Green method for producing nickel-cobalt-manganese new energy raw material from laterite nickel ore based on hydrometallurgy

Abstract

A green method for producing a nickel-cobalt-manganese new energy raw material from laterite nickel ore based on hydrometallurgy, mainly comprising ore blending, ore washing, ore separation, pressurization leaching or oxygen pressure leaching, cyclic leaching and neutralization, counter-current washing, multi-segment removal of iron chromium aluminum, multi-segment synthesis of nickel-cobalt-manganese hydroxide, ion extraction, preparation of a nickel-cobalt-manganese mixed salt solution, preparation of a separate nickel-cobalt-manganese salt solution, preparation of a nickel-cobalt-manganese mixed salt crystal, preparation of a separate nickel-cobalt-manganese salt crystal, preparation of a ternary precursor, comprehensive treatment of wastewater, waste gas, and waste residue, and other techniques and processes. Efficient simultaneous extraction of nickel-cobalt-manganese is achieved; ferrochrome, copper, zinc, scandium and other valuable metal elements are effectively recovered; a nickel-cobalt-manganese raw material meeting the requirement of a high-nickel ternary battery is produced; and a ternary precursor material directly used for manufacturing of the ternary battery is manufactured.

Description

A green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore Technical Field

[0001] The present invention relates to the fields of metallurgy technology and new energy materials, and in particular to a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore. Background Art

[0002] With the development of battery and energy storage technologies, the variety of batteries is increasing. Batteries made from various materials are expanding their market reach by leveraging their respective advantages. Among them, lithium iron phosphate batteries and ternary lithium batteries are the two dominant types of power lithium batteries in the new energy vehicle sector. As the two major technology approaches for power lithium batteries, lithium iron phosphate batteries and ternary lithium batteries each have their own advantages and disadvantages in terms of performance. Compared to lithium iron phosphate batteries, ternary lithium batteries, due to their higher energy density and excellent low-temperature performance, are the power of choice for long-range and high-end vehicles, demonstrating promising market prospects.

[0003] As the name suggests, ternary lithium batteries are primarily composed of the three elements nickel, cobalt, and manganese. The upstream supply chain includes nickel, cobalt, and manganese mineral resources, nickel-cobalt-manganese ternary raw materials, and ternary precursors (also known as ternary "cores" or "cores"). The midstream includes ternary lithium battery positive electrode materials, separators, electrolytes, and negative electrode materials. The downstream includes ternary battery cells, battery management systems, and packs. Nickel, cobalt, and manganese minerals and raw materials have become key factors restricting the cost and development of ternary new energy. Nickel resources and nickel raw materials are particularly crucial for high-capacity ternary batteries. High nickel content equates to high capacity and long battery life. Ultra-high nickel ternary materials containing over 55% nickel can support a range of over 800 kilometers. With the global development of electrification, nickel has become a globally scarce resource.

[0004] Laterite nickel ore is distributed in tropical countries within 22 degrees north and south of the equator, concentrated in the tropical and subtropical regions of the Pacific Rim. These include Cuba and Brazil in the Americas; Indonesia and the Philippines in Southeast Asia; and Australia, New Caledonia, and Papua New Guinea in Oceania. 70% of my country's nickel ore reserves are concentrated in Gansu, followed by Xinjiang, Yunnan, Jilin, Sichuan, Shaanxi, Qinghai, and Hubei provinces, which together account for 27% of the country's total nickel reserves. Laterite nickel ore contains all three elements: nickel, cobalt, and manganese. Low-grade laterite nickel ore, particularly those containing less than 1.3% nickel, has a nickel-cobalt-manganese ratio of 10:0.6-1.5:1.0-5.0, creating the perfect combination for high-nickel, low-cobalt ternary materials – a gift from nature. However, existing smelting technologies have long focused solely on nickel extraction, or nickel and cobalt extraction, without considering the simultaneous extraction of both, resulting in a significant waste of resources. For example, the current RKEF and the developing oxygen-enriched side-blowing technology can only extract nickel while losing cobalt and manganese, resulting in high carbon emissions. For example, the CN108913883A patent only focuses on the extraction of nickel and part of cobalt, ignoring the utilization of manganese, ignoring green design and clean production, which is a waste of current laterite nickel ore resources and cannot meet the global green development and dual-carbon economy trends. The present invention overcomes the defects of existing technologies and processes and is a green technology and process for the simultaneous extraction of nickel, cobalt and manganese from low-grade laterite nickel ore. It not only achieves efficient simultaneous extraction of nickel, cobalt and manganese, but also adopts green technology and clean production processes that save energy and reduce emissions, effectively circulates and safely disposes of wastewater, waste residue and waste gas, achieves energy conservation, carbon reduction and pollution reduction, and implements the maximum comprehensive recovery of nickel, cobalt and manganese, effectively resolving the contradiction between the demand for new energy and the strategic scarce resources of nickel, cobalt and manganese, and fully complies with the global green development and dual-carbon economy trends.

[0005] Summary of the Invention

[0006] The purpose of the present invention is to provide a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore, which is used to solve the problems in the prior art of poor removal of impurity metal elements such as iron and aluminum, low simultaneous extraction quality of nickel, cobalt and manganese products, which are difficult to be directly used for the preparation of ternary precursors, and lack of effective comprehensive utilization of multiple metal resources such as chromium, manganese, copper, zinc and scandium in laterite nickel ore.

[0007] To solve the above technical problems, the present invention provides a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore, comprising the following steps:

[0008] (1) The laterite nickel ore raw material is subjected to ore blending, ore washing, ore dressing, ore grinding and dense pre-treatment processes to obtain chromite and laterite nickel ore slurry; the chromite is separated and obtained in the ore dressing process, and the ratio of nickel, cobalt and manganese in the laterite nickel ore slurry is adapted to the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor;

[0009] (2) mixing the laterite nickel ore slurry with a reducing agent and a leaching accelerator and then performing pressure leaching or oxygen pressure leaching to obtain a mixed slurry consisting of a leachate containing nickel, cobalt and manganese and a leach residue containing iron, aluminum and silicon;

[0010] (3) subjecting a mixed slurry consisting of a leachate containing nickel, cobalt and manganese and a leach residue containing iron, aluminum and silicon to cyclic leaching and multi-stage neutralization in sequence to obtain a neutralized slurry;

[0011] (4) diluting the neutralized slurry obtained by the cyclic leaching and multi-stage neutralization treatment, performing multi-stage countercurrent washing and neutralizing the tailings, and recovering the iron metal from the resulting tailings by a reduction roasting-magnetic separation method;

[0012] (5) The final liquid phase after multi-stage countercurrent washing is subjected to multi-stage iron removal, aluminum chromium concentration and separation under the condition of adding a neutralizer and a precipitation promoter; the multi-stage iron removal consists of a first stage of iron removal, aluminum chromium removal, and a second stage or more of iron removal, and the liquid phase after the first stage of iron removal is subjected to the second stage of iron removal, the slag phase after the first stage of iron removal is returned and subjected to multi-stage countercurrent washing again, and the slag phase after the second stage or more of iron removal is reused and subjected to cyclic leaching and multi-stage neutralization treatment again;

[0013] (6) the tail liquid phase after multi-stage iron, aluminum and chromium removal is subjected to multi-stage synthesis of nickel, cobalt and manganese, and the obtained nickel, cobalt and manganese mixed hydroxide is subjected to acid dissolution and liquid phase extraction to obtain a pure liquid, or the tail liquid phase after multi-stage iron, aluminum and chromium removal is directly subjected to liquid phase extraction to obtain a pure liquid, the pure liquid is a solution composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts; the pure liquid is evaporated and concentrated to obtain pure crystals, the pure crystals are crystals composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts, and the liquid phase extraction includes liquid phase co-extraction and liquid phase selective extraction;

[0014] (7) using the nickel-cobalt-manganese mixed salt solution as a mother liquor, or using the water-soluble solution of the nickel-cobalt-manganese mixed salt crystals as a mother liquor, adding the nickel salt, cobalt salt, and manganese salt solution or crystals to the mother liquor according to the nickel-cobalt-manganese content ratio in the nickel-cobalt-manganese ternary precursor, adjusting the nickel-cobalt-manganese content ratio in the mother liquor, and performing a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor;

[0015] Alternatively, based on the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor, solutions of nickel salt, cobalt salt and manganese salt or aqueous solutions of nickel salt, cobalt salt and manganese salt crystals are mixed and formulated so that the ratio of nickel, cobalt and manganese in the formulated mixed solution matches the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor, and a controlled precipitation reaction is carried out with a precipitant and a complexing agent under a protective atmosphere to prepare the nickel-cobalt-manganese ternary precursor;

[0016] Among them, the multi-stage synthesis of nickel, cobalt and manganese consists of a first-stage synthesis of nickel, cobalt and manganese, and a second and above-stage synthesis of nickel, cobalt and manganese. The liquid phase after the first-stage synthesis of nickel, cobalt and manganese undergoes the second-stage synthesis of nickel, cobalt and manganese. The tail slag phase of the multi-stage iron, aluminum and chromium removal undergoes a first-stage synthesis of nickel, cobalt and manganese. After the first-stage synthesis of nickel, cobalt and manganese, a nickel, cobalt and manganese mixed hydroxide is obtained. The nickel, cobalt and manganese mixed hydroxide synthesized in the tail stage of the multi-stage synthesis of nickel, cobalt and manganese is returned and subjected to cyclic leaching and multi-stage neutralization treatment again.

[0017] The beneficial effect of the present invention is that, different from the prior art, the present invention provides a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore. The method belongs to green technology and green method, and mainly includes ore blending, ore washing, ore dressing, pressurized or oxygen pressure leaching, cyclic leaching and neutralization, countercurrent washing, multi-stage iron, aluminum and chromium removal, multi-stage synthesis of nickel, cobalt and manganese hydroxide, ion extraction, nickel, cobalt and manganese salt mixed solution or nickel, cobalt and manganese salt independent solution, nickel, cobalt and manganese salt mixed crystal preparation or nickel, cobalt and manganese independent salt crystal preparation, ternary precursor preparation, comprehensive treatment of wastewater, waste gas and waste residue, etc., to achieve simultaneous and efficient extraction of nickel, cobalt and manganese, and effectively recover valuable metal elements such as chromium iron, copper, zinc and scandium, to produce nickel, cobalt and manganese raw materials that meet the needs of high-nickel ternary batteries, and to manufacture ternary precursor materials (also known as ternary "cores" and ternary "cores") directly used in the manufacture of ternary batteries, thereby achieving energy saving, pollution reduction and carbon reduction, and promoting the green transformation of laterite nickel ore from traditional smelting to new energy raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG1 is a flow chart of an embodiment of a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to the present invention. DETAILED DESCRIPTION

[0019] 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.

[0020] Please refer to Figure 1, which is a flow chart of the green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in the present invention. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in the present invention comprises the following steps:

[0021] (1) The laterite nickel ore raw material is subjected to the pre-treatment steps of ore blending, ore washing, ore dressing, ore grinding and thickening to obtain chromite and laterite nickel ore slurry. In this step, the pre-treatment steps include ore blending, ore washing, ore dressing, ore grinding and thickening. Through the ore blending step, the ratio of nickel, cobalt and manganese content in the laterite nickel ore slurry is basically adapted to the ratio of nickel, cobalt and manganese content in the nickel-cobalt-manganese ternary precursor. The ore dressing step is specifically gravity sorting and magnetic sorting performed in sequence. Before gravity sorting, the laterite nickel ore raw material can be coarsely classified, and then a multi-stage gravity sorting step can be set to collect the ore with finer particles to form the laterite nickel ore slurry, and the ore with coarser particles is magnetically sorted. After magnetic sorting, chromite is obtained to achieve the recovery of chromium metal resources. Here, gravity sorting can adopt gravity separation methods such as spiral chute and shaking table. The specific gravity sorting classification and magnetic sorting conditions can be adapted according to actual conditions and are not limited here. In this embodiment, the laterite nickel ore raw material is a mixture of any one or more of ultra-low-grade laterite nickel ore, low-grade laterite nickel ore, and medium-high-grade laterite nickel ore; the nickel content of the ultra-low-grade laterite nickel ore is less than 0.8%, the nickel content of the low-grade laterite nickel ore is 0.8-1.5%, and the nickel content of the medium-high-grade laterite nickel ore is greater than 1.5%; the laterite nickel ore slurry concentration is 36-43%, and the slurry capacity ratio is 160-200m 3 / ton of metallic nickel; the Cr content in the chromite is greater than 30% and the Fe content is less than 40%.

[0022] (2) The laterite nickel ore pulp is mixed with a reducing agent and a leaching accelerator and then subjected to pressure leaching or oxygen pressure leaching to obtain a mixed slurry consisting of a leachate containing nickel, cobalt and manganese and a leaching residue containing iron, aluminum and silicon. In this step, the mass ratio of the laterite nickel ore pulp to the lignite is 1000:(0.2-1.8). The acid leaching process can be selected from pressure leaching or oxygen pressure leaching. In this embodiment, after pressure leaching or oxygen pressure leaching, the Ni content in the obtained leaching residue containing nickel, cobalt and manganese is less than 0.05%, the Co content is less than 0.005%, and the Mn content is less than 0.05%. The process conditions for pressure leaching are: temperature 220-260°C, pressure 3.0-4.0MPa, and acid consumption 15-25 tons / ton of nickel; the process conditions for oxygen pressure leaching are: temperature 180-220°C, pressure 1.5-2.5MPa, and acid consumption 25-40 tons / ton of nickel. Introducing a reducing agent, such as lignite, ferrous sulfate, sodium sulfite, or sodium bisulfite, before the pressure or oxygen pressure leaching step can, on the one hand, inhibit the conversion of divalent manganese ions to a higher valence state, facilitating subsequent manganese extraction; on the other hand, facilitates the conversion of hexavalent chromium to trivalent chromium during the subsequent multi-stage neutralization process, facilitating chromium removal. Leaching accelerators, such as sodium sulfate or copper sulfate, can be used to accelerate the leaching of nickel, cobalt, and manganese during the pressure or oxygen pressure leaching process.

[0023] (3) The mixed slurry consisting of the leachate containing nickel, cobalt and manganese and the leach residue containing iron, aluminum and silicon is subjected to cyclic leaching and multi-stage neutralization in sequence to obtain a neutralized slurry. In this step, the process conditions of the cyclic leaching are: controlling the temperature to 95-105°C and reducing the residual acid concentration from 30-50g / L to below 5g / L; the process conditions of the multi-stage neutralization treatment are: controlling the pH to 0.8-2 by adding a neutralizing agent; the neutralizing agent is an alkaline mixture of any one or more of lime milk, limestone, sodium hydroxide, magnesia ore and magnesium hydroxide. Since the reducing agent has been added in step (2), a reducing agent such as ferrous sulfate, sodium sulfite, sodium bisulfite, etc. can be added again during the cyclic leaching and multi-stage neutralization treatment as a supplement to the reducing agent in step (2) to ensure that the chromium ions are fully reduced to trivalent. In this embodiment, sulfuric acid is used for pressure leaching or oxygen pressure leaching and then tested, and the content of pollutants in the exhaust gas is as follows: solid particulate matter <8mg / m 3 , sulfur dioxide <32mg / m 3 , sulfuric acid mist <10mg / m 3 If it meets the emission standards, it can be discharged directly, or the waste heat of the exhaust gas or steam can be reused to improve the utilization rate.

[0024] (4) The neutralized slurry obtained by the cyclic leaching and multi-stage neutralization treatment is diluted, multi-stage countercurrent washing and tailings neutralized, and iron metal is recovered from the obtained tailings by reduction roasting and magnetic separation. In this step, the washing stages of the multi-stage countercurrent washing are 3-9 stages, the ratio of washing water to slag phase is 1:1-7:1, the Ni content of the terminal washing water is less than 0.1g / L, and the nickel content in the neutralized tailings is less than 0.06%; in the multi-stage neutralization process, the slag phase is put into a neutral state by adding an appropriate amount of neutralizing agent, and the slag phase after neutralization is separated by solid-liquid separation of a thickener to obtain tailings, the pH of the tailings is 6-9, and the tailings mainly contain iron elements. Subsequently, the iron metal is recovered by reduction roasting and magnetic separation. In this embodiment, the metal element content in the tailings leachate after the iron metal is recovered is as follows: Ni<3.0mg / L, Cu<0.02mg / L, Zn<0.2mg / L, Cr 6+ <0.15mg / L. The tailings after iron metal recovery meet the direct discharge standards and can be discharged directly, which is in line with green and environmentally friendly production expectations.

[0025] (5) The final liquid phase after multi-stage countercurrent washing is subjected to multi-stage iron removal, aluminum chromium concentration and separation under the condition of adding a neutralizing agent and a precipitation promoter. In this step, the multi-stage iron removal consists of a first stage of iron removal, aluminum chromium removal and a second stage and above of iron removal, and the liquid phase after the first stage of iron removal is subjected to the second stage of iron removal, the slag phase after the first stage of iron removal is returned and subjected to multi-stage countercurrent washing again, and the slag phase after the second stage and above of iron removal is reused and subjected to cyclic leaching and multi-stage neutralization treatment again. Among them, the process conditions for multi-stage iron removal are: the number of process stages is 2-7 stages, the control temperature is 55-90°C, and the pH is 2.5-5.5; the neutralizing agent is a mixture of any one or more of lime milk, limestone, sodium hydroxide, magnesia ore, and magnesium hydroxide; the precipitation promoter is a mixture of any one or more of organic polymers and inorganic polymers, such as polyacrylamide, polyaluminum chloride, etc., which are not limited here.

[0026] In a specific embodiment, the process conditions for the one-stage iron removal and aluminum chromium removal are as follows: adding a neutralizing agent, charging compressed air, controlling the pH to 2.5-4.0, the temperature to 70-90°C, and the reaction time to 1-2h; wherein, the mass ratio of the oxygen content in the compressed air to the reduced carbon content of the lignite during the pressure leaching or oxygen pressure leaching process is 1:(0.95-0.85), to ensure that the oxygen content of the compressed air is just enough to oxidize the iron to ferric iron, while also avoiding the conversion of the reduced trivalent chromium into hexavalent chromium again. In this process, the ratio of oxygen content to reducing agent needs to be strictly controlled. In actual operation, the content of divalent iron ions in the one-stage iron removal and aluminum chromium removal process can be monitored in real time, and the amount of reducing agent added during the cyclic leaching and multi-stage neutralization treatment can be adaptively adjusted according to the level of divalent iron ions to meet the control requirements of just oxidizing iron to ferric iron and not converting trivalent chromium into hexavalent chromium. After the first stage of iron, aluminum and chromium removal is completed, a considerable amount of nickel, cobalt and manganese still exists in the slag phase. Recycling the slag phase after the first stage of iron, aluminum and chromium removal and performing multi-stage countercurrent washing again is conducive to the full extraction of nickel, cobalt and manganese in the slag phase. Since the reducing agent is introduced in the aforementioned steps (2) and (3) to maintain the trivalent chromium ions, the chromium ions are precipitated in the form of Cr(OH)3 during the first stage of iron, aluminum and chromium removal, thereby achieving the simultaneous removal of iron, aluminum and chromium metals.

[0027] In a specific embodiment, the process conditions for the second and above iron, aluminum and chromium removal are as follows: controlling the pH to be 4.0-5.5, the temperature to be 55-80°C, and the reaction time to be 2-10h. In the process of the second and above iron, aluminum and chromium removal, the remaining iron, aluminum and chromium in the liquid phase can be further removed synchronously, thereby improving the removal efficiency of impurity metal elements, so as to ensure that a purer nickel, cobalt and manganese product can be extracted subsequently; and the purpose of recycling the slag phase after the second and above iron, aluminum and chromium removal and then performing the cyclic leaching and multi-stage neutralization treatment is that a certain amount of nickel, cobalt and manganese elements will still remain in the slag phase after the second and above iron, aluminum and chromium removal, and recycling it again can extract as much nickel, cobalt and manganese as possible; at the same time, due to the large difference in pH value between the second and above iron, aluminum and chromium removal and the cyclic leaching-multi-stage neutralization treatment, the recycling of the slag phase after the second and above iron, aluminum and chromium removal can reduce the amount of neutralizer used in the cyclic leaching-first neutralization treatment to a certain extent, thereby achieving the purpose of cost saving. In actual operation, the content of divalent iron ions in the second and above iron-aluminum-chromium removal processes can be monitored in real time, and the amount of air added in the second stage of iron-aluminum-chromium removal process can be adaptively adjusted according to the level of divalent iron ions. For example, if the amount of compressed air charged in the first stage of iron-aluminum-chromium removal is too low, a certain amount of air needs to be added in the second and above stages of iron-aluminum-chromium removal processes to further oxidize the iron into trivalent iron, further precipitate the residual iron, and at the same time prevent the trivalent chromium from being converted into hexavalent chromium.

[0028] (6) The tail liquid phase after multi-stage iron, aluminum and chromium removal is subjected to multi-stage synthesis of nickel, cobalt and manganese, and the obtained nickel, cobalt and manganese mixed hydroxide is subjected to acid dissolution and liquid phase extraction to obtain a pure liquid, or the tail liquid phase after multi-stage iron, aluminum and chromium removal is directly subjected to liquid phase extraction to obtain a pure liquid, the pure liquid is a solution composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts; the pure liquid is evaporated and concentrated to obtain pure crystals, the pure crystals are crystals composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts, and the liquid phase extraction includes liquid phase co-extraction and liquid phase selective extraction. Among them, the nickel, cobalt and manganese mixed salt is a mixed salt of battery-grade nickel sulfate, cobalt sulfate and manganese sulfate, the nickel salt is battery-grade nickel sulfate, the cobalt salt is battery-grade cobalt sulfate, and the manganese salt is battery-grade manganese sulfate; the obtained high-concentration pure liquid or pure crystals are used for the subsequent preparation of nickel, cobalt and manganese ternary precursors.

[0029] As can be seen from FIG1 , there are two subsequent treatment methods for the liquid phase after multi-stage iron, aluminum, and chromium removal in the process of the present invention, both of which can obtain a high-concentration pure liquid (i.e., a solution composed of any one or more of a nickel-cobalt-manganese mixed salt, a nickel salt, a cobalt salt, and a manganese salt):

[0030] First, the tail liquid phase after multi-stage iron, aluminum and chromium removal is directly subjected to liquid phase extraction. This method can more quickly obtain a soluble mixed solution containing nickel, cobalt and manganese elements for the subsequent preparation of ternary precursors, which significantly simplifies the process flow and improves the extraction efficiency of nickel, cobalt and manganese elements. At the same time, the multi-stage precipitation method can be used to comprehensively recover valuable metals such as copper, zinc and scandium in the extract.

[0031] Second, the multi-stage nickel-cobalt-manganese synthesis consists of a first-stage nickel-cobalt-manganese synthesis and two or more stages of nickel-cobalt-manganese synthesis. The liquid phase after the first stage of nickel-cobalt-manganese synthesis undergoes the second stage of nickel-cobalt-manganese synthesis. The tail stage of the multi-stage nickel-cobalt-manganese synthesis, after removing iron, aluminum, and chromium, undergoes the first stage of nickel-cobalt-manganese synthesis. A nickel-cobalt-manganese mixed hydroxide is obtained after the first stage of nickel-cobalt-manganese synthesis. The nickel-cobalt-manganese mixed hydroxide synthesized at the tail stage of the multi-stage nickel-cobalt-manganese synthesis is returned and subjected to a circular leaching and multi-stage neutralization treatment. This allows the small amount of nickel, cobalt, and manganese remaining in the slag phase after the second stage of nickel and cobalt removal to be re-entered into the process for extraction, thereby improving the final extraction rate of nickel, cobalt, and manganese elements. At the same time, the tail stage of the multi-stage nickel-cobalt-manganese synthesis liquid phase is discharged after wastewater treatment. The nickel-cobalt-manganese mixed hydroxide has a Ni content of 35-45%, a Co content of 2.5-5.0%, and a Mn content of 6-12%.

[0032] In a specific embodiment, the metal element content of the wastewater after treatment is as follows: Cu<0.01mg / L, Cd<0.001mg / L, Zn<0.05mg / L, Pb<0.027mg / L, Ni<0.1mg / L, Cr 6+ <0.05mg / L, Fe<0.027mg / L, Co<0.008mg / L, the discharged wastewater meets the wastewater discharge standards and can be discharged directly, in line with green and environmentally friendly production expectations.

[0033] In one specific embodiment, the process conditions for the one-stage synthesis of nickel, cobalt and manganese are as follows: adding a neutralizing agent and seed crystals, controlling the pH value to 6.5-7.4, the temperature to 50-70°C, and the reaction time to 5-7h; the seed crystals are derived from the crystals obtained by controlled crystallization in the two-stage and above synthesis of nickel, cobalt and manganese.

[0034] In a specific embodiment, the process conditions for the second-stage and above synthesis of nickel, cobalt and manganese are as follows: controlling the pH value to be 7.5-10.0, the temperature to be 40-90°C, and the reaction time to be 0.5-1.5h; in the second-stage and above synthesis of nickel, cobalt and manganese, the crystals prepared by controlling the crystallization are combined with the tail liquid phase of the multi-stage iron, aluminum and chromium removal to carry out the first-stage synthesis of nickel, cobalt and manganese, and the efficiency of the first-stage synthesis of nickel, cobalt and manganese is accelerated by utilizing the introduced crystal seeds; and the introduced crystal seeds are prepared synchronously within the process flow, without the need for additional preparation of crystal seeds, thereby improving the preparation efficiency.

[0035] (7) The nickel-cobalt-manganese mixed salt solution is used as a mother liquor, or the water-soluble solution of the nickel-cobalt-manganese mixed salt crystals is used as a mother liquor. According to the ratio of nickel, cobalt and manganese contents in the nickel-cobalt-manganese ternary precursor, the solutions or crystals of the nickel salt, cobalt salt and manganese salt are added to the mother liquor, and the ratio of nickel, cobalt and manganese contents in the mother liquor is adjusted. The nickel, cobalt and manganese contents are subjected to a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor; or, the ratio of nickel, cobalt and manganese contents is adjusted according to the ratio of nickel, cobalt and manganese contents in the nickel-cobalt-manganese ternary precursor, and the solutions of the nickel salt, cobalt salt and manganese salt or the water-soluble solutions of the nickel salt, cobalt salt and manganese salt crystals are mixed and prepared so that the ratio of nickel, cobalt and manganese contents in the prepared mixed solution matches the ratio of nickel, cobalt and manganese contents in the nickel-cobalt-manganese ternary precursor, and a controlled precipitation reaction is carried out with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor.

[0036] It can be seen that a variety of raw material compounding methods can be used to prepare nickel-cobalt-manganese ternary precursors, such as:

[0037] I) Using the nickel-cobalt-manganese mixed salt solution obtained in step 9) as a mother liquor, adding the nickel salt, cobalt salt, and manganese salt solutions obtained in step 9) to the mother liquor according to the ratio of nickel, cobalt, and manganese in the nickel-cobalt-manganese ternary precursor, adjusting the ratio of nickel, cobalt, and manganese in the mother liquor, and performing a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor.

[0038] II) Using the aqueous solution of the nickel-cobalt-manganese mixed salt crystals obtained in step 9) as a mother liquor, the nickel salt, cobalt salt, and manganese salt crystals obtained in step 9) are dissolved in water according to the ratio of nickel, cobalt, and manganese in the nickel-cobalt-manganese ternary precursor, and then added to the mother liquor. The ratio of nickel, cobalt, and manganese in the mother liquor is adjusted, and a controlled precipitation reaction is carried out with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor.

[0039] III) The nickel salt, cobalt salt and manganese salt solution obtained in step 9) are subjected to a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere according to the nickel, cobalt and manganese content ratio in the nickel-cobalt-manganese ternary precursor to prepare a nickel-cobalt-manganese ternary precursor.

[0040] IV) The aqueous solution of the nickel salt, cobalt salt and manganese salt obtained in step 9) is subjected to a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere according to the ratio of nickel, cobalt and manganese contents in the nickel-cobalt-manganese ternary precursor to prepare a nickel-cobalt-manganese ternary precursor.

[0041] Of course, other raw material compounding methods can also be used to prepare nickel-cobalt-manganese ternary precursors, which will not be elaborated here.

[0042] The chemical formula of the nickel-cobalt-manganese ternary precursor prepared in this step is Ni x Co y Mn z(OH)2, where 0 < x < 1, 0 ≤ y < 1, 0 ≤ z < 1, and x + y + z = 1; the nickel-cobalt-manganese ternary precursor meets the preparation requirements of cathode materials for ternary power batteries, including ordinary ternary materials, high-voltage ternary materials, high-nickel / ultra-high-nickel ternary materials, lithium-rich manganese-based materials, etc. The cross-sectional structure of the nickel-cobalt-manganese ternary precursor is radially arranged or non-radially arranged; the pore distribution state of the nickel-cobalt-manganese ternary precursor is any one of uniform pore distribution, concentrated pore distribution inside the pores, concentrated pore distribution outside the pores, and multi-layer annular pore distribution; the distribution state of nickel, cobalt, and manganese elements in the nickel-cobalt-manganese ternary precursor is any one of uniform distribution, double-layer or multi-layer core-shell distribution, gradient distribution, full-concentration gradient distribution, and double-gradient distribution.

[0043] The specific process steps of the above nickel-cobalt-manganese ternary precursor are as follows:

[0044] a) Using the above raw material compounding method, according to the content ratio of nickel, cobalt, and manganese in the nickel-cobalt-manganese ternary precursor, prepare a mixed salt solution A with a total metal ion concentration of 1-2 mol / L; if synthesizing a core-shell or gradient structure precursor, multiple salt solutions with different concentrations need to be prepared according to the formula.

[0045] b) Prepare a doping element solution B with a concentration of 0.01-0.1 mol / L from the soluble salt of the doping element. Preferably, the doping element is one or more of aluminum, magnesium, zirconium, titanium, yttrium, tungsten, molybdenum, calcium, niobium, lanthanum, indium, strontium, tantalum, iron, copper, zinc, boron, fluorine, vanadium. If there is no doping in the precursor, this step can be omitted.

[0046] c) Prepare a coating solution C with a concentration of 0.1-1 mol / L from the soluble salt of the coating element. Preferably, the coating element is one or more of cobalt, manganese, aluminum, magnesium, zirconium, titanium, yttrium, tungsten, molybdenum, calcium, niobium, lanthanum, indium, strontium, tantalum, iron, copper, zinc. If there is no coating in the precursor, this step can be omitted.

[0047] d) Add a certain amount of pure water to the reaction kettle, and add a precipitating agent and a complexing agent to adjust the pH of the bottom liquid to 12-13, and the concentration of the complexing agent is 0.1-20 g / L. Preferably, the stirring paddle of the reaction kettle can be selected from one or more combinations of a straight-blade open turbine stirring paddle, an inclined-blade open turbine stirring paddle, an inclined-blade disk turbine stirring paddle, etc. The addition amount of pure water is 1:3-9:10 of the volume of the reaction kettle. The precipitating agent is one or more of potassium hydroxide, sodium hydroxide, or sodium carbonate, and the best choice is industrial liquid alkali; the complexing agent is one or more of ammonia water, ammonium bicarbonate, citric acid, oxalic acid, acetic acid, EDTA, and the most preferred is ammonia water.

[0048] e) Under a nitrogen atmosphere, add the mixed salt solution, doping element solution (omit this solution if undoped), precipitant, and complexing agent to the reactor via a metering system for a controlled precipitation reaction. Maintain the reaction pH at 9-13, the complexing agent concentration at 0.1-20 g / L, the temperature at 40-80°C, and the reactor stirring speed at 50-500 rpm. Monitor the D50 during the reaction. Stop the reaction when the D50 reaches 2-20 μm to obtain a ternary precursor slurry.

[0049] f) The coating layer solution, the precipitant and the complexing agent are continuously added to the reactor in parallel, the reaction conditions are kept unchanged, and the reaction is stopped after 1-20 hours to obtain a coated ternary precursor slurry.

[0050] g) washing, drying, screening, removing iron from the obtained precursor slurry, and packaging to obtain a ternary precursor material.

[0051] In one embodiment, the D50 of the nickel-cobalt-manganese ternary precursor is 2-20 μm and the tap density is 0.5-2.6 g / cm 3 , specific surface area BET is 2-50m 2 / g.

[0052] (11) After the nickel-cobalt-manganese ternary precursor is prepared, the nickel-cobalt-manganese ternary precursor is reacted with lithium carbonate or lithium hydroxide at high temperature to synthesize the positive electrode material for the ternary power battery according to the ratio of nickel, cobalt and manganese content in the positive electrode material for the ternary power battery.

[0053] The effect of the green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore is described below by means of specific examples. All the following examples are implemented using a limonite-type laterite nickel ore in Indonesia. After measurement (hereinafter referred to as mass percentage), the nickel content in the ore is 1.32%, the cobalt content is 0.12%, the Cr2O3 content is 2.78%, the MnO content is 1.03%, the Al2O3 content is 7.86%, the SiO2 content is 14.72%, and the Fe content is 41.25%; thus, according to the measurement results, the sample behaves as a typical low-grade limonite-type laterite nickel ore.

[0054] Example 1

[0055] The specific steps of the green technology for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in this embodiment are as follows:

[0056] 1) The raw laterite nickel ore is subjected to blending, washing, beneficiation, grinding, and thickening pretreatment steps to obtain chromite and laterite nickel ore slurries. A combined gravity and magnetic separation process is used during the beneficiation process to obtain a smelting-grade chromite concentrate having a Cr2O3 content of 34.62% and a chromium-iron ratio of 1.53. The blending step is used to adjust the nickel, cobalt, and manganese content ratios in the laterite nickel ore slurry to be similar to those in the nickel-cobalt-manganese ternary precursor.

[0057] 2) The obtained laterite nickel ore slurry is concentrated to a concentration of 36%, and lignite powder is added at a mass ratio of the laterite nickel ore slurry to lignite of 1000:1. The slurry is then fed into a high-pressure reactor together with a sodium sulfate leaching accelerator, and a leaching reaction is carried out under high-pressure leaching conditions of a temperature of 255° C., a pressure of 4.0 MPa, and an acid consumption of 20 tons / ton of nickel.

[0058] 3) The slurry after high-pressure leaching is circulated and leached and multi-stage neutralized, followed by a multi-stage countercurrent washing process with 6 washing stages and a ratio of wash water to slag phase of 4:1. After solid-liquid separation in a thickener, an appropriate amount of lime milk neutralizer is added to the slag phase to keep the slag phase in a neutral state of pH = 6.7. The metallic iron is then recovered and the tailings are discharged.

[0059] 4) The liquid phase obtained from the multi-stage countercurrent washing is further subjected to a first-stage iron, aluminum, and chromium removal process. The process conditions for this first-stage iron, aluminum, and chromium removal are: a controlled temperature of 85°C, a pH of 3.0, and a reaction time of 1 hour. The slag phase after the first-stage iron, aluminum, and chromium removal is recycled for further CCD countercurrent washing. The liquid phase after the first-stage iron, aluminum, and chromium removal is subjected to a second-stage iron, aluminum, and chromium removal process. The process conditions for this second-stage iron, aluminum, and chromium removal are: a controlled temperature of 79°C, a pH of 4.8, and a reaction time of 3 hours. The slag phase after the second-stage iron, aluminum, and chromium removal is recycled for further cyclic leaching and neutralization.

[0060] 5) A neutralizing agent is added to the medium after the second stage of iron, aluminum and chromium removal, and a first stage of nickel, cobalt and manganese synthesis is carried out. After the first stage of nickel, cobalt and manganese synthesis, a nickel, cobalt and manganese mixed hydroxide is obtained. The process conditions for the first stage of nickel, cobalt and manganese synthesis are as follows: pH value is 7.0, reaction temperature is 66°C, reaction time is 3h, and the introduced seed crystals are derived from the crystals obtained by crystallization during the second stage of nickel, cobalt and manganese synthesis. The liquid phase of the first stage of nickel, cobalt and manganese synthesis is subjected to the second stage of nickel, cobalt and manganese synthesis. The slag phase of the second stage of nickel, cobalt and manganese synthesis is recycled for cyclic leaching and neutralization treatment again. The liquid phase of the second stage of nickel, cobalt and manganese synthesis is discharged after wastewater treatment. The process conditions for the second stage of nickel, cobalt and manganese synthesis are as follows: pH value is controlled to 8.0, reaction temperature is 50°C, crystallized crystals in the second stage of nickel, cobalt and manganese synthesis are combined with the liquid phase after the second stage of iron, aluminum and chromium removal and subjected to the first stage of nickel, cobalt and manganese synthesis, accelerating the first stage of nickel, cobalt and manganese synthesis.

[0061] 6) The nickel-cobalt-manganese mixed hydroxide is subjected to liquid phase selective extraction using P204 and P507 to obtain battery-grade nickel-cobalt-manganese mixed salt crystals, nickel sulfate crystals, cobalt sulfate crystals, and manganese sulfate crystals, respectively. The nickel-cobalt-manganese mixed salt crystals are dissolved in water and used as a mother liquor. The nickel sulfate crystals, cobalt sulfate crystals, and manganese sulfate crystals are prepared into a mixed salt solution A with a total metal concentration of 2 mol / L in a molar ratio of nickel:cobalt:manganese of 80:10:10.

[0062] 7) Magnesium sulfate was prepared into a 0.01 mol / L doping element solution B, and cobalt sulfate was prepared into a 1 mol / L coating layer solution C. Pure water was added to a reactor, and the pH of the base solution was adjusted to 13 by adding 32% industrial liquid caustic soda and 16% aqueous ammonia, with an ammonia concentration of 10 g / L. The reactor was equipped with a double-layer agitator, with an upper layer equipped with a pitched-blade disc turbine impeller and a lower layer equipped with a straight-blade open turbine impeller.

[0063] 8) Under a nitrogen atmosphere, mixed salt solution A, doping element solution B, 32% industrial liquid caustic soda, and 16% aqueous ammonia were added concurrently to a reactor for a controlled precipitation reaction. The pH was maintained at 12-12.5, the ammonia concentration was controlled at 10 g / L, the temperature was controlled at 65°C, and the rotation speed was controlled at 300 RPM. The D50 (D50) value was monitored during the reaction. The reaction was terminated when it reached 5 μm, yielding a Mg-doped NCM811 ternary precursor slurry.

[0064] 9) The coating solution C, 32% industrial liquid alkali and 16% ammonia water are added to the reactor in parallel, and the reaction pH is maintained at 11.5-12. The other conditions are consistent with step 8). The reaction is stopped after 3 hours to obtain Co(OH)2-coated, Mg-doped NCM811 ternary precursor slurry. After washing, drying, screening, iron removal and packaging, Co(OH)2-coated, Mg-doped NCM811 ternary precursor material is obtained.

[0065] Example 2

[0066] The specific steps of the green technology for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in this embodiment are as follows:

[0067] 1) The raw laterite nickel ore is subjected to blending, washing, beneficiation, grinding, and thickening pretreatment steps to obtain chromite and laterite nickel ore slurries. A combined gravity and magnetic separation process is used to obtain a smelting-grade chromite concentrate with a Cr2O3 content of 33.82% and a chromium-iron ratio of 1.41. The blending step is used to adjust the nickel, cobalt, and manganese content in the laterite nickel ore slurry to a similar ratio to that in the nickel-cobalt-manganese ternary precursor.

[0068] 2) The obtained laterite nickel ore slurry is concentrated to a concentration of 36%, and lignite powder is added at a mass ratio of the laterite nickel ore slurry to lignite of 1000:0.8. The slurry is then fed into a high-pressure reactor together with a sodium sulfate leaching accelerator, and a leaching reaction is carried out under high-pressure leaching conditions of a temperature of 255° C., a pressure of 4.0 MPa, and an acid consumption of 20 tons / ton of nickel.

[0069] 3) The slurry after high-pressure leaching is circulated and leached and multi-stage neutralized, followed by a multi-stage countercurrent washing process with 6 washing stages and a ratio of wash water to slag phase of 4:1. After solid-liquid separation in a thickener, an appropriate amount of lime milk neutralizer is added to the slag phase to keep the slag phase in a neutral state of pH = 6.7. The metallic iron is then recovered and the tailings are discharged.

[0070] 4) The liquid phase obtained from the multi-stage countercurrent washing is further subjected to a first-stage iron, aluminum, and chromium removal process. The process conditions for this first-stage iron, aluminum, and chromium removal are: a controlled temperature of 85°C, a pH of 3.0, and a reaction time of 1 hour. The slag phase after the first-stage iron, aluminum, and chromium removal is recycled for further CCD countercurrent washing. The liquid phase after the first-stage iron, aluminum, and chromium removal is subjected to a second-stage iron, aluminum, and chromium removal process. The process conditions for this second-stage iron, aluminum, and chromium removal are: a controlled temperature of 79°C, a pH of 4.8, and a reaction time of 3 hours. The slag phase after the second-stage iron, aluminum, and chromium removal is recycled for further cyclic leaching and neutralization.

[0071] 5) A neutralizing agent is added to the medium after the second stage of iron, aluminum and chromium removal, and a first stage of nickel, cobalt and manganese synthesis is carried out. After the first stage of nickel, cobalt and manganese synthesis, a nickel, cobalt and manganese mixed hydroxide is obtained. The process conditions for the first stage of nickel, cobalt and manganese synthesis are as follows: pH value is 7.0, reaction temperature is 66°C, reaction time is 3h, and the introduced seed crystals are derived from the crystals obtained by crystallization during the second stage of nickel, cobalt and manganese synthesis. The liquid phase of the first stage of nickel, cobalt and manganese synthesis is subjected to the second stage of nickel, cobalt and manganese synthesis. The slag phase of the second stage of nickel, cobalt and manganese synthesis is recycled for cyclic leaching and neutralization treatment again. The liquid phase of the second stage of nickel, cobalt and manganese synthesis is discharged after wastewater treatment. The process conditions for the second stage of nickel, cobalt and manganese synthesis are as follows: pH value is controlled to 8.0, reaction temperature is 50°C, crystallized crystals in the second stage of nickel, cobalt and manganese synthesis are combined with the liquid phase after the second stage of iron, aluminum and chromium removal and subjected to the first stage of nickel, cobalt and manganese synthesis, accelerating the first stage of nickel, cobalt and manganese synthesis.

[0072] 6) The nickel-cobalt-manganese mixed hydroxide is subjected to liquid phase selective extraction using P204 and P507 to obtain a battery-grade nickel-cobalt-manganese mixed salt solution, a nickel sulfate solution, a cobalt sulfate solution, and a manganese sulfate solution, respectively. The nickel-cobalt-manganese mixed salt solution is used as the mother liquor, and the nickel sulfate solution, the cobalt sulfate solution, and the manganese sulfate solution are prepared in a nickel:cobalt:manganese molar ratio of 70:10:20 to prepare a mixed salt solution A with a total metal concentration of 2 mol / L.

[0073] 7) At 12m 3 Add 8m 3Pure water, and add 32% industrial liquid alkali and 16% ammonia water to adjust the pH of the bottom liquid to 12, and the ammonia concentration is 15g / L. Among them, the reactor is a single-layer inclined blade disc turbine impeller.

[0074] 8) Under a nitrogen atmosphere, add mixed salt solution A, doping element solution B, 32% industrial liquid caustic soda, and 16% ammonia water to the reactor via a metering system for a controlled precipitation reaction. Maintain the reaction pH at 12-12.5; the ammonia concentration at 15 g / L; the temperature at 60°C; and the rotation speed at 400 RPM. Monitor the D50 value during the reaction.

[0075] 9) When D50 reaches 6 μm, the stirring speed is reduced to 300 RPM, and a 20% sodium citrate solution of the second complexing agent is added at the same time, maintaining the concentration of sodium citrate at 10 g / L. When D50 reaches 10 μm, the feeding of the second complexing agent sodium citrate solution is stopped, the speed is adjusted back to 400 RPM and the reaction is continued. When D50 reaches 12 μm, the feeding is stopped to obtain an NCM712 ternary precursor slurry with an annular pore distribution. After washing, drying, screening, iron removal, and packaging, a Co(OH)2-coated, Mg-doped NCM712 ternary precursor material is obtained. Scanning electron microscopy observation shows that the pores of the Co(OH)2-coated, Mg-doped NCM712 ternary precursor material are annularly distributed.

[0076] Example 3

[0077] The specific steps of the green technology for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in this embodiment are as follows:

[0078] 1) The raw laterite nickel ore is subjected to blending, washing, beneficiation, grinding, and thickening pretreatment steps to obtain chromite and laterite nickel ore slurries. A combined gravity and magnetic separation process is used to obtain a smelting-grade chromite concentrate with a Cr2O3 content of 32.85% and a chromium-iron ratio of 1.56. The blending step is used to adjust the nickel, cobalt, and manganese content in the laterite nickel ore slurry to a similar ratio to that in the nickel-cobalt-manganese ternary precursor.

[0079] 2) The obtained laterite nickel ore slurry is concentrated to a concentration of 36%, and lignite powder is added at a mass ratio of the laterite nickel ore slurry to lignite of 1000:0.9. The slurry is then fed into a high-pressure reactor together with a sodium sulfate leaching accelerator, and a leaching reaction is carried out under high-pressure leaching conditions of a temperature of 255° C., a pressure of 4.0 MPa, and an acid consumption of 20 tons / ton of nickel.

[0080] 3) The slurry after high-pressure leaching is circulated and leached and multi-stage neutralized, followed by a multi-stage countercurrent washing process with 6 washing stages and a ratio of wash water to slag phase of 4:1. After solid-liquid separation in a thickener, an appropriate amount of lime milk neutralizer is added to the slag phase to keep the slag phase in a neutral state of pH = 6.7. The metallic iron is then recovered and the tailings are discharged.

[0081] 4) The liquid phase obtained from the multi-stage countercurrent washing is further subjected to a first-stage iron, aluminum, and chromium removal process. The process conditions for this first-stage iron, aluminum, and chromium removal are: a controlled temperature of 85°C, a pH of 3.0, and a reaction time of 1 hour. The slag phase after the first-stage iron, aluminum, and chromium removal is recycled for further CCD countercurrent washing. The liquid phase after the first-stage iron, aluminum, and chromium removal is subjected to a second-stage iron, aluminum, and chromium removal process. The process conditions for this second-stage iron, aluminum, and chromium removal are: a controlled temperature of 79°C, a pH of 4.8, and a reaction time of 3 hours. The slag phase after the second-stage iron, aluminum, and chromium removal is recycled for further cyclic leaching and neutralization.

[0082] 5) A neutralizing agent is added to the medium after the second stage of iron, aluminum and chromium removal, and a first stage of nickel, cobalt and manganese synthesis is carried out. After the first stage of nickel, cobalt and manganese synthesis, a nickel, cobalt and manganese mixed hydroxide is obtained. The process conditions for the first stage of nickel, cobalt and manganese synthesis are as follows: pH value is 7.0, reaction temperature is 66°C, reaction time is 3h, and the introduced seed crystals are derived from the crystals obtained by crystallization during the second stage of nickel, cobalt and manganese synthesis. The liquid phase of the first stage of nickel, cobalt and manganese synthesis is subjected to the second stage of nickel, cobalt and manganese synthesis. The slag phase of the second stage of nickel, cobalt and manganese synthesis is recycled for cyclic leaching and neutralization treatment again. The liquid phase of the second stage of nickel, cobalt and manganese synthesis is discharged after wastewater treatment. The process conditions for the second stage of nickel, cobalt and manganese synthesis are as follows: pH value is controlled to 8.0, reaction temperature is 50°C, crystallized crystals in the second stage of nickel, cobalt and manganese synthesis are combined with the liquid phase after the second stage of iron, aluminum and chromium removal and subjected to the first stage of nickel, cobalt and manganese synthesis, accelerating the first stage of nickel, cobalt and manganese synthesis.

[0083] 6) The nickel, cobalt and manganese mixed hydroxides were subjected to liquid phase selective extraction using P204 and P507 to obtain battery-grade nickel sulfate crystals, cobalt sulfate crystals, and manganese sulfate crystals, respectively. The nickel sulfate crystals, cobalt sulfate crystals, and manganese sulfate crystals were dissolved in water to prepare nickel sulfate solutions, cobalt sulfate solutions, and manganese sulfate solutions, respectively, each having a metal concentration of 1.5 mol / L.

[0084] 7) Under nitrogen atmosphere protection, nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution, 32% industrial liquid caustic soda, and 15% ammonia water are added to a multi-layer paddle-shaped reactor in parallel through a metering system for a coprecipitation reaction. The flow rates of the nickel sulfate, cobalt sulfate, and manganese sulfate solutions vary in a gradient, but the total flow rate remains unchanged. At the start of feeding, the flow ratio of nickel sulfate, cobalt sulfate, and manganese sulfate is 98:1:1, and at the end of feeding, the flow ratio of nickel sulfate, cobalt sulfate, and manganese sulfate is 30:20:50. The reaction pH is maintained at 11.5-12; the ammonia concentration is controlled at 10 g / L; the temperature is controlled at 50° C.; and the rotation speed is controlled at 200 rpm. D50 was monitored during the reaction. The reaction was stopped when D50 reached 18 μm to obtain a full concentration gradient ternary precursor slurry with a core of NCM98 / 1 / 1 and a shell of NCM30 / 20 / 50. After washing, drying, screening, iron removal and packaging, a full concentration gradient ternary precursor material with a core of NCM98 / 1 / 1 and a shell of NCM30 / 20 / 50 was obtained.

[0085] Example 4

[0086] The specific steps of the green technology for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore in this embodiment are as follows:

[0087] 1) The laterite nickel ore raw material undergoes blending, washing, beneficiation, grinding, and thickening pretreatment steps to obtain chromite and laterite nickel ore slurries. A combined gravity and magnetic separation process is used during the beneficiation process to obtain a smelting-grade chromite concentrate having a Cr2O3 content of 35.11% and a chromium-iron ratio of 1.33. The blending step is used to adjust the nickel, cobalt, and manganese content in the laterite nickel ore slurry to a similar ratio as that in the nickel-cobalt-manganese ternary precursor.

[0088] 2) The obtained laterite nickel ore slurry is concentrated to a concentration of 36%, and lignite powder is added at a mass ratio of the laterite nickel ore slurry to lignite of 1000:1.1. The slurry is then fed into a high-pressure reactor together with a sodium sulfate leaching accelerator, and a leaching reaction is carried out under high-pressure leaching conditions of a temperature of 255° C., a pressure of 4.0 MPa, and an acid consumption of 20 tons / ton of nickel.

[0089] 3) The slurry after high-pressure leaching is circulated and leached and multi-stage neutralized, followed by a multi-stage countercurrent washing process with 6 washing stages and a ratio of wash water to slag phase of 4:1. After solid-liquid separation in a thickener, an appropriate amount of lime milk neutralizer is added to the slag phase to keep the slag phase in a neutral state of pH = 6.7. The metallic iron is then recovered and the tailings are discharged.

[0090] 4) The liquid phase obtained from the multi-stage countercurrent washing is further subjected to a first-stage iron, aluminum, and chromium removal process. The process conditions for this first-stage iron, aluminum, and chromium removal are: a controlled temperature of 85°C, a pH of 3.0, and a reaction time of 1 hour. The slag phase after the first-stage iron, aluminum, and chromium removal is recycled for further CCD countercurrent washing. The liquid phase after the first-stage iron, aluminum, and chromium removal is subjected to a second-stage iron, aluminum, and chromium removal process. The process conditions for this second-stage iron, aluminum, and chromium removal are: a controlled temperature of 79°C, a pH of 4.8, and a reaction time of 3 hours. The slag phase after the second-stage iron, aluminum, and chromium removal is recycled for further cyclic leaching and neutralization.

[0091] 5) A neutralizing agent is added to the medium after the second stage of iron, aluminum and chromium removal, and a first stage of nickel, cobalt and manganese synthesis is carried out. After the first stage of nickel, cobalt and manganese synthesis, a nickel, cobalt and manganese mixed hydroxide is obtained. The process conditions for the first stage of nickel, cobalt and manganese synthesis are as follows: pH value is 7.0, reaction temperature is 66°C, reaction time is 3h, and the introduced seed crystals are derived from the crystals obtained by crystallization during the second stage of nickel, cobalt and manganese synthesis. The liquid phase of the first stage of nickel, cobalt and manganese synthesis is subjected to the second stage of nickel, cobalt and manganese synthesis. The slag phase of the second stage of nickel, cobalt and manganese synthesis is recycled for cyclic leaching and neutralization treatment again. The liquid phase of the second stage of nickel, cobalt and manganese synthesis is discharged after wastewater treatment. The process conditions for the second stage of nickel, cobalt and manganese synthesis are as follows: pH value is controlled to 8.0, reaction temperature is 50°C, crystallized crystals in the second stage of nickel, cobalt and manganese synthesis are combined with the liquid phase after the second stage of iron, aluminum and chromium removal and subjected to the first stage of nickel, cobalt and manganese synthesis, accelerating the first stage of nickel, cobalt and manganese synthesis.

[0092] 6) The nickel, cobalt and manganese mixed hydroxides were subjected to liquid phase selective extraction using P204 and P507 to obtain battery-grade nickel sulfate solution, cobalt sulfate solution, and manganese sulfate solution, respectively. The nickel sulfate solution, cobalt sulfate solution and manganese sulfate solution were prepared into a mixed salt solution A with a total metal concentration of 2 mol / L at a molar ratio of nickel:cobalt:manganese of 90:5:5.

[0093] 7) Adjust nitrogen purity to 95% with compressed air. Under a 95% nitrogen atmosphere, add mixed salt solution A, doping element solution B, 32% industrial liquid caustic soda, and 16% ammonia water to the reactor via a metering system for a co-precipitation reaction. Maintain the reaction pH at 11-11.5; the ammonia concentration at 8 g / L; the temperature at 45°C; and the rotational speed at 250 RPM. Monitor the D50 during the reaction. Stop feeding when the D50 reaches 20 μm to obtain a loose, porous NCM90 / 5 / 5 ternary precursor slurry with radially arranged primary particles. After washing, drying, screening, iron removal, and packaging, a loose, porous NCM90 / 5 / 5 ternary precursor slurry with radially arranged primary particles is obtained.

[0094] The following tests are conducted on multiple indicators in the above-mentioned embodiments 1 to 4.

[0095] Test 1

[0096] The extraction rates of nickel, cobalt, and manganese in Examples 1-4 (calculated based on the mass ratio of the resulting nickel-cobalt-manganese mixed salt, nickel sulfate, cobalt sulfate, and manganese sulfate solutions or crystals relative to the laterite nickel ore raw material) were tested and calculated, and the slurry production capacity ratio of the laterite nickel ore raw materials after the pretreatment process in Examples 1-4 was tested and calculated, and the results are shown in Table 1. It can be seen that the slurry production capacity in Examples 1-4 is relatively high, which can promote the subsequent leaching process to increase production capacity and reduce energy consumption; the Ni extraction rates obtained using the above-mentioned embodiments all reached over 94%, the Co extraction rates all reached over 92%, and the Mn extraction rates all reached over 90%. The extraction rate of existing laterite nickel ore hydrometallurgical process can be found in the paper ("Basic Theory and Process Research of Hydrometallurgical Extraction of Low-Grade Nickel Laterite Ore", PhD thesis of Central South University, Li Dong). The paper records that the leaching rates of Ni, Co, and Mn are 82.5%, 70.3%, and 80.0%, respectively. It can be seen that the extraction rates of nickel, cobalt, and manganese elements of the present invention are all higher than the extraction effect of laterite nickel ore by existing processes.

[0097] Table 1

[0098] Test 2

[0099] The contents of valuable metal elements in the manganese sulfate, nickel sulfate, and cobalt sulfate solutions (i.e., pure solutions) obtained in Examples 1 to 4 were tested, and the results are shown in Tables 2 to 4.

[0100] Table 2 Test table of valuable metal element content in manganese sulfate solution

[0101] Table 3 Test table of valuable metal element content in nickel sulfate solution

[0102] Table 4 Test table of valuable metal element content in cobalt sulfate solution

[0103] It can be seen from Table 2 that the contents of valuable metals in the obtained manganese sulfate solution are: Mn>120g / L, Ca<3.0mg / L, Mg<3.0mg / L, Cu<1.0mg / L, Zn<1.0mg / L, Fe<2.0mg / L, Pb<5.0mg / L, Cd<1.0mg / L, Cr<1.0mg / L, Si<5.0mg / L, and Al<2.0mg / L. As can be seen from Table 3, the valuable metal contents in the obtained nickel sulfate solution are as follows: Ni>120g / L, Mn<2.0mg / L, Cu<1.0mg / L, Zn<1.0mg / L, Fe<1.5mg / L, Ca<5.0mg / L, Mg<5.0mg / L, Cr<2.0mg / L, Si<5.0mg / L, Pb<5.0mg / L, Al<1.0mg / L, Cd<2.5mg / L. As can be seen from Table 4, the valuable metal contents in the obtained cobalt sulfate solution are as follows: Co>110g / L, Cu<2.0mg / L, Zn<2.0mg / L, Fe<3.5mg / L, Ca<5.0mg / L, Mg<5.0mg / L, Cr<3.0mg / L, Si<5.0mg / L, Pb<5.0mg / L, Al<1.0mg / L, Cd<1.5mg / L. It is not difficult to see that the obtained manganese sulfate solution, nickel sulfate solution and cobalt sulfate solution contain high levels of Mn, Ni and Co respectively, while the amounts of other valuable metal elements are small, which proves that battery-grade nickel-cobalt-manganese mixed sulfate, manganese sulfate, nickel sulfate and cobalt sulfate can be extracted by the above method and can be directly used in the preparation of ternary precursors.

[0104] Test 3

[0105] The exhaust gas discharged after high pressure acid leaching in step 2) of Examples 1 to 4 was tested. The results are shown in Table 5. The content of pollutants in the exhaust gas is as follows: solid particulate matter <8 mg / m 3 , sulfur dioxide <32mg / m 3 , sulfuric acid mist <10mg / m 3 It can be seen that the wastewater discharged by the above methods meets the waste gas emission standards and can be discharged directly, which is in line with the green and environmentally friendly production expectations.

[0106] Table 5

[0107] Test 4

[0108] The tailings after iron recovery in step 3) of Examples 1 to 4 were subjected to solid waste leaching toxicity testing, and the results are shown in Table 6 (the actual measured content is much less than 0.001, denoted as "ND" in the table). As can be seen from Table 5, the tailings leachate after iron recovery meets the solid waste leaching toxicity standard requirements and can be directly discharged, meeting the production expectations of green and environmentally friendly production.

[0109] Table 6

[0110] Test 5

[0111] The metal element test was performed on the wastewater treatment of the liquid phase of the two-stage synthesis of nickel, cobalt and manganese in step 5) of Examples 1 to 4. The results are shown in Table 7. The metal contents of the wastewater after treatment are as follows: Cu<0.01mg / L, Cd<0.001mg / L, Zn<0.05mg / L, Pb<0.027mg / L, Ni<0.1mg / L, Cr 6+ <0.05mg / L, Fe<0.027mg / L, Co<0.008mg / L. It can be seen that the wastewater discharged by the above methods meets the wastewater discharge standards and meets the green and environmentally friendly production expectations.

[0112] Table 7

[0113] Different from the existing technology, the present invention provides a green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore. The method belongs to green technology and green method, and mainly includes ore blending, ore washing, ore dressing, pressurized or oxygen pressure leaching, cyclic leaching and neutralization, countercurrent washing, multi-stage iron, aluminum and chromium removal, multi-stage synthesis of nickel, cobalt and manganese hydroxide, ion extraction, nickel, cobalt and manganese salt mixed solution or nickel, cobalt and manganese salt independent solution, nickel, cobalt and manganese salt mixed crystal preparation or nickel, cobalt and manganese independent salt crystal preparation, ternary precursor preparation, comprehensive treatment of wastewater, waste gas and waste residue, etc., to achieve simultaneous and efficient extraction of nickel, cobalt and manganese, and effective recovery of valuable metal elements such as chromium iron, copper, zinc, and scandium, to produce nickel, cobalt and manganese raw materials that meet the needs of high-nickel ternary batteries, and to manufacture ternary precursor materials (also known as ternary "cores" and ternary "cores") directly used in the manufacture of ternary batteries, thereby achieving energy conservation, pollution reduction and carbon reduction, and promoting the green transformation of laterite nickel ore from traditional smelting to new energy raw materials.

[0114] 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.

[0115] 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 green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore, characterized in that: The steps include: (1) After the laterite nickel ore raw material is subjected to ore blending, ore washing, ore dressing, ore grinding and dense pre-treatment processes, chromite and laterite nickel ore slurry are obtained; the chromite is obtained by sorting in the ore dressing process, and the ratio of nickel, cobalt and manganese in the laterite nickel ore slurry is consistent with the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor; (2) mixing the laterite nickel ore slurry with a reducing agent and a leaching promoter, and then performing pressure leaching or oxygen pressure leaching to obtain a mixed slurry consisting of a leaching solution containing nickel, cobalt and manganese and a leaching residue containing iron, aluminum and silicon; (3) subjecting a mixed slurry consisting of a leaching solution containing nickel, cobalt and manganese and a leaching residue containing iron, aluminum and silicon to cyclic leaching and multi-stage neutralization in sequence to obtain a neutralized slurry; (4) diluting the neutralized slurry obtained by the cyclic leaching and multi-stage neutralization treatment, performing multi-stage countercurrent washing and tailings neutralization, and recovering iron metal from the tailings obtained by reduction roasting-magnetic separation; (5) The final liquid phase after the multi-stage countercurrent washing is subjected to multi-stage iron removal, aluminum chromium concentration and separation under the condition of adding a neutralizing agent and a precipitation promoter; the multi-stage iron removal is composed of a first stage of iron removal, aluminum chromium removal and a second stage of iron removal, and the liquid phase after the first stage of iron removal is subjected to the second stage of iron removal, the slag phase after the first stage of iron removal is returned and subjected to multi-stage countercurrent washing again, and the slag phase after the second stage of iron removal is reused and subjected to cyclic leaching and multi-stage neutralization treatment again; (6) The tail liquid phase after the multi-stage iron, aluminum and chromium removal is subjected to multi-stage synthesis of nickel, cobalt and manganese, and the obtained nickel, cobalt and manganese mixed hydroxide is subjected to acid dissolution and liquid phase extraction to obtain a pure liquid, or the tail liquid phase after the multi-stage iron, aluminum and chromium removal is directly subjected to liquid phase extraction to obtain a pure liquid, and the pure liquid is a solution composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts; the pure liquid is evaporated and concentrated to obtain pure crystals, and the pure crystals are crystals composed of any one or more of nickel, cobalt and manganese mixed salts, nickel salts, cobalt salts and manganese salts, and the liquid phase extraction includes liquid phase co-extraction and liquid phase selective extraction; (7) using the nickel-cobalt-manganese mixed salt solution as a mother liquor, or using the water-soluble solution of the nickel-cobalt-manganese mixed salt crystals as a mother liquor, adding the nickel salt, cobalt salt, manganese salt solution or crystals to the mother liquor according to the nickel-cobalt-manganese content ratio in the nickel-cobalt-manganese ternary precursor, adjusting the nickel-cobalt-manganese content ratio in the mother liquor, and performing a controlled precipitation reaction with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor; Alternatively, according to the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor, a solution of nickel salt, cobalt salt and manganese salt or a water-soluble solution of nickel salt, cobalt salt and manganese salt crystals is mixed and prepared, so that the ratio of nickel, cobalt and manganese in the prepared mixed solution matches the ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary precursor, and a controlled precipitation reaction is carried out with a precipitant and a complexing agent under a protective atmosphere to prepare a nickel-cobalt-manganese ternary precursor; Among them, the multi-stage synthetic nickel-cobalt-manganese is composed of a first-stage synthetic nickel-cobalt-manganese and a second-stage and above synthetic nickel-cobalt-manganese, and the liquid phase after the first-stage synthetic nickel-cobalt-manganese is subjected to the second-stage synthetic nickel-cobalt-manganese, the tail-stage liquid phase of the multi-stage iron, aluminum and chromium removal is subjected to a first-stage synthetic nickel-cobalt-manganese treatment, and the nickel-cobalt-manganese mixed hydroxide is obtained after the first-stage synthetic nickel-cobalt-manganese, and the nickel-cobalt-manganese mixed hydroxide synthesized in the tail-stage of the multi-stage synthetic nickel-cobalt-manganese is returned and subjected to cyclic leaching and multi-stage neutralization treatment again.

2. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: The laterite nickel ore raw material is a mixture of any one or more of ultra-low-grade laterite nickel ore, low-grade laterite nickel ore, medium-high-grade laterite nickel ore; The nickel content of the ultra-low-grade laterite nickel ore is less than 0.8%, the nickel content of the low-grade laterite nickel ore is 0.8-1.5%, and the nickel content of the medium-high-grade laterite nickel ore is greater than 1.5%.

3. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: The laterite nickel ore slurry concentration is 36-43%, and the slurry capacity ratio is 160-200m 3 / ton of nickel metal; The chromite has a Cr content greater than 30% and a Fe content less than 40%.

4. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: The mineral separation is specifically gravity separation and magnetic separation carried out in sequence.

5. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: After the pressure leaching or oxygen pressure leaching, the obtained leached slag containing nickel, cobalt and manganese has a Ni content of less than 0.05%, a Co content of less than 0.005%, and a Mn content of less than 0.05%; After the pressure leaching or oxygen pressure leaching with sulfuric acid, the content of pollutants in the exhaust gas is as follows: solid particles <8mg / m 3 , sulfur dioxide <32mg / m 3 , sulfuric acid mist <10mg / m 3 .

6. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: The mass ratio of the laterite nickel ore slurry to the reducing agent is 1000:(0.2-1.8), and the reducing agent is lignite; The leaching accelerator is any one or more of sodium sulfate and copper sulfate.

7. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The process conditions of the pressure leaching are: temperature 220-260°C, pressure 3.0-4.0MPa, acid consumption 15-25 tons / ton of nickel; The process conditions of oxygen pressure leaching are: temperature 180-220° C., pressure 1.5-2.5 MPa, and acid consumption 25-40 tons / ton of nickel.

8. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The process conditions of the cyclic leaching are: controlling the temperature at 95-105°C and reducing the residual acid concentration from 30-50g / L to below 5g / L; The process conditions of the multi-stage neutralization treatment are: controlling the pH to 0.8-2 by adding a neutralizing agent.

9. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical laterite nickel ore according to claim 1, characterized in that: The multi-stage countercurrent washing has 3-9 washing stages, the ratio of washing water to slag phase is 1:1-7:1, the Ni content of the terminal washing water is less than 0.1 g / L, and the nickel content of the tailings after neutralization is less than 0.06%.

10. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 9, characterized in that: A neutralizing agent is added to neutralize the tailings after the multi-stage countercurrent washing. The metal element content in the tailings leaching solution after the iron metal is recovered is as follows: Ni<3.0mg / L, Cu<0.02mg / L, Zn<0.2mg / L, Cr 6+ <0.15mg / L.

11. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The process conditions for multi-stage iron, aluminum and chromium removal are as follows: the number of process stages is 2-7, the temperature is controlled at 55-90° C., and the pH is 2.5-5.

5.

12. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 11, characterized in that: The process conditions for the one-stage iron, aluminum and chromium removal are: adding a neutralizing agent, charging compressed air, controlling the pH to 2.5-4.0, the temperature to 70-90° C., and the reaction time to 1-2 hours.

13. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 11, characterized in that: The process conditions for the second and above stages of iron, aluminum and chromium removal are: controlling the pH to 4.0-5.5, the temperature to 55-80°C, and the reaction time to 2-10h.

14. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The process conditions for the one-stage synthesis of nickel, cobalt and manganese are: adding a neutralizing agent and a seed crystal, controlling the pH value to be 6.5-7.4, the temperature to be 50-70° C., and the reaction time to be 5-7 hours; The seed crystals are derived from crystals obtained by controlled crystallization in the second and above stages of synthesizing nickel, cobalt and manganese.

15. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The process conditions for synthesizing nickel, cobalt and manganese in the second stage and above are: controlling the pH value to be 7.5-10.0, the temperature to be 40-90° C., and the reaction time to be 0.5-1.5 h; In the two-stage and above nickel-cobalt-manganese synthesis process, the crystals prepared by controlled crystallization are combined with the tail liquid phase of the multi-stage iron, aluminum and chromium removal to carry out the one-stage nickel-cobalt-manganese synthesis.

16. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The tail liquid phase of the multi-stage synthesis of nickel, cobalt and manganese is discharged after wastewater treatment. The metal element content of the wastewater after treatment is as follows: Cu<0.01mg / L, Cd<0.001mg / L, Zn<0.05mg / L, Pb<0.027mg / L, Ni<0.1mg / L, Cr 6+ <0.05mg / L, Fe<0.027mg / L, Co<0.008mg / L.

17. [Corrected 25.07.2023 in accordance with Rule 91] A green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to any one of claims 1, 8, 10, 12 and 14, characterized in that: The neutralizing agent is a mixture of any one or more of lime milk, limestone, sodium hydroxide, magnesia ore, and magnesium hydroxide: The precipitation accelerator is a mixture of any one or more of an organic polymer and an inorganic polymer.

18. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The nickel-cobalt-manganese mixed hydroxide has a Ni content of 35-45%, a Co content of 2.5-5.0% and a Mn content of 6-12%.

19. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The tail liquid phase after the multi-stage iron, aluminum and chromium removal is subjected to liquid phase extraction, and the obtained raffinate is used to recover the valuable metals copper, zinc and scandium through a multi-stage precipitation method.

20. The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgy of laterite nickel ore according to claim 1, characterized in that: The nickel-cobalt-manganese mixed salt is a mixed salt of battery-grade nickel sulfate, cobalt sulfate and manganese sulfate, the nickel salt is battery-grade nickel sulfate, the cobalt salt is battery-grade cobalt sulfate, and the manganese salt is battery-grade manganese sulfate.

21. [Corrected 25.07.2023 in accordance with Rule 91] The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 1, characterized in that: The chemical formula of the nickel-cobalt-manganese ternary precursor is Ni x Co y Mn z (OH)2, where 0 < x < 1, 0 ≤ y < 1, 0 ≤ z < 1, and x + y + z = 1; The nickel-cobalt-manganese ternary precursor meets the requirements for preparing positive electrode materials for ternary power batteries, including ordinary ternary materials, high-voltage ternary materials, high-nickel / ultra-high-nickel ternary materials, and lithium-rich manganese-based materials.

22. [Corrected 25.07.2023 in accordance with Rule 91] The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 1, characterized in that: The D50 of the nickel-cobalt-manganese ternary precursor is 2-20 μm and the tap density is 0.5-2.6 g / cm 3 , specific surface area BET is 2-50m 2 / g.

23. [Corrected 25.07.2023 in accordance with Rule 91] The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 1, characterized in that: The cross-sectional structure of the nickel-cobalt-manganese ternary precursor is radially arranged or non-radially arranged; The pore distribution state of the nickel-cobalt-manganese ternary precursor is any one of uniform pore distribution, concentrated pore distribution inside, concentrated pore distribution outside, and multi-layer annular pore distribution; The distribution state of the nickel, cobalt and manganese elements in the nickel, cobalt and manganese ternary precursor is any one of uniform distribution, double-layer or multi-layer core-shell distribution, gradient distribution, full concentration gradient distribution and double gradient distribution.

24. [Corrected 25.07.2023 in accordance with Rule 91] The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 1, characterized in that: The process conditions of the controlled precipitation reaction are: controlling the pH to 9-13, the complexing agent concentration to 0.1-20 g / L, the temperature to 40-80° C., and the stirring speed of the reactor to 50-500 rpm; The precipitant is a mixture of one or more of potassium hydroxide, sodium hydroxide or sodium carbonate; The complexing agent is a mixture of one or more of ammonia water, ammonium carbonate, citric acid, oxalic acid, acetic acid and EDTA.

25. [Corrected 25.07.2023 in accordance with Rule 91] A green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 24, characterized in that: The controlled precipitation reaction also includes a doping step, specifically preparing a 0.01-0.1 mol / L doping element solution with a soluble salt of the doping element for doping; The doping element is one or more of aluminum, magnesium, zirconium, titanium, yttrium, tungsten, molybdenum, calcium, niobium, lanthanum, indium, strontium, tantalum, iron, copper, zinc, boron, fluorine, and vanadium.

26. [Corrected 25.07.2023 in accordance with Rule 91] A green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 25, characterized in that: The controlled precipitation reaction and doping further include a coating step, specifically preparing a 0.1-1 mol / L doping element solution with a soluble salt of the doping element for coating; The coating element is one or more of cobalt, manganese, aluminum, magnesium, zirconium, titanium, yttrium, tungsten, molybdenum, calcium, niobium, lanthanum, indium, strontium, tantalum, iron, copper and zinc.

27. [Corrected 25.07.2023 in accordance with Rule 91] A green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 24, characterized in that: The stirring device of the reactor adopts any one or more combinations of straight-blade open turbine stirring propeller, inclined-blade open turbine stirring propeller, and inclined-blade disc turbine stirring propeller.

28. [Corrected 25.07.2023 in accordance with Rule 91] The green method for producing nickel, cobalt and manganese new energy raw materials by hydrometallurgical method of laterite nickel ore according to claim 1, characterized in that: The positive electrode material for a ternary power battery is prepared from the nickel-cobalt-manganese ternary precursor and the lithium-containing raw material, and the specific steps are: According to the content ratio of nickel, cobalt and manganese in the positive electrode material for the ternary power battery, the nickel, cobalt and manganese ternary precursor is reacted with lithium carbonate or lithium hydroxide at high temperature to synthesize the positive electrode material for the ternary power battery.

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