Improving method for main component in nickel-cobalt hydroxide intermediate product
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-07-07
- Publication Date
- 2026-08-13
Smart Images
Figure CN2025107302_13082026_PF_FP_ABST
Abstract
Description
Methods for increasing the main component in nickel-cobalt hydroxide intermediate products
[0001] This disclosure claims priority to Chinese Patent Application No. 202510145095.4, filed on February 10, 2025, entitled “Method for Improving the Main Component in Nickel-Cobalt Hydroxide Intermediate Products”, the entire contents of which are incorporated herein by reference. Technical Field
[0002] This disclosure relates to the field of nickel-cobalt hydrometallurgical technology, and more specifically, to a method for improving the main component in a nickel-cobalt hydroxide intermediate product. Background Technology
[0003] Currently, high-pressure leaching hydrometallurgy of limonite-type laterite nickel ore is one of the main processes in nickel metallurgy. The process flow is as follows: leaching—iron and aluminum removal—nickel and cobalt precipitation to obtain nickel-cobalt hydroxide (MHP) intermediate product; this nickel-cobalt hydroxide intermediate product is then subjected to acid dissolution—impurity removal, and extraction to separate impurities from nickel and cobalt to obtain the final nickel-cobalt product.
[0004] The inventors of this disclosure recognize that the above-mentioned process has the following problems: the content of impurities such as magnesium and manganese in the product is too high, approximately 1-5% and 5-8% respectively, while the content of nickel and cobalt is too low, approximately 35-41% and 1-2% respectively. Simultaneously, a large amount of basic sulfate is generated during the precipitation process, resulting in a high sulfate content and a low nickel and cobalt content. The presence of impurities increases the cost of subsequent refining production. Therefore, providing an efficient treatment method to solve the above problems is of great significance.
[0005] In view of this, this disclosure is hereby made. Summary of the Invention
[0006] In view of the above problems, the purpose of this disclosure is to provide a method for improving the main components in nickel-cobalt hydroxide intermediate products, so as to solve the problems of high content of impurities such as magnesium and manganese, high content of sulfate, and the resulting increase in subsequent refining production costs in the existing nickel-cobalt hydroxide intermediate products.
[0007] To achieve the above objectives, according to one aspect of this disclosure, a method for enhancing the main components in a nickel-cobalt hydroxide intermediate product is provided. The nickel-cobalt hydroxide intermediate product includes hydroxides of nickel ions, cobalt ions, manganese ions, and magnesium ions, as well as a basic sulfate. The enhancement method includes: step S100, performing a first activation on a slurry of the nickel-cobalt hydroxide intermediate product using an alkaline substance to obtain a first activated product slurry; step S200, adjusting the solid content of the first activated product slurry; step S300, performing a second activation on the first activated product slurry using a reducing agent to obtain a second activated product slurry; step S400, performing solid-liquid separation on the second activated product slurry to obtain a second activated product filter cake; and step S500, adding the second activated product filter cake to a nickel-cobalt containing solution for a conversion reaction to obtain nickel-cobalt hydroxide and a converted liquid.
[0008] One optional technical solution is that, in step S100 above, the solid content of the nickel-cobalt hydroxide intermediate product slurry is 0.1% to 35%, preferably 5% to 20%.
[0009] One optional technical solution is that, in step S100 above, the nickel-cobalt hydroxide intermediate product slurry is obtained by pretreatment of the nickel-cobalt hydroxide intermediate product, and the nickel-cobalt hydroxide intermediate product is either a nickel-cobalt hydroxide slurry or a nickel-cobalt hydroxide filter cake.
[0010] One optional technical solution is that, in step S100 above, when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide slurry, the nickel-cobalt hydroxide slurry is concentrated or diluted to obtain a nickel-cobalt hydroxide intermediate product slurry; when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide filter cake, the nickel-cobalt hydroxide filter cake is pulped to obtain a nickel-cobalt hydroxide intermediate product slurry.
[0011] One optional technical solution is that, in step S100 above, the alkaline substance is selected from any one or more of sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
[0012] One optional technical solution is that, in the above step S100, the temperature of the first activation is 25℃~260℃, preferably 80℃~150℃, and the time of the first activation is 0.1h~10h, preferably 2h~8h.
[0013] One optional technical solution is that, in step S100 above, the mass of the alkaline substance is 0.05% to 20% of the dry weight of the nickel-cobalt hydroxide intermediate product slurry, preferably 0.5% to 5%.
[0014] One optional technical solution is that, in step S300 above, the reducing agent is selected from any one or more of sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and sulfur dioxide.
[0015] One optional technical solution is that, in step S300 above, the temperature of the second activation is 25℃~260℃, preferably 80℃~150℃, and the time of the second activation is 0.1h~10h, preferably 2h~8h.
[0016] One optional technical solution is that, in step S300 above, the amount of the sulfurous acid group from the reducing agent is 0.1 to 5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate product slurry, preferably 0.2 to 1.5 times.
[0017] One optional technical solution is that, in step S200 above, the solid content of the first activated product slurry is 0.1% to 35%, preferably 5% to 20%; the process of adjusting the solid content of the first activated product slurry includes: concentrating or diluting the first activated product slurry; or sequentially performing solid-liquid separation and slurrying treatment on the first activated product slurry.
[0018] One optional technical solution is that, in step S500 above, the temperature of the conversion reaction is 25℃~260℃, preferably 80~150℃, the time of the conversion reaction is 0.1h~10h, preferably 2h~8h, and the liquid-solid ratio of the conversion reaction is 1~10:1, preferably 3~10:1.
[0019] One optional technical solution is that, in step S500 above, the nickel-cobalt hydroxide intermediate product is obtained from a nickel-cobalt-containing solution by a precipitation method, wherein the precipitation method is selected from any one of the following: magnesium oxide precipitation method, magnesium hydroxide precipitation method, sodium hydroxide lithium precipitation method, potassium hydroxide lithium precipitation method, calcium oxide precipitation method, and calcium hydroxide precipitation method.
[0020] One optional technical solution is that, in step S500 above, the nickel-cobalt solution includes a laterite nickel ore leaching system, which is selected from any one or more of the following: laterite nickel ore sulfuric acid leaching solution, laterite nickel ore hydrochloric acid leaching solution, and laterite nickel ore nitric acid leaching solution.
[0021] Applying the technical solution of this disclosure can significantly increase the total nickel and cobalt content in nickel-cobalt hydroxide to over 50%, while effectively reducing the content of impurities such as magnesium and manganese, thus optimizing product quality. The reduction in impurity content decreases the complexity and cost of subsequent refining and separation processes, improving the overall economic efficiency of the hydrometallurgical process. The method of this disclosure can effectively decompose basic sulfates in the product, reducing the sulfate content and avoiding the negative impacts of sulfate on downstream processes, such as equipment corrosion. The method of this disclosure has good applicability to different precipitation methods and systems, enhancing the flexibility and adaptability of the process. Therefore, through the method of this disclosure, the nickel and cobalt content in the product can be increased, impurity content reduced, subsequent processing costs decreased, sulfate issues improved, and the process exhibits high flexibility and strong applicability, ultimately improving the economic efficiency and environmental friendliness of the hydrometallurgical process.
[0022] To achieve the foregoing and related objectives, one or more aspects of this disclosure include features that will be described in detail below and specifically pointed out in the claims. The following description and accompanying drawings illustrate certain exemplary aspects of this disclosure. However, these aspects indicate only a few of the various ways in which the principles of this disclosure can be applied. Furthermore, this disclosure is intended to include all such aspects and their equivalents. Attached Figure Description
[0023] Other objects and results of this disclosure will become more apparent and readily understood upon reference to the following description taken in conjunction with the accompanying drawings and the claims, and with a more complete understanding of this disclosure. The accompanying drawings, which form part of this disclosure, are used to provide a further understanding of this disclosure. The illustrative embodiments of this disclosure and their descriptions are used to explain this disclosure and do not constitute an undue limitation of this disclosure. In the drawings:
[0024] Figure 1 shows a flowchart of a method for enhancing the main component in a nickel-cobalt hydroxide intermediate product according to an embodiment of the present disclosure.
[0025] In all the accompanying drawings, the same reference numerals indicate similar or corresponding features or functions. Detailed Implementation
[0026] In the following description, numerous specific details are set forth for illustrative purposes and to provide a thorough understanding of one or more embodiments. However, it will be apparent that the embodiments and features described herein can be combined with each other without conflict; these embodiments can also be implemented without these specific details. In other instances, well-known structures and devices are shown in block diagram form for ease of description of one or more embodiments.
[0027] The specific embodiments of this disclosure will now be described in detail with reference to the accompanying drawings.
[0028] As described in the background section, the existing nickel-cobalt hydroxide intermediate product has a high content of impurities such as magnesium and manganese, and a high content of sulfate, which leads to an increase in the cost of subsequent refining production. In order to solve this technical problem, this disclosure provides a method for improving the main components in the nickel-cobalt hydroxide intermediate product.
[0029] To address the aforementioned problems, this disclosure provides a method for enhancing the main components in a nickel-cobalt hydroxide intermediate product. The nickel-cobalt hydroxide intermediate product includes hydroxides of nickel ions, cobalt ions, manganese ions, and magnesium ions, as well as a basic sulfate. The enhancement method includes: step S100, performing a first activation on a slurry of the nickel-cobalt hydroxide intermediate product using an alkaline substance to obtain a first activated product slurry; step S200, adjusting the solid content of the first activated product slurry; step S300, performing a second activation on the first activated product slurry using a reducing agent to obtain a second activated product slurry; step S400, performing solid-liquid separation on the second activated product slurry to obtain a second activated product filter cake; and step S500, adding the second activated product filter cake to a nickel-cobalt containing solution for a conversion reaction to obtain nickel-cobalt hydroxide and a converted liquid.
[0030] The method disclosed herein can significantly increase the total nickel and cobalt content in nickel-cobalt hydroxide to over 50%, while effectively reducing the content of impurities such as magnesium and manganese, thus optimizing product quality. The reduction in impurity content decreases the complexity and cost of subsequent refining and separation processes, improving the overall economic efficiency of the hydrometallurgical process. This method can effectively decompose basic sulfates in the product, reducing sulfate content and avoiding the negative impacts of sulfate on downstream processes, such as equipment corrosion. This method has good applicability to different precipitation methods and systems, enhancing the flexibility and adaptability of the process. Therefore, the method disclosed herein can increase the nickel and cobalt content in the product, reduce impurity content, reduce subsequent processing costs, improve sulfate control, and offers high flexibility and strong applicability, thus improving the overall economic efficiency and environmental friendliness of the hydrometallurgical process.
[0031] Specifically, the alkaline activation mechanism in step S100 enhances the reactivity of certain impurities (such as magnesium hydroxide) in the nickel-cobalt hydroxide intermediate, making them more readily replaceable with nickel-cobalt ions in subsequent conversion processes. The importance of solid content adjustment and solid-liquid separation in steps S200 and S400 lies in the fact that the solid content of the slurry directly affects the efficiency and energy required for subsequent reactions. An appropriate slurry concentration maximizes the reaction contact area, accelerates the reaction rate, and reduces processing energy consumption. The reducing activation mechanism in step S300 involves the addition of a reducing agent to reduce high-valence manganese, converting it into low-valence manganese hydroxide, thereby increasing the reactivity of manganese and facilitating its replacement reaction with nickel-cobalt ions. The conversion reaction principle in step S500 involves the conversion reaction in a nickel-cobalt-containing solution, essentially utilizing the activated nickel-cobalt hydroxide intermediate to replace nickel-cobalt ions in the solution, ultimately generating higher-purity nickel-cobalt hydroxide. Simultaneously, impurity ions are released into the solution, facilitating subsequent separation and processing.
[0032] Furthermore, the synergistic effect of the first alkaline activation and the second reducing activation steps can specifically treat the main impurities in the nickel-cobalt hydroxide intermediate, such as magnesium hydroxide and high-valent manganese. By changing their chemical forms, these impurities are more easily replaced by nickel-cobalt ions in subsequent conversion reactions, thereby improving the purity of the product. The order of the first alkaline activation and the second reducing activation steps helps to further ensure that the manganese in the slurry of the second activated product is divalent manganese, thus ensuring the efficiency and effectiveness of the conversion reaction.
[0033] In a preferred embodiment, in order to improve the activity of magnesium hydroxide and manganese hydroxide in the conversion reaction and reduce the risk of them being oxidized after being left for a long time, the filter cake of the second activated product is returned to the aforementioned conversion reaction within 10 minutes, more preferably within 3 minutes.
[0034] Adjusting the solid content is crucial for improving the reaction efficiency of the activation and conversion processes. Too low a solid content can reduce the concentration of alkaline substances in the nickel-cobalt hydroxide intermediate slurry, affecting the reaction rate. Too high a solid content may reduce reaction efficiency due to increased system viscosity. Therefore, based on improving the purity and reaction efficiency of the final nickel-cobalt hydroxide product, in some preferred embodiments of this disclosure, in step S100, the solid content of the nickel-cobalt hydroxide intermediate slurry is 0.1% to 35%, preferably 5% to 20%, which further contributes to improving the efficiency of the activation and conversion reactions, promoting the replacement reaction between nickel-cobalt ions and impurity ions, and reducing energy consumption and processing costs. The solid content of the nickel-cobalt hydroxide intermediate product slurry can be 0.1%, 0.3%, 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, or 35%, and is not limited to any value between 0.1% and 35%.
[0035] In some embodiments of this disclosure, in step S100 above, the nickel-cobalt hydroxide intermediate product slurry is obtained by pretreatment of the nickel-cobalt hydroxide intermediate product, which is either a nickel-cobalt hydroxide slurry or a nickel-cobalt hydroxide filter cake.
[0036] Nickel-cobalt hydroxide intermediates can have a wide range of sources. For example, nickel-cobalt hydroxide intermediates obtained by high-pressure leaching hydrometallurgy of laterite nickel ore can be nickel-cobalt hydroxide slurry or nickel-cobalt hydroxide filter cake. After some pretreatment, nickel-cobalt hydroxide in this form can be used to obtain nickel-cobalt hydroxide intermediate slurry suitable for step S100, which facilitates subsequent activation treatment.
[0037] In some embodiments of this disclosure, in step S100 above, when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide slurry, the nickel-cobalt hydroxide slurry is concentrated or diluted to obtain a nickel-cobalt hydroxide intermediate product slurry; when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide filter cake, the nickel-cobalt hydroxide filter cake is pulped to obtain a nickel-cobalt hydroxide intermediate product slurry.
[0038] By using nickel-cobalt hydroxide slurry or nickel-cobalt hydroxide filter cake as raw materials, and through slurrying, concentration or dilution treatment, the uniformity of the nickel-cobalt hydroxide intermediate product slurry and the reaction contact area are improved, which is conducive to the smooth progress of subsequent activation and conversion reaction processes.
[0039] In some embodiments of this disclosure, in step S100 above, the alkaline substance is selected from any one or more of sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
[0040] Activation with alkaline substances such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide helps to improve the reactivity of magnesium hydroxide in nickel-cobalt hydroxide intermediates, accelerates its displacement reaction with nickel-cobalt ions, and effectively reduces the magnesium content in nickel-cobalt hydroxide products.
[0041] Performing the first activation under suitable temperature conditions helps to maximize the reaction efficiency of the first activation. In some embodiments of this disclosure, in step S100, the preferred temperature for the first activation is 25℃ to 260℃, preferably 80℃ to 150℃, and the preferred activation time is 0.1h to 10h, preferably 2h to 8h. This helps to reduce energy consumption, minimize side reactions, and improve the purity and quality of the nickel-cobalt hydroxide product. The temperature for the first activation can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 120℃, 150℃, 180℃, 200℃, 230℃, or 260℃, and is not limited to any value within the range of 25℃ to 260℃. The activation time for the first time can be 0.1h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 9h or 10h, but is not limited to any value from 0.1h to 10h.
[0042] The amount of alkaline substance used is crucial to the activation effect of nickel-cobalt hydroxide intermediate products. A suitable amount of alkaline substance helps activate impurities without creating an excessively alkaline environment. In some embodiments of this disclosure, preferably in step S100, the mass of the alkaline substance is 0.05% to 20% of the dry weight of the nickel-cobalt hydroxide intermediate product slurry, more preferably 0.5% to 5%, thereby further improving the stability of the nickel-cobalt hydroxide product and the efficiency of subsequent processing. The mass of the alkaline substance can be 0.05%, 0.1%, 0.3%, 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, 15%, or 20% of the dry weight of the nickel-cobalt hydroxide intermediate product slurry, and is not limited to any value within the range of 0.05% to 20%.
[0043] In some embodiments of this disclosure, in step S300 above, the reducing agent is selected from any one or more of sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and sulfur dioxide.
[0044] The first activation using reducing agents such as sodium sulfite and potassium sulfite effectively reduced the valence state of manganese in the nickel-cobalt hydroxide intermediate, improved its reactivity, promoted the substitution reaction between manganese and nickel-cobalt ions, and reduced the manganese content in the final nickel-cobalt hydroxide product.
[0045] Performing a second activation under suitable temperature and time conditions can maximize the efficiency of the second activation. In some preferred embodiments of this disclosure, in step S300 above, the temperature of the second activation is 25℃~260℃, preferably 80℃~150℃, and the time of the second activation is 0.1h~10h, preferably 2h~8h. This helps to further reduce energy waste, while reducing the occurrence of side reactions and improving the purity and quality of the final nickel-cobalt hydroxide product. The temperature of the second activation can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 120℃, 150℃, 180℃, 200℃, 230℃, or 260℃, and is not limited to any value within the range of 25℃~260℃. The time for the second activation can be 0.1h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 9h or 10h, but is not limited to any value from 0.1h to 10h.
[0046] In some embodiments of this disclosure, in step S300 above, the amount of sulfurous acid groups derived from the reducing agent is 0.1 to 5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate slurry.
[0047] The amount of sulfite groups in the reducing agent is 0.1 to 5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate product, preferably 0.2 to 1.5 times. This ratio is beneficial for improving the effective reduction of high-valence manganese, while reducing the risk of excessive addition of reducing agent and simplifying subsequent processing. The amount of sulfite groups in the reducing agent can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.3, 2.5, 2.8, 3, 3.5, 4, 4.5, or 5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate product, and is not limited to any value within the range of 0.1 to 5 times.
[0048] In some embodiments of this disclosure, in step S200 above, the solid content of the first activated product slurry is 0.1% to 35%, preferably 5% to 20%; the process of adjusting the solid content of the first activated product slurry includes: concentrating or diluting the first activated product slurry; or sequentially performing solid-liquid separation and slurrying treatment on the first activated product slurry. The solid content of the first activated product slurry can be 0.1%, 0.3%, 0.5%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, or 35%, and is not limited to any value from 0.1% to 35%.
[0049] Adjusting the solid content of the first activated product slurry helps optimize the conditions for the second activation, thereby improving the efficiency of the second activation, while reducing energy consumption and improving the overall economic efficiency of the process.
[0050] Optimizing parameters such as temperature, time, and liquid-solid ratio in the conversion reaction helps to maximize the displacement reaction between nickel-cobalt ions and impurities, improve metal recovery rate, and reduce energy consumption and processing costs. Therefore, in some embodiments of this disclosure, in step S500, the preferred temperature of the conversion reaction is 25℃~260℃, preferably 80~150℃; the preferred time is 0.1h~10h, preferably 2h~8h; and the preferred liquid-solid ratio is 1~10:1, preferably 3~10:1. The conversion reaction temperature can be 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 120℃, 150℃, 180℃, 200℃, 230℃, or 260℃, and is not limited to any value within the range of 25℃~260℃. The conversion reaction time can be 0.1h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 9h, or 10h, and is not limited to any value from 0.1h to 10h. The liquid-to-solid ratio of the conversion reaction can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, and is not limited to any value from 1 to 10:1.
[0051] In some embodiments of this disclosure, in step S500 above, the nickel-cobalt hydroxide intermediate product is obtained from a nickel-cobalt-containing solution by a precipitation method, wherein the precipitation method is selected from any one of magnesium oxide precipitation, magnesium hydroxide precipitation, lithium sodium hydroxide precipitation, lithium potassium hydroxide precipitation, calcium oxide precipitation, and calcium hydroxide precipitation.
[0052] Different precipitation methods affect the original composition of nickel-cobalt hydroxide intermediate products. The optimized precipitation methods mentioned above are beneficial for providing raw materials for nickel-cobalt hydroxide intermediate products that are more suitable for subsequent processing, thereby improving the efficiency of the method for enhancing the main components in the entire nickel-cobalt hydroxide intermediate product.
[0053] Different leaching systems (sulfuric acid, hydrochloric acid, nitric acid) affect the solubility and chemical form of impurities in nickel-cobalt hydroxide. Selecting a suitable leaching system helps to further optimize impurity separation and improve nickel-cobalt recovery efficiency. In some embodiments of this disclosure, preferably in step S500, the nickel-cobalt-containing solution includes a laterite nickel ore leaching post-system, selected from any one or more of laterite nickel ore sulfuric acid leaching post-solution, laterite nickel ore hydrochloric acid leaching post-solution, and laterite nickel ore nitric acid leaching post-solution, thereby facilitating further impurity separation and improving nickel-cobalt recovery rate.
[0054] Furthermore, the preferred application of the method for enhancing the main components in the nickel-cobalt hydroxide intermediate product disclosed herein is a nickel-cobalt hydroxide intermediate product obtained by precipitation after sulfuric acid leaching of laterite nickel ore. This nickel-cobalt hydroxide intermediate product contains 35-41% nickel, 3-4% cobalt, 1-5% magnesium, 5-8% manganese, and 4-5% sulfate. Through the method for enhancing the main components in the nickel-cobalt hydroxide intermediate product, the final nickel-cobalt hydroxide product contains 45-50% nickel, 3-5% cobalt, 0.05-1% magnesium, 0.5-2% manganese, and 0.5-1.5% sulfate.
[0055] The preferred nickel-cobalt-containing solution is the intermediate product of nickel-cobalt hydroxide and nickel-cobalt sulfate recovered from the liquid precipitation after iron and aluminum removal in the hydrometallurgical process of laterite nickel ore, wherein Ni 2+ The content is 2-6 g / L, Co 2+ The content is 0.1–0.5 g / L, Mg 2+ The content is 2-10 g / L, Mn 2+ The content is 1-5 g / L.
[0056] The present disclosure will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed by the present disclosure.
[0057] The following examples illustrate the processing of nickel-cobalt hydroxide intermediates and nickel-cobalt sulfate solution recovered from the liquid precipitation after iron and aluminum removal in the hydrometallurgical process of laterite nickel ore. The ionic composition of the nickel-cobalt sulfate solution is as follows:
[0058] Example 1
[0059] Methods for enhancing the main components in the intermediate product of nickel hydroxide / cobalt hydroxide recovery from the liquid precipitation after iron and aluminum removal in the hydrometallurgical process of laterite nickel ore:
[0060] Referring to the flowchart of the method for improving the main components in the nickel-cobalt hydroxide intermediate product shown in Figure 1, the nickel-cobalt hydroxide intermediate product filter cake obtained by precipitation in the sulfate system contains 39% nickel, 3% cobalt, 2% magnesium, 7% manganese, and 4% sulfate. It is then slurried with water to a solid content of 20%, yielding a nickel-cobalt hydroxide intermediate product slurry. Sodium hydroxide is added to the nickel-cobalt hydroxide intermediate product slurry for the first activation. The mass of sodium hydroxide is 2% of the dry weight of the nickel-cobalt hydroxide intermediate product slurry. The first activation temperature is 150°C, and the time is 2 hours, yielding a first activated product slurry. This first activated product slurry is then filtered and slurried again to a solid content of 20%.
[0061] Sodium sulfite was added to the first activated product slurry with a solid content of 20% for a second activation. The amount of sulfite groups was 0.2 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate product slurry. The second activation was carried out at 150°C for 2 hours to obtain a second activated product slurry. The second activated product slurry was then filtered, and the resulting filter cake was added to a nickel-cobalt sulfate solution within 3 minutes. A conversion reaction was carried out at a liquid-to-solid ratio of 3:1 at 150°C for 2 hours. After filtration and washing, a high-quality nickel-cobalt hydroxide product was obtained, containing 48% nickel, 4% cobalt, 0.1% magnesium, 0.8% manganese, and 0.6% sulfate.
[0062] Example 2
[0063] The only difference between this embodiment and Example 1 is that the solid content of the nickel-cobalt hydroxide intermediate slurry is 5%, and the final product is nickel-cobalt hydroxide. After testing, it is found that the nickel content is 48.5%, the cobalt content is 4.5%, the magnesium content is 0.08%, the manganese content is 0.6%, and the sulfate content is 0.5%.
[0064] Example 3
[0065] The only difference between this embodiment and Example 1 is that the solid content of the nickel-cobalt hydroxide intermediate slurry is 35%, and the final product is nickel-cobalt hydroxide. After testing, it is found that the nickel content is 48.7%, the cobalt content is 3.5%, the magnesium content is 0.3%, the manganese content is 1.2%, and the sulfate content is 0.8%.
[0066] Example 4
[0067] The only difference between this embodiment and Example 1 is that the solid content of the nickel-cobalt hydroxide intermediate slurry is 0.1%, and the final product is nickel-cobalt hydroxide. After testing, it is found that the nickel content is 48%, the cobalt content is 4%, the magnesium content is 0.1%, the manganese content is 0.8%, and the sulfate content is 0.6%.
[0068] Example 5
[0069] The only difference between this embodiment and Example 1 is that ammonium hydroxide is added to the nickel-cobalt hydroxide intermediate product slurry for the first activation, and finally nickel-cobalt hydroxide is obtained. After testing, its nickel content is 47.7%, cobalt content is 3.8%, magnesium content is 0.1%, manganese content is 0.8%, and sulfate content is 1.3%.
[0070] Example 6
[0071] The only difference between this embodiment and Example 1 is that the first activation temperature is 80°C and the first activation time is 8 hours, ultimately yielding nickel cobalt hydroxide. Testing revealed that it contained 48.9% nickel, 3.7% cobalt, 0.1% magnesium, 0.8% manganese, and 0.8% sulfate.
[0072] Example 7
[0073] The only difference between this embodiment and Example 1 is that the first activation temperature is 60°C and the first activation time is 10 hours, ultimately yielding nickel cobalt hydroxide. Testing revealed that it contained 47.7% nickel, 3.7% cobalt, 0.1% magnesium, 0.8% manganese, and 1.2% sulfate.
[0074] Example 8
[0075] The only difference between this embodiment and Example 1 is that the mass of sodium hydroxide is 5% of the dry weight of the nickel-cobalt hydroxide intermediate slurry, and the final product is nickel-cobalt hydroxide. After testing, it is found that the nickel content is 48.2%, the cobalt content is 4.3%, the magnesium content is 0.1%, the manganese content is 0.8%, and the sulfate content is 0.5%.
[0076] Example 9
[0077] The only difference between this embodiment and Example 1 is that the mass of sodium hydroxide is 0.4% of the dry weight of the nickel-cobalt hydroxide intermediate slurry, and the final product is nickel-cobalt hydroxide. After testing, it is found that the nickel content is 47.8%, the cobalt content is 3.8%, the magnesium content is 0.1%, the manganese content is 0.8%, and the sulfate content is 1.3%.
[0078] Example 10
[0079] The only difference between this embodiment and Example 1 is that the reducing agent is ammonium sulfite, and the final product is nickel cobalt hydroxide. The nickel content is 48.3%, the cobalt content is 4.1%, the magnesium content is 0.1%, the manganese content is 1.2%, and the sulfate content is 0.6%.
[0080] Example 11
[0081] The only difference between this embodiment and Example 1 is that the second activation temperature is 80°C and the second activation time is 8 hours, ultimately yielding nickel cobalt hydroxide. Testing revealed that it contained 47.5% nickel, 3.9% cobalt, 0.1% magnesium, 1.2% manganese, and 0.6% sulfate.
[0082] Example 12
[0083] The only difference between this embodiment and Example 1 is that the second activation temperature is 60°C and the second activation time is 10 hours, ultimately yielding nickel cobalt hydroxide. Testing revealed that it contained 48.1% nickel, 3.7% cobalt, 0.1% magnesium, 1.5% manganese, and 0.6% sulfate.
[0084] Example 13
[0085] The only difference between this embodiment and Example 1 is that the amount of sulfite groups is 1.5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate slurry, resulting in nickel-cobalt hydroxide. Testing showed that it contained 48.5% nickel, 4.6% cobalt, 0.1% magnesium, 0.5% manganese, and 0.6% sulfate.
[0086] Example 14
[0087] The only difference between this embodiment and Example 1 is that the amount of sulfite groups is 0.1 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate slurry, resulting in nickel-cobalt hydroxide. Testing showed that it contained 47.6% nickel, 3.8% cobalt, 0.1% magnesium, 1.5% manganese, and 0.6% sulfate.
[0088] Example 15
[0089] The only difference between this embodiment and Example 1 is that the obtained second activated product filter cake is added to a nickel cobalt sulfate solution within 10 minutes to finally obtain nickel cobalt hydroxide. The analysis showed that it contained 47.6% nickel, 3.8% cobalt, 0.1% magnesium, 1.2% manganese, and 0.6% sulfate.
[0090] Comparative Example 1
[0091] The filter cake of nickel-cobalt hydroxide intermediate product obtained by precipitation in a sulfate system contained 39% nickel, 3% cobalt, 2% magnesium, 7% manganese, and 4% sulfate. It was slurried with water until the solid content reached 20%, yielding a nickel-cobalt hydroxide intermediate product slurry. Sodium sulfite was added to the nickel-cobalt hydroxide intermediate product slurry for the first activation at 150℃ for 2 hours, yielding a first activated product slurry. This first activated product slurry was then filtered and slurried again until the solid content reached 20%.
[0092] Sodium hydroxide was added to the first activated product slurry with a solid content of 20% for a second activation at 150°C for 2 hours, resulting in a second activated product slurry. The second activated product slurry was then filtered, and the resulting filter cake was added to a nickel-cobalt sulfate solution containing 3 g / L nickel and 0.3 g / L cobalt. The conversion reaction was carried out at a liquid-to-solid ratio of 3:1 at 150°C for 2 hours. After filtration and washing, a high-quality nickel-cobalt hydroxide product was obtained, containing 45% nickel, 3% cobalt, 0.1% magnesium, 4% manganese, and 0.6% sulfate.
[0093] It should be noted that the solid content of the nickel-cobalt hydroxide intermediate product slurry in Example 4 is 0.1%, which has little impact on the quality of the final nickel-cobalt hydroxide product. The main impact is that it leads to increased water consumption, which makes the wastewater treatment more complicated and prolongs the treatment time, thus hindering cost reduction.
[0094] As can be seen from the above description, the embodiments of this disclosure achieve the following technical effects:
[0095] The method disclosed herein can significantly increase the total nickel and cobalt content in nickel-cobalt hydroxide to over 50%, while effectively reducing the content of impurities such as magnesium and manganese, thus optimizing product quality. The reduction in impurity content decreases the complexity and cost of subsequent refining and separation processes, improving the overall economic efficiency of the hydrometallurgical process. This method can effectively decompose basic sulfates in the product, reducing sulfate content and avoiding the negative impacts of sulfate on downstream processes, such as equipment corrosion. The method disclosed herein has good applicability to different precipitation methods and systems, enhancing the flexibility and adaptability of the process. Therefore, the method disclosed herein can increase the nickel and cobalt content in the product, reduce impurity content, reduce subsequent processing costs, improve sulfate control, and offers high flexibility and strong applicability, thereby improving the overall economic efficiency and environmental friendliness of the hydrometallurgical process.
[0096] The above are merely preferred embodiments of this disclosure and are not intended to limit this disclosure. Various modifications and variations can be made to this disclosure by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the scope of protection of this disclosure.
Claims
1. A method for enhancing the main component in a nickel-cobalt hydroxide intermediate product, wherein the nickel-cobalt hydroxide intermediate product comprises hydroxides of nickel ions, cobalt ions, manganese ions, and magnesium ions, and a basic sulfate, characterized in that, The lifting method includes: Step S100: The nickel-cobalt hydroxide intermediate product slurry is activated for the first time using an alkaline substance to obtain the first activated product slurry. Step S200: Adjust the solid content of the first activated product slurry; Step S300: The first activated product slurry is activated a second time using a reducing agent to obtain the second activated product slurry; Step S400: Perform solid-liquid separation on the second activated product slurry to obtain the second activated product filter cake; In step S500, the filter cake of the second activated product is added to a nickel-cobalt-containing solution for conversion reaction to obtain nickel-cobalt hydroxide and the converted liquid.
2. The method for improving the main component in the nickel-cobalt hydroxide intermediate product according to claim 1, characterized in that, In step S100, the solid content of the nickel-cobalt hydroxide intermediate product slurry is 0.1% to 35%.
3. The method for improving the main component in the nickel-cobalt hydroxide intermediate product according to claim 2, characterized in that, In step S100, the nickel-cobalt hydroxide intermediate product slurry is obtained by pretreatment of the nickel-cobalt hydroxide intermediate product, which is either a nickel-cobalt hydroxide slurry or a nickel-cobalt hydroxide filter cake.
4. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to claim 3, characterized in that, In step S100, when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide slurry, the nickel-cobalt hydroxide slurry is concentrated or diluted to obtain the nickel-cobalt hydroxide intermediate product slurry; when the nickel-cobalt hydroxide intermediate product is a nickel-cobalt hydroxide filter cake, the nickel-cobalt hydroxide filter cake is pulped to obtain the nickel-cobalt hydroxide intermediate product slurry.
5. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S100, the alkaline substance is selected from any one or more of sodium hydroxide, potassium hydroxide, and ammonium hydroxide.
6. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S100, the temperature of the first activation is 25℃~260℃, and the time of the first activation is 0.1h~10h.
7. The method for improving the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S100, the mass of the alkaline substance is 0.05% to 20% of the dry weight of the nickel-cobalt hydroxide intermediate product slurry.
8. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S300, the reducing agent is selected from any one or more of sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and sulfur dioxide.
9. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S300, the temperature of the second activation is 25℃~260℃, and the time of the second activation is 0.1h~10h.
10. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S300, the amount of sulfurous acid groups derived from the reducing agent is 0.1 to 5 times the amount of manganese ions in the nickel-cobalt hydroxide intermediate product slurry.
11. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S200, the solid content of the first activated product slurry is 0.1% to 35%. The process of adjusting the solid content of the first activated product slurry includes: The first activated product slurry is concentrated or diluted. Alternatively, the first activated product slurry can be subjected to solid-liquid separation and slurry treatment sequentially.
12. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S500, the temperature of the conversion reaction is 25℃~260℃, the time of the conversion reaction is 0.1h~10h, and the liquid-solid ratio of the conversion reaction is 1~10:
1.
13. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to any one of claims 1 to 4, characterized in that, In step S500, the nickel-cobalt hydroxide intermediate product is obtained from a nickel-cobalt-containing solution by a precipitation method, wherein the precipitation method is selected from any one of magnesium oxide precipitation, magnesium hydroxide precipitation, lithium sodium hydroxide precipitation, lithium potassium hydroxide precipitation, calcium oxide precipitation, and calcium hydroxide precipitation.
14. The method for enhancing the main component in the nickel-cobalt hydroxide intermediate product according to claim 13, characterized in that, In step S500, the nickel-cobalt-containing solution includes a laterite nickel ore leaching system, which is selected from any one or more of the following: laterite nickel ore sulfuric acid leaching solution, laterite nickel ore hydrochloric acid leaching solution, and laterite nickel ore nitric acid leaching solution.