easier to handle and recycle, reducing the complexity and cost of subsequent treatment.

[0042] In one embodiment of the present application, the above-mentioned alkaline precipitant is a mixture of sodium hydroxide, magnesium oxide, and basic magnesium carbonate. The mass ratio of sodium hydroxide, magnesium oxide, and basic magnesium carbonate is 10 - 30:20 - 50:20 - 70, and the oxidant is air. The total molar amount of oxygen in the oxidant is 1 - 20 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0043] By using a mixture of sodium hydroxide, magnesium oxide, and basic magnesium carbonate, the pH value of the solution can be comprehensively adjusted to be within the range most suitable for metal precipitation. Each alkaline precipitant has its specific buffering capacity and pH adjustment characteristics. The combined use can more precisely control the pH conditions and promote the co-precipitation of nickel, cobalt, and manganese. The presence of magnesium oxide may affect the crystal structure of the precipitate, thereby improving the thermal stability, mechanical strength, and purity of the precipitate. The introduction of basic magnesium carbonate may further improve the morphology and particle size distribution of the precipitate, making the precipitate more uniform and easier to separate and handle. Air, as a low-cost oxidant containing a certain proportion of oxygen, can meet the demand for manganese oxidation. By controlling the molar amount of oxygen in the air, sufficient oxidation capacity can be provided under economically feasible conditions to oxidize divalent manganese to higher valence manganese and then precipitate and recover it. Controlling the molar ratio of oxygen in the air to the molar ratio of manganese in the solution can adjust the oxidation rate and degree to ensure the effective oxidation of manganese without introducing excessive impurities. This is very important for maintaining the purity and recovery efficiency of the precipitate. Using air as an oxidant, compared with chemical oxidants, has fewer by-products, reduces the burden of subsequent wastewater treatment, lowers production costs, and improves environmental friendliness at the same time.

[0044] In one embodiment of the present application, the dosage of the above-mentioned oxidant is 0.5 - 10 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0045] The dosage of the oxidant within the range of 0.5 to 10 times the molar ratio of manganese can promote the full oxidation of manganese ions, thereby improving the precipitation efficiency of manganese. An appropriate amount of oxidant can oxidize the divalent manganese ions that are not easily precipitated in the solution into high-valent manganese ions, and the latter are more likely to form precipitates under alkaline conditions, achieving a high recovery rate of manganese. Under oxidation conditions, not only manganese ions are oxidized, but metal ions such as nickel and cobalt may also undergo redox reactions, thereby promoting the coprecipitation of these metals. This helps to recover multiple valuable metals at one time, reduce subsequent separation steps, and improve the economic benefits of overall metal recovery. Controlling the dosage of the oxidant can better adjust the intensity and rate of the oxidation reaction, and avoid the decomposition of metal precipitates or the generation of unwanted by-products caused by over-oxidation. This is very important for ensuring the purity and stability of the precipitate.

[0046] In an embodiment of the present application, the dosage of the above-mentioned oxidant is 0.8 to 3 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution.

[0047] At a dosage of 0.8 to 3 times the molar ratio of manganese, the oxidant can accurately oxidize the manganese ions in the solution to a high valence state and promote their precipitation. The use of the oxidant within this range avoids the low recovery efficiency caused by insufficient oxidation and prevents unnecessary side effects caused by excessive oxidant, such as the over-oxidation of other metal ions or the generation of difficult-to-treat by-products.

[0048] In an embodiment of the present application, the temperature of the above precipitation reaction is 25°C to 200°C, and the time of the precipitation reaction is 1 to 300 min.

[0049] The setting of the reaction temperature directly affects the reaction rate and the efficiency of metal precipitation. A higher temperature (close to 200°C) can accelerate the reaction between metal ions and the alkaline precipitant in the solution and promote the formation of precipitates. This is beneficial to shortening the production cycle and improving production efficiency. A lower temperature (such as room temperature 25°C) can reduce energy consumption and costs, and at the same time avoid the decomposition or denaturation of precipitates caused by high temperature, maintaining product quality. The setting of the reaction time ensures the completeness of the precipitation reaction. A longer reaction time (up to 300 min) gives metal ions enough time to contact and react with the precipitant, improving the recovery rate of metals, especially those with slower reaction kinetics. A shorter time (at least 1 min) indicates that under appropriate temperature and oxidant conditions, the precipitation reaction can proceed rapidly, which is beneficial to continuous production operations and improves the flexibility and efficiency of the production line. Within the above temperature and time ranges, the precipitation conditions of metal ions can be optimized, and the selectivity of precipitation can be improved. This means that target metals such as nickel, cobalt, and manganese can precipitate preferentially during the reaction, while other metal ions that are not desired to precipitate remain in the solution, which is beneficial to subsequent metal separation and purification, reduces the generation of by-products, and improves product purity.

[0050] In one embodiment of the present application, the temperature of the above precipitation reaction is 30°C to 150°C, and the time of the precipitation reaction is 30 to 120 min.

[0051] It can effectively accelerate the chemical reaction between metal ions and the precipitant, and shorten the time to reach precipitation equilibrium. Compared with lower temperatures, the temperature in this range can increase the reaction rate, enabling metal ions to form precipitates more quickly, which is suitable for continuous and large-scale production processes and improves production efficiency. At the same time, the temperature is not too high, avoiding unnecessary energy consumption and possible damage to the precipitate structure, and maintaining the controllability of product quality and production cost. Controlling the reaction time within 30 to 120 min not only ensures the full precipitation of metal ions but also avoids additional costs caused by too long time, such as energy consumption and equipment occupancy costs. The setting of a shorter time meets the pursuit of efficiency in industrial production, while the 120-min upper limit ensures that even in the case of high metal ion concentration or slow reaction kinetics, the metal can still be completely precipitated, further improving the versatility and adaptability of the method.

[0052] In one embodiment of the present application, the above nickel-cobalt-manganese heavy metal solution is selected from any one or more of the post-iron-aluminum liquid in the field of laterite nickel ore hydrometallurgy, the battery material black powder leaching liquid in the field of lithium battery recycling, and the copper-cobalt solution in copper-cobalt hydrometallurgy.

[0053] The selection of the above nickel-cobalt-manganese heavy metal solution means that the method of the present invention can be applied to multiple industries and fields, including but not limited to metal mining, waste battery recycling, and alloy smelting. This versatility not only broadens the application scope of the method but also improves its practicability in different industrial environments and reduces the cost of developing dedicated technologies for specific industries.

[0054] The following further describes the present application in detail with specific embodiments, and these embodiments should not be construed as limiting the scope claimed by the present application.

[0055] Example 1

[0056] Refer to Figure 1 the process flow chart of the method for manganese recovery in laterite nickel ore shown, and perform the above recovery process:

[0057] In the post-iron-aluminum liquid in the laterite nickel ore hydrometallurgy process, the nickel content is 3 g / L, the cobalt content is 0.3 g / L, and the manganese content is 3 g / L. Sodium hydroxide is added in an amount of 1 times the stoichiometric molar ratio of the chemical reaction with nickel, cobalt, and manganese for precipitation reaction. The temperature is 60°C, and the reaction time is 120 min. At the same time, oxygen is introduced for oxidation, and the oxygen dosage is 3 times the molar ratio of manganese in the post-iron-aluminum liquid. After the reaction, liquid-solid separation is performed to obtain nickel-cobalt-manganese hydroxide products and a magnesium-containing solution.

[0058] The manganese content of the obtained nickel cobalt manganese hydroxide product is 15.0%, the manganese precipitation rate reaches 98.5%, and manganese is recovered.

[0059] Example 2

[0060] The difference from Example 1 is that in the laterite nickel ore hydrometallurgy process, the solution after iron and aluminum removal contains 1 g / L of nickel, 0.1 g / L of cobalt, and 1.5 g / L of manganese, and a nickel cobalt manganese hydroxide product and a magnesium-containing solution are obtained.

[0061] The manganese content of the obtained nickel cobalt manganese hydroxide product is 23%, the manganese precipitation rate reaches 98.0%, and manganese is recovered.

[0062] Example 3

[0063] The difference from Example 1 is that in the laterite nickel ore hydrometallurgy process, the solution after iron and aluminum removal contains 8 g / L of nickel, 8 g / L of cobalt, and 6 g / L of manganese, and a nickel cobalt manganese hydroxide product and a magnesium-containing solution are obtained.

[0064] The manganese content of the obtained nickel cobalt manganese hydroxide product is 7%, the manganese precipitation rate reaches 99.0%, and manganese is recovered.

[0065] Example 4

[0066] The difference from Example 1 is that in the laterite nickel ore hydrometallurgy process, the solution after iron and aluminum removal contains 10 g / L of nickel, 10 g / L of cobalt, and 10 g / L of manganese, and a nickel cobalt manganese hydroxide product and a magnesium-containing solution are obtained.

[0067] The manganese content of the obtained nickel cobalt manganese hydroxide product is 24%, the manganese precipitation rate reaches 99.3%, and manganese is recovered.

[0068] Example 5

[0069] The difference from Example 1 is that the alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, the mass ratio of sodium hydroxide to magnesium oxide is 10:90, the oxidant is hydrogen peroxide, and finally a nickel cobalt manganese hydroxide product and a magnesium-containing solution are obtained.

[0070] The manganese content of the obtained nickel cobalt manganese hydroxide product is 15.3%, the manganese precipitation rate reaches 98.6%, and manganese is recovered.

[0071] Example 6

[0072] The difference from Example 1 is that the alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, the mass ratio of sodium hydroxide to magnesium oxide is 90:10, the oxidant is hydrogen peroxide, and finally a nickel cobalt manganese hydroxide product and a magnesium-containing solution are obtained.

[0073] The manganese content of the obtained nickel cobalt manganese hydroxide product is 15.2%, the manganese precipitation rate reaches 98.7%, and manganese is recovered.

[0074] Example 7

[0075] It is different from Example 1 in that the alkaline precipitant is a mixture of calcium hydroxide and magnesium oxide, and the mass ratio of calcium hydroxide to magnesium oxide is 90:10. The oxidant is sodium hypochlorite, and finally a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution are obtained.

[0076] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 5.0%, the manganese precipitation rate reaches 98.2%, and manganese is recovered.

[0077] Example 8

[0078] It is different from Example 1 in that the alkaline precipitant is a mixture of calcium hydroxide and magnesium oxide, and the mass ratio of calcium hydroxide to magnesium oxide is 10:90. The oxidant is sodium hypochlorite, and finally a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution are obtained.

[0079] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 13.0%, the manganese precipitation rate reaches 98.3%, and manganese is recovered.

[0080] Example 9

[0081] It is different from Example 1 in that the alkaline precipitant is a mixture of sodium hydroxide, magnesium oxide and basic magnesium carbonate, and the mass ratio of sodium hydroxide, magnesium oxide and basic magnesium carbonate is 10:20:70. The oxidant is air, and the total molar amount of oxygen in the oxidant is 5 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution. Finally, a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution are obtained.

[0082] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 15.5%, the manganese precipitation rate reaches 98.7%, and manganese is recovered.

[0083] Example 10

[0084] It is different from Example 1 in that the alkaline precipitant is a mixture of sodium hydroxide, magnesium oxide and basic magnesium carbonate, and the mass ratio of sodium hydroxide, magnesium oxide and basic magnesium carbonate is 30:50:20. The oxidant is air, and the total molar amount of oxygen in the oxidant is 10 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal solution. Finally, a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution are obtained.

[0085] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 15.6%, the manganese precipitation rate reaches 98.4%, and manganese is recovered.

[0086] Example 11

[0087] The difference from Example 5 is that the alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the alkaline precipitant is added at 1.2 times the stoichiometric molar ratio of the chemical reaction with nickel, cobalt and manganese for precipitation reaction, and finally nickel-cobalt-manganese hydroxide product and magnesium-containing solution are obtained.

[0088] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 14.5%, the manganese precipitation rate reaches 99.0%, and manganese is recovered.

[0089] Example 12

[0090] The difference from Example 5 is that the alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the alkaline precipitant is added at 0.9 times the stoichiometric molar ratio of the chemical reaction with nickel, cobalt and manganese for precipitation reaction, and finally nickel-cobalt-manganese hydroxide product and magnesium-containing solution are obtained.

[0091] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 15.0%, the manganese precipitation rate reaches 90.0%, and manganese is recovered.

[0092] Example 13

[0093] The difference from Example 5 is that the alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the alkaline precipitant is added at 5 times the stoichiometric molar ratio of the chemical reaction with nickel, cobalt and manganese for precipitation reaction, and finally nickel-cobalt-manganese hydroxide product and magnesium-containing solution are obtained.

[0094] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 3%, the manganese precipitation rate reaches 99.7%, and manganese is recovered.

[0095] Example 14

[0096] The difference from Example 5 is that the oxidant is hydrogen peroxide, and the dosage of hydrogen peroxide is 0.8 times the molar ratio of manganese in the solution after iron and aluminum removal. Finally, nickel-cobalt-manganese hydroxide product and magnesium-containing solution are obtained.

[0097] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 12.0%, the manganese precipitation rate reaches 80.0%, and manganese is recovered.

[0098] Example 15

[0099] The difference from Example 5 is that the oxidant is hydrogen peroxide, and the dosage of hydrogen peroxide is 0.5 times the molar ratio of manganese in the solution after iron and aluminum removal. Finally, nickel-cobalt-manganese hydroxide product and magnesium-containing solution are obtained.

[0100] The manganese content rate of the obtained nickel-cobalt-manganese hydroxide product is 8%, the manganese precipitation rate reaches 50%, and manganese is recovered.

[0101] Example 16

[0102] The difference from Example 5 is that the oxidant is hydrogen peroxide, and the dosage of hydrogen peroxide is 10 times the molar ratio of manganese in the solution after iron and aluminum removal. Finally, nickel cobalt manganese hydroxide product and magnesium-containing solution are obtained.

[0103] The manganese content rate of the obtained nickel cobalt manganese hydroxide product is 15.0%, the manganese precipitation rate reaches 99.8%, and manganese is recovered.

[0104] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0105] The principle on which this application is based is to change the redox environment in the heavy metal solution containing nickel, cobalt and manganese by adding an oxidant during the precipitation process, so that manganese can precipitate together with nickel and cobalt under alkaline conditions. Specifically, when an appropriate oxidant is added to the solution, divalent manganese can be oxidized to a higher valence state, making it easier to form a stable and insoluble precipitate under alkaline conditions and precipitate out together with the hydroxides of nickel and cobalt, thus realizing the efficient recovery of manganese. The above treatment has the following technical effects: First, manganese can be recovered from the liquid phase at one time, avoiding the loss of manganese, significantly improving the recovery rate of manganese, and reducing resource waste; Second, a specific alkali is used as the precipitant to control the composition and structure of the precipitate, and an intermediate product (MHP) rich in manganese is obtained. Such an intermediate product rich in manganese provides raw materials for the subsequent preparation of high-value nickel cobalt manganese alloys or battery materials; Third, this method recovers manganese during the nickel and cobalt precipitation process, avoiding additional manganese recovery steps, simplifying the entire hydrometallurgical process flow, reducing production costs, and improving production efficiency; Fourth, by optimizing the process, the generation of tailings is reduced, the environmental pollution is reduced, and a more environmentally friendly metal recovery and treatment process is realized; Fifth, this method is not only applicable to the solution after iron and aluminum removal in the hydrometallurgy process of laterite nickel ore, but also applicable to the treatment of heavy metal-containing solutions in multiple fields such as lithium battery recycling and copper cobalt hydrometallurgy, and has broad industrial application prospects.

[0106] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for recovering manganese from laterite nickel ore, characterized in that, The method includes: Sequentially performing a precipitation reaction and liquid-solid separation on substances including an alkaline precipitant, an oxidant, and a nickel-cobalt-manganese heavy metal-containing solution to obtain a nickel-cobalt-manganese hydroxide product and a magnesium-containing solution.

2. The method for recovering manganese from laterite nickel ore according to claim 1, characterized in that, In the nickel-cobalt-manganese heavy metal-containing solution, the concentration of nickel ions is 0.1 - 100 g / L, the concentration of cobalt ions is 0.1 - 100 g / L, and the concentration of manganese ions is 0.1 - 100 g / L.

3. The method for recovering manganese from laterite nickel ore according to claim 2, wherein In the nickel-cobalt-manganese heavy metal-containing solution, the concentration of nickel ions is 1 - 8 g / L, the concentration of cobalt ions is 0.1 - 8 g / L, and the concentration of manganese ions is 0.5 - 6 g / L.

4. The method for recovering manganese from laterite nickel ore according to any one of claims 1 to 3, characterized in that, The alkaline precipitant is selected from any one or more of hydroxides, alkali metal oxides, alkaline earth metal oxides, carbonates, bicarbonates, and basic carbonates; and / or the alkaline precipitant is selected from any one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonium hydroxide, lithium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, and basic magnesium carbonate.

5. The method for recovering manganese from laterite nickel ore according to claim 4, characterized in that, The oxidant is selected from any one or more of a mixture of oxygen and sulfur dioxide, air, oxygen, enriched oxygen, ozone, hydrogen peroxide, persulfate, hypochlorite, and perchlorate.

6. The method for recovering manganese from laterite nickel ore according to any one of claims 1 to 3, characterized in that, The dosage of the alkaline precipitant is 0.9 - 5 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal-containing solution.

7. The method for recovering manganese from laterite nickel ore according to claim 6, characterized in that, The dosage of the alkaline precipitant is 0.8 - 2 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal-containing solution.

8. The method for recovering manganese from laterite nickel ore according to claim 5, characterized in that, The alkaline precipitant is a mixture of sodium hydroxide and magnesium oxide, and the mass ratio of sodium hydroxide to magnesium oxide is 10 - 90:10 - 90. The oxidant is ozone and / or hydrogen peroxide.

9. The method for recovering manganese from laterite nickel ore according to claim 5, characterized in that The alkaline precipitant is a mixture of calcium hydroxide and magnesium oxide, and the mass ratio of calcium hydroxide to magnesium oxide is 10 - 90:10 - 90. The oxidant is hypochlorite and / or perchlorate.

10. The method for recovering manganese from laterite nickel ore according to claim 5, wherein, The alkaline precipitant is a mixture of sodium hydroxide, magnesium oxide, and basic magnesium carbonate, and the mass ratio of sodium hydroxide, magnesium oxide, and basic magnesium carbonate is 10 - 30:20 - 50:20 - 70. The oxidant is air, and the total molar amount of oxygen in the oxidant is 1 - 20 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal-containing solution.

11. The method for recovering manganese from laterite nickel ore according to any one of claims 1 to 3, characterized in that, The dosage of the oxidant is 0.5 - 10 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal-containing solution.

12. The method for recovering manganese in laterite nickel ore according to claim 11, wherein, The dosage of the oxidant is 0.8 - 3 times the molar ratio of manganese in the nickel-cobalt-manganese heavy metal-containing solution.

13. The method for recovering manganese from laterite nickel ore according to any one of claims 1 to 3, characterized in that, The temperature of the precipitation reaction is 25°C - 200°C, and the time of the precipitation reaction is 1 - 300 min.

14. The method for recovering manganese from laterite nickel ore according to claim 13, wherein The temperature of the precipitation reaction is 30°C - 150°C, and the time of the precipitation reaction is 30 - 120 min.

15. The method for recovering manganese from laterite nickel ore according to any one of claims 1 to 3, characterized in that, The nickel-cobalt-manganese heavy metal-containing solution is selected from any one or more of the post-iron-aluminum liquid in the field of laterite nickel ore hydrometallurgy, the black powder leaching solution of battery materials in the field of lithium battery recycling, and the copper-cobalt solution in copper-cobalt hydrometallurgy.

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