Magnesium and manganese separation method in laterite-nickel ore hydrometallurgy
By adding neutralizing agents and carbon dioxide to the laterite nickel ore hydrometallurgical process for flotation-gravity sedimentation treatment, the problem of incomplete separation of magnesium and manganese ions in the liquid after nickel, cobalt and manganese precipitation was solved, and efficient separation and resource recycling were achieved.
Patent Information
- Application Number
- CN202480010174.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-09-25
- Filing Date
- 2024-10-04
- Publication Date
- 2025-09-05
Smart Images
Figure CN120603967A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for separating magnesium and manganese in laterite nickel ore hydrometallurgy. Background Art
[0002] Laterite nickel ore is formed by long-term weathering and metamorphism of ultramafic rocks containing iron-magnesium silicate minerals. The upper layer is limonite, composed primarily of iron oxides, while the middle layer is a transition layer and the lower layer is a magnesian-silicon nickel ore layer. Laterite nickel ore is abundant, has low mining costs, and is undergoing mature smelting processes. It can produce a variety of intermediate products, including nickel oxide and ferronickel, making it a major source of nickel resources in the future.
[0003] Currently, wet acid leaching is commonly used to extract nickel, cobalt, and manganese from laterite nickel ore. Specifically, the raw laterite nickel ore undergoes a wet process of "ore dressing pretreatment - high-pressure acid leaching - pre-neutralization - CCD washing - iron and aluminum removal - nickel, cobalt, and manganese precipitation" to obtain nickel, cobalt, and manganese hydroxide materials for the preparation of ternary precursors.
[0004] In this process, after the nickel-cobalt-manganese precipitation step, the resulting nickel-cobalt-manganese precipitation solution also contains a large amount of manganese and magnesium ions. However, in existing processes, the nickel-cobalt-manganese precipitation solution is usually not effectively separated from the manganese and magnesium elements, resulting in the ineffective recycling of these metal ions, resulting in a waste of resources. Therefore, it is necessary to propose a new treatment method to solve the above-mentioned problems existing in the existing technology. Summary of the Invention
[0005] The present invention aims to provide a method for separating magnesium and manganese in laterite nickel ore hydrometallurgy. The method aims to address the problem that, in the existing nickel, cobalt and manganese precipitation step of laterite nickel ore acid leaching, the manganese and manganese precipitation liquid is not effectively separated, resulting in the ineffective recycling of these metal ions and a waste of resources.
[0006] In a first aspect, the present invention provides a method for separating magnesium and manganese in laterite nickel ore hydrometallurgy, comprising the following steps: S1, adding a neutralizing agent to the laterite nickel ore acid leaching solution to carry out a reaction, and after the reaction, performing an iron-aluminum slag sedimentation treatment to obtain a liquid after iron and aluminum removal; S2, adding a neutralizing agent to the liquid after iron and aluminum removal to carry out nickel, cobalt and manganese precipitation treatment to obtain nickel, cobalt and manganese hydroxide and a liquid after nickel, cobalt and manganese precipitation; S3, introducing carbon dioxide into the liquid after nickel, cobalt and manganese precipitation to carry out flotation-gravity sedimentation treatment to obtain an upper emulsion and a lower emulsion, and then pressing the upper emulsion and the lower emulsion to obtain magnesium carbonate and manganese carbonate, respectively.
[0007] In the present invention, the inventors have discovered that after introducing excess carbon dioxide into the solution after nickel, cobalt and manganese precipitation, the carbon dioxide and the magnesium and manganese ions in the solution after nickel, cobalt and manganese precipitation fully react under gas buoyancy to obtain an emulsion. Under the action of gravity, the emulsion is separated into upper and lower layers of emulsion, and the upper and lower emulsions are further subjected to filter presses to obtain magnesium carbonate and manganese carbonate, respectively. The above separation process achieves efficient separation of magnesium and manganese ions in the solution after nickel, cobalt and manganese precipitation, and the entire separation process is simple, environmentally friendly, and convenient for large-scale promotion and application.
[0008] In some embodiments, in step S1, the laterite nickel ore acid leaching solution includes the following components: 2-5 g / L iron, 4-8 g / L aluminum, 5-7 g / L nickel, 0.4-0.8 g / L cobalt, 3-5 g / L manganese, and 6-10 g / L magnesium.
[0009] In the laterite nickel ore acid leaching solution provided by the present invention, the iron content can be, for example, 2 g / L, 2.5 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L or other values within the range; the aluminum content can be, for example, 4 g / L, 4.5 g / L, 5 g / L, 5.5 g / L, 6 g / L, 6.5 g / L, 7 g / L, 7.5 g / L, 8 g / L or other values within the range; the nickel content can be, for example, 5 g / L, 5.5 g / L, 6 g / L, 6.5 g / L, 7 g / L, 7.5 g / L, 8 g / L or other values within the range. or other values within this range; the cobalt content may be, for example, 0.4 g / L, 0.5 g / L, 0.6 g / L, 0.7 g / L, 0.8 g / L or other values within this range; the manganese content may be, for example, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L or other values within this range; the magnesium content may be, for example, 6 g / L, 6.5 g / L, 7 g / L, 7.5 g / L, 8 g / L, 8.5 g / L, 9 g / L, 9.5 g / L, 10 g / L or other values within this range.
[0010] In some embodiments, in step S1, the neutralizing agent is selected from at least one of sodium hydroxide, sodium carbonate, magnesium oxide, and potassium hydroxide.
[0011] In some embodiments, in step S1, the reaction step specifically includes: reacting for 4-8 hours, for example, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or other values within the range, at a pH value of 2-6 (for example, 2, 3, 4, 5, 6 or other values within the range) and a temperature of 60-80°C (for example, 60°C, 65°C, 70°C, 75°C, 80°C or other values within the range).
[0012] In the present invention, the pH value of the reaction is controlled to be 2-3, so that iron and aluminum are precipitated in the laterite nickel ore acid leaching solution, thereby achieving iron and aluminum removal.
[0013] In some embodiments, in step S1, during the iron-aluminum slag sedimentation treatment, a step of adding clay is further included, and the mass concentration of the clay is 5-10% (W / V), for example, 5%, 6%, 7%, 8%, 9%, 10% or other values within this range.
[0014] In the present invention, the mass concentration of clay refers to the ratio of the mass of clay to the volume of the laterite nickel ore acid leaching solution.
[0015] In the method for separating magnesium and manganese in laterite nickel ore hydrometallurgy provided by the present invention, the iron and aluminum removal step is usually to add alkali solution for reaction, so that the iron and aluminum generate hydroxide precipitation and can settle down, thereby realizing the separation of nickel, cobalt and manganese from iron and aluminum impurities in the leachate; however, since the generated iron and aluminum hydroxides are mostly in the form of colloids, there are problems such as separation difficulty and incompleteness in the subsequent solid-liquid separation process; based on this, the inventors further found that when clay is added during the sedimentation of iron and aluminum slag, since clay itself is a mineral, its surface has a negative charge; therefore, on the one hand, clay can adsorb iron and aluminum slag colloid to form larger flocs and accelerate sedimentation. At the same time, the clay surface has a negative charge, which can neutralize the positive charge of the iron hydroxide colloid particles, reduce the electrostatic repulsion between the colloid particles, promote the aggregation of particles, form larger flocs, and further improve the sedimentation effect of the iron and aluminum slag colloid.
[0016] In some embodiments, in step S2, the neutralizing agent is selected from at least one of sodium hydroxide, sodium carbonate, magnesium oxide, and potassium hydroxide.
[0017] In some embodiments, in step S2, the nickel, cobalt and manganese precipitation treatment step specifically includes: reacting for 3-6 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours or other values within the range, at a pH value of 7-9 (for example, 7, 7.5, 8, 8.5, 9 or other values within the range) and a temperature of 70-90°C (for example, 70°C, 75°C, 80°C, 85°C, 90°C or other values within the range).
[0018] In the present invention, the pH value in the nickel, cobalt and manganese precipitation step is controlled to 7-8, so that nickel, cobalt and part of manganese in the solution after iron and aluminum removal are precipitated, and the obtained nickel, cobalt and manganese hydroxide is used to prepare the ternary precursor.
[0019] In some embodiments, the method further includes calcining the magnesium carbonate in step S3 to obtain magnesium oxide and carbon dioxide.
[0020] In some embodiments, the magnesium oxide is further recycled as a neutralizing agent to the iron and aluminum slag precipitation treatment step and the nickel, cobalt and manganese precipitation treatment step.
[0021] In some embodiments, the process further includes recycling carbon dioxide to the flotation-gravity sedimentation treatment step.
[0022] In the present invention, the separated magnesium carbonate is calcined, and the obtained products magnesium oxide and carbon dioxide can be recycled, thereby further improving the utilization rate of the separated products.
[0023] In some embodiments, in step S3, the filtrate obtained by the filter press can be mixed with a neutralizing agent to obtain a neutralized solution, which is then reacted with the laterite nickel ore acid leachate and the iron and aluminum removed solution. Through the above treatment, comprehensive utilization of the filtrate is achieved.
[0024] The beneficial effects of the present invention are as follows: different from the prior art, the present invention sequentially performs iron-aluminum slag sedimentation treatment and nickel-cobalt-manganese precipitation treatment on laterite nickel ore acid leaching solution to obtain a nickel-cobalt-manganese precipitation liquid; further, after excessive carbon dioxide is introduced into the nickel-cobalt-manganese precipitation liquid, the carbon dioxide and magnesium and manganese ions in the nickel-cobalt-manganese precipitation liquid fully react under gas floating to obtain an emulsion; the emulsion is separated into upper and lower layers under the action of gravity to obtain an upper emulsion and a lower emulsion; the upper and lower emulsions are further subjected to filter pressing to obtain magnesium carbonate and manganese carbonate respectively; the above separation process realizes efficient separation of magnesium and manganese ions in the nickel-cobalt-manganese precipitation liquid, and the entire separation process is simple, green and environmentally friendly, and convenient for large-scale promotion and application; in addition, after the separation product of the present invention is calcined, the obtained product can be reused, thereby improving the utilization rate of the separation product. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 The present invention is a flow chart of the method for separating magnesium and manganese in laterite nickel ore hydrometallurgy. DETAILED DESCRIPTION
[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0027] For experimental methods in the examples where specific conditions are not specified, generally conventional conditions and conditions described in the manual or conditions recommended by the manufacturer were followed. The general equipment, materials, reagents, etc. used were all commercially available unless otherwise specified.
[0028] See also Figure 1, which is a flow chart of the magnesium and manganese separation method in the laterite nickel ore hydrometallurgy of the present invention. Specifically, the separation method comprises the following steps: S1, adding a neutralizing agent to the laterite nickel ore acid leaching solution to react, and after the reaction, performing iron and aluminum slag sedimentation treatment to obtain a liquid after iron and aluminum removal; S2, adding a neutralizing agent to the liquid after iron and aluminum removal to precipitate nickel, cobalt and manganese to obtain nickel, cobalt and manganese hydroxide and a liquid after nickel, cobalt and manganese precipitation; S3, introducing carbon dioxide into the liquid after nickel, cobalt and manganese precipitation to perform flotation-gravity sedimentation treatment to obtain an upper emulsion and a lower emulsion, and then pressing the upper emulsion and the lower emulsion to obtain magnesium carbonate and manganese carbonate, respectively.
[0029] Example 1 A method for separating magnesium and manganese in laterite nickel ore hydrometallurgy, characterized by comprising the following steps: S1. Adding sodium hydroxide to a laterite nickel ore acid leaching solution (comprising the following components: 3 g / L iron, 6 g / L aluminum, 6 g / L nickel, 0.6 g / L cobalt, 4 g / L manganese, and 8 g / L magnesium), reacting for 6 hours at a pH of 2 and a temperature of 70° C. to obtain an iron-aluminum slag colloidal solution, adding clay having a mass concentration of 8% to the iron-aluminum slag colloidal solution to perform iron-aluminum slag sedimentation treatment to obtain a solution after iron and aluminum removal; S2. Add sodium hydroxide to the solution after iron and aluminum removal, and react at a pH of 9 and a temperature of 80° C. for 5 hours to obtain nickel-cobalt-manganese hydroxide and a solution after nickel-cobalt-manganese precipitation; S3. Excess carbon dioxide is introduced into the liquid after nickel, cobalt and manganese precipitation to perform flotation-gravity sedimentation treatment to obtain an upper emulsion and a lower emulsion, and then the upper emulsion and the lower emulsion are filter-filtered to obtain magnesium carbonate and manganese carbonate, respectively; the magnesium carbonate is calcined to obtain magnesium oxide and carbon dioxide; wherein the magnesium oxide is reused as a neutralizing agent in the iron and aluminum slag sedimentation treatment step and the nickel, cobalt and manganese precipitation treatment step, and the carbon dioxide is reused in the flotation-gravity sedimentation treatment step.
[0030] Example 2 A method for separating magnesium and manganese in laterite nickel ore hydrometallurgy, characterized by comprising the following steps: S1. Adding sodium carbonate to a laterite nickel ore acid leaching solution (comprising the following components: 2 g / L iron, 8 g / L aluminum, 5 g / L nickel, 0.8 g / L cobalt, 3 g / L manganese, and 10 g / L magnesium), reacting for 4 hours at a pH of 4 and a temperature of 60° C. to obtain an iron-aluminum slag colloidal solution, adding clay having a mass concentration of 10% to the iron-aluminum slag colloidal solution to perform iron-aluminum slag sedimentation treatment to obtain a solution after iron and aluminum removal; S2. Sodium carbonate is added to the solution after iron and aluminum removal, and the reaction is carried out at a pH of 7.5 and a temperature of 90° C. for 6 hours to obtain nickel-cobalt-manganese hydroxide and a solution after nickel-cobalt-manganese precipitation; S3. Excess carbon dioxide is introduced into the liquid after nickel, cobalt and manganese precipitation to perform flotation-gravity sedimentation treatment to obtain an upper emulsion and a lower emulsion, and then the upper emulsion and the lower emulsion are filter-filtered to obtain magnesium carbonate and manganese carbonate, respectively; the magnesium carbonate is calcined to obtain magnesium oxide and carbon dioxide; wherein the magnesium oxide is reused as a neutralizing agent in the iron and aluminum slag sedimentation treatment step and the nickel, cobalt and manganese precipitation treatment step, and the carbon dioxide is reused in the flotation-gravity sedimentation treatment step.
[0031] Example 3 A method for separating magnesium and manganese in laterite nickel ore hydrometallurgy, characterized by comprising the following steps: S1. Potassium hydroxide is added to a laterite nickel ore acid leaching solution (comprising the following components: 5 g / L iron, 4 g / L aluminum, 7 g / L nickel, 0.4 g / L cobalt, 5 g / L manganese, and 6 g / L magnesium). The reaction is carried out at a pH of 6 and a temperature of 80° C. for 8 hours to obtain an iron-aluminum slag colloidal solution. Clay having a mass concentration of 5% is added to the iron-aluminum slag colloidal solution to perform iron-aluminum slag sedimentation treatment to obtain a solution after iron and aluminum removal. S2. Add sodium hydroxide to the solution after iron and aluminum removal, and react for 3 hours at a pH of 8 and a temperature of 70° C. to obtain nickel-cobalt-manganese hydroxide and a solution after nickel-cobalt-manganese precipitation; S3. Excess carbon dioxide is introduced into the liquid after nickel, cobalt and manganese precipitation to perform flotation-gravity sedimentation treatment to obtain an upper emulsion and a lower emulsion, and then the upper emulsion and the lower emulsion are filter-filtered to obtain magnesium carbonate and manganese carbonate, respectively; the magnesium carbonate is calcined to obtain magnesium oxide and carbon dioxide; wherein the magnesium oxide is reused as a neutralizing agent in the iron and aluminum slag sedimentation treatment step and the nickel, cobalt and manganese precipitation treatment step, and the carbon dioxide is reused in the flotation-gravity sedimentation treatment step.
[0032] Based on the magnesium carbonate and manganese carbonate obtained after the filter press in step S3 of Example 1-3, the magnesium and manganese recovery rates relative to the solution after nickel, cobalt and manganese precipitation in step S2 were calculated, and the results are shown in Table 1 below.
[0033] Table 1 Magnesium and manganese recovery results
[0034] It can be seen from the results in Table 1 that the separation process of the present invention can achieve efficient separation of magnesium and manganese in the solution after nickel, cobalt and manganese precipitation.
[0035] In summary, the separation process of the present invention realizes the efficient separation of magnesium and manganese ions in the liquid after nickel, cobalt and manganese precipitation, and the entire separation process is simple, green and environmentally friendly, and convenient for large-scale promotion and application. In addition, after the separation product of the present invention is calcined, the obtained product can be reused, thereby improving the utilization rate of the separation product.
[0036] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For any details not described in individual embodiments, reference may be made to the description in other embodiments.
[0037] The above-described embodiments merely illustrate the implementation methods of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.
Claims
1. A method for separating magnesium and manganese in laterite nickel ore hydrometallurgy, characterized in that: The steps include: S1, adding a neutralizing agent to the laterite nickel ore acid leaching solution to react, and after the reaction, performing iron and aluminum slag sedimentation treatment to obtain a liquid after iron and aluminum removal; S2, adding a neutralizing agent to the iron- and aluminum-removed liquid to perform nickel-cobalt-manganese precipitation treatment to obtain nickel-cobalt-manganese hydroxide and nickel-cobalt-manganese precipitation liquid; S3. Carbon dioxide is introduced into the solution after precipitation of nickel, cobalt and manganese for flotation-gravity sedimentation to obtain an upper emulsion and a lower emulsion, and then the upper emulsion and the lower emulsion are filter-filtered to obtain magnesium carbonate and manganese carbonate, respectively.
2. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S1, the laterite nickel ore acid leaching solution includes the following components: 2-5 g / L iron, 4-8 g / L aluminum, 5-7 g / L nickel, 0.4-0.8 g / L cobalt, 3-5 g / L manganese, and 6-10 g / L magnesium.
3. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S1, the neutralizing agent is selected from at least one of sodium hydroxide, sodium carbonate, magnesium oxide and potassium hydroxide.
4. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S1, the reaction step specifically includes: reacting for 4-8 hours at a pH value of 2-6 and a temperature of 60-80°C.
5. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S1, during the iron-aluminum slag sedimentation treatment process, the step of adding clay is also included, and the mass concentration of the clay is 5-10%.
6. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S2, the neutralizing agent is selected from at least one of sodium hydroxide, sodium carbonate, magnesium oxide and potassium hydroxide.
7. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: In step S2, the nickel, cobalt and manganese precipitation treatment step specifically includes: reacting for 3-6 hours at a pH value of 7-9 and a temperature of 70-90°C.
8. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 1, characterized in that: The method further includes calcining the magnesium carbonate in step S3 to obtain magnesium oxide and carbon dioxide.
9. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 8, characterized in that: The method further includes recycling the magnesium oxide as a neutralizing agent to the iron-aluminum slag sedimentation treatment step and / or the nickel-cobalt-manganese precipitation treatment step.
10. The method for separating magnesium and manganese in laterite nickel ore hydrometallurgy according to claim 8, characterized in that: The method further includes recycling the carbon dioxide to the flotation-gravity sedimentation treatment step.