Process for the recovery of nickel, cobalt and manganese from a material containing nickel, cobalt and manganese

Abstract

The application specifically discloses a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, which comprises the following steps: a first leaching process, a pH adjusting process, a first solid-liquid separation process, a first impurity removal process, a second leaching process and a second impurity removal process. The method for recovering nickel, cobalt and manganese from the material containing nickel, cobalt and manganese provided by the application does not need to add oxidants and reducing agents, the pH value of the first mixed slurry obtained in the first leaching process is adjusted by adding alkali, the pressure filtration time of liquid-solid separation can be effectively reduced, the amount of auxiliary materials used in the subsequent impurity removal process can also be reduced, the solid manganese concentrate obtained after the second leaching process can be washed simply, the manganese concentrate can be directly sold, the subsequent manganese extraction process is omitted, the extraction cost of manganese is reduced, and the economic benefit is further improved. Therefore, the recovery method provided by the application has the characteristics of low cost and good economic benefit.

Description

Technical Field

[0001] This application belongs to the field of hydrometallurgical technology, and in particular relates to a method for recovering nickel, cobalt and manganese from nickel-containing materials. Background Technology

[0002] Nickel-cobalt-manganese (NCM)-containing materials are important raw materials for the preparation of battery-grade nickel sulfate and battery-grade cobalt sulfate. In related technologies, the recovery of nickel, cobalt, and manganese from NCM-containing materials is usually divided into reduction leaching and oxidation leaching. However, the above two leaching methods require the addition of a large amount of reducing agent or oxidizing agent, resulting in high costs.

[0003] In view of this, this application provides a method for recovering nickel, cobalt, and manganese from materials containing nickel, cobalt, and manganese. Summary of the Invention

[0004] This application is made in view of the above-mentioned technical problems. The purpose is to provide a method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials, so as to reduce the cost of recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials and thus improve economic efficiency.

[0005] To address the aforementioned technical problems, this application provides a method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials, the method comprising the following steps:

[0006] In the first leaching step, the nickel-cobalt-manganese-containing material is mixed with a first leaching agent and subjected to a first leaching treatment to obtain a first mixed slurry.

[0007] In the pH adjustment step, alkali is added to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3, thereby obtaining the first mixed solution;

[0008] First solid-liquid separation: The first mixture is subjected to first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt;

[0009] The first impurity removal step involves subjecting the first leachate to a first impurity removal treatment to obtain a salt solution containing nickel and cobalt.

[0010] In the second leaching process, the first leaching residue is mixed with the second leaching agent to leach out the nickel and cobalt in the first leaching residue, thereby obtaining a second mixture.

[0011] The second impurity removal process involves subjecting the second mixture to a second impurity removal treatment to obtain a solid containing manganese concentrate and a second filtrate.

[0012] The aforementioned method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials employs a two-stage leaching process. In the first leaching stage, no oxidizing or reducing agents are added, effectively improving the working environment and saving on auxiliary material costs. Adjusting the pH of the first mixed slurry to 1.5-3 using alkali reduces the amount of auxiliary materials used in the subsequent first impurity removal process, thereby reducing the amount of nickel and cobalt carried away by the sedimentation of auxiliary material residue and improving the overall nickel-cobalt recovery rate. It also reduces the pressure filtration time for the first solid-liquid separation. Furthermore, the second impurity removal process treats the second mixed liquor to obtain manganese-containing concentrate. Washing this concentrate yields directly marketable manganese concentrate, eliminating the need for subsequent manganese extraction, reducing manganese extraction costs, and further improving economic efficiency. Therefore, the method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials provided in this application is characterized by low cost and high economic benefits.

[0013] In some embodiments, the first leaching step includes:

[0014] The pulping step involves mixing the nickel-cobalt-manganese-containing material with a solvent to obtain a slurry, wherein the solvent includes water and / or the second filtrate;

[0015] In the first leaching step, the slurry and the first leaching agent are mixed and subjected to a first leaching treatment to obtain a first mixed slurry.

[0016] In the first leaching process, the nickel-cobalt-manganese-containing material is first mixed and slurried with a solvent, which can disperse the nickel-cobalt-manganese-containing material, effectively prevent the material from clogging the pipeline, and make the material react more fully in the subsequent first leaching reaction.

[0017] In some embodiments, the first leaching treatment satisfies at least one of the following conditions:

[0018] I) The endpoint pH is 0–1;

[0019] II) The first leaching temperature is 70–100℃;

[0020] Ⅲ) The first leaching time is 1h to 8h.

[0021] Controlling the pH of the first mixed slurry to 0-1 is beneficial for the leaching of nickel and cobalt in the first mixed slurry.

[0022] In some embodiments, the nickel-cobalt-manganese-containing material comprises a mixture of nickel-cobalt hydroxide.

[0023] In some embodiments, the alkali includes at least one of nickel hydroxide, cobalt hydroxide, or a mixture thereof; further, the alkali includes a mixture of nickel and cobalt hydroxide, and the mass ratio of the mixture of nickel and cobalt hydroxide in the alkali to the mixture of nickel and cobalt hydroxide in the nickel-cobalt-manganese-containing material is (1-3):(17-19).

[0024] In some embodiments, the second leaching treatment satisfies at least one of the following conditions:

[0025] I) The endpoint pH is -1 to 0;

[0026] II) The second leaching temperature is 70–100℃;

[0027] Ⅲ) The second leaching time is 1h to 6h.

[0028] The second leaching process, using high temperature and high acid, is more conducive to the leaching of nickel and cobalt.

[0029] In some embodiments, during the second impurity removal process, 5 to 15 minutes before the end of the second leaching treatment, a flocculant is added for a second impurity removal treatment, resulting in a solid containing manganese concentrate and a second filtrate. Using the flocculant to aggregate particles from the second leaching process for filtration facilitates the separation of the solid containing manganese concentrate and the second filtrate in the second impurity removal process. The second filtrate is then returned to the pulping step in the first leaching process, thus fully utilizing the residual leaching agent in the second filtrate. This reduces the amount of the first leaching agent used and inhibits the leaching of manganese from the first leaching solution.

[0030] In some embodiments, the amount of flocculant added is 1% to 10% of the mass of the second mixture.

[0031] In some embodiments, the method further includes:

[0032] In the washing process, the solid material of the manganese concentrate is washed with a washing solution to obtain manganese concentrate and a washing liquid. The washing liquid is then returned to the second leaching process. Returning the washing liquid to the second leaching process reduces the amount of second leaching agent used and allows for the recovery of residual manganese concentrate from the washing liquid, thereby improving the overall manganese yield.

[0033] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0034] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0035] Figure 1 This is a flowchart of a method for recovering nickel, cobalt, and manganese from materials containing nickel, cobalt, and manganese, as described in this application. Detailed Implementation

[0036] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0037] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0038] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0039] Unless otherwise specified, the pressures mentioned in this application are gauge pressures, where gauge pressure = absolute pressure - standard atmospheric pressure. For example, an evaporation decomposition pressure of 0.2 MPa means that the gauge pressure of the evaporation decomposition pressure is 0.2 MPa, and the absolute pressure is (0.2 + 0.1013) MPa.

[0040] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0041] The general inventive concept of this application is to provide a method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials. The method involves mixing the nickel-cobalt-manganese-containing material with a first leaching agent for a first leaching treatment, then adding alkali to adjust the pH to 1.5-3, followed by a first solid-liquid separation to obtain a first leaching solution and a first leaching residue. The first leaching solution is then subjected to a first impurity removal treatment to obtain a salt solution containing nickel and cobalt. The first leaching residue is then mixed with a second leaching agent to leach out the nickel and cobalt from the first leaching residue, resulting in a second mixed solution. The second mixed solution is then subjected to a second impurity removal treatment to obtain a solid containing manganese concentrate and a second filtrate. In this method, no oxidizing or reducing agents are added in the first leaching step, thus reducing the amount of auxiliary materials used. Adjusting the pH value of the first leaching solution reduces the amount of auxiliary materials required in the subsequent first impurity removal treatment of the first leaching slurry, and also reduces the amount of nickel and cobalt residue carried away by the slag, improving the overall recovery rate of nickel and cobalt. Furthermore, the alkali added to the first leaching slurry adjusts the pH of the first mixed slurry to 1.5-3, which also helps to reduce the pressure filtration time of the first solid-liquid separation, improving production efficiency. Simultaneously, the solid matter containing manganese concentrate obtained in the second impurity removal step can be directly sold as manganese concentrate after simple washing, eliminating the need for subsequent manganese extraction, reducing manganese extraction costs, and further improving economic efficiency. Therefore, this method for recovering nickel, cobalt, and manganese from materials containing these materials saves on auxiliary materials, reduces recovery costs, and improves the overall recovery rate and economic efficiency of nickel, cobalt, and manganese.

[0042] Based on the above overall concept, and referring to Figure 1 As shown in the embodiment of this application, a method for recovering nickel, cobalt, and manganese from a material containing these materials is provided. The method includes the following steps:

[0043] In the first leaching step, the nickel-cobalt-manganese-containing material is mixed with a first leaching agent and subjected to a first leaching treatment to obtain a first mixed slurry.

[0044] In the pH adjustment step, alkali is added to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3, thereby obtaining the first mixed solution;

[0045] First solid-liquid separation: The first mixture is subjected to first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt;

[0046] The first impurity removal step involves subjecting the first leachate to a first impurity removal treatment to obtain a salt solution containing nickel and cobalt.

[0047] In the second leaching process, the first leaching residue is mixed with the second leaching agent to leach out the nickel and cobalt in the first leaching residue, thereby obtaining a second mixture.

[0048] The second impurity removal process involves subjecting the second mixture to a second impurity removal treatment to obtain a solid containing manganese concentrate and a second filtrate.

[0049] It should be noted that the nickel-cobalt-manganese-containing materials include mixtures of nickel-cobalt hydroxide. Manganese concentrate refers to ore with a manganese content of 30% or more.

[0050] In the pH adjustment process, the alkali includes at least one of nickel hydroxide, cobalt hydroxide, or a mixture thereof. Specifically, the alkali includes a mixture of nickel hydroxide and cobalt hydroxide, and the mass ratio of the mixture of nickel hydroxide and cobalt hydroxide in the alkali to the mixture of nickel hydroxide and cobalt hydroxide in the nickel-cobalt-manganese-containing material is (1-3):(13-19). For example, the mass ratio of the mixture of nickel hydroxide and cobalt hydroxide in the alkali to the mixture of nickel hydroxide and cobalt hydroxide in the nickel-cobalt-manganese-containing material can be controlled to any ratio within the range of 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 2:17, 2:18, 2:19, 3:17, 3:18, 3:19, and (1-3):(13-19).

[0051] In the pH adjustment process, the pH value of the first mixed slurry is adjusted to 1.5 to 3 after adding alkali. For example, the pH value of the first mixed slurry after adjustment can be controlled to any value within the range of 1.5, 2, 2.5, 3 and 1.5 to 3.

[0052] In the above embodiments, both the first leaching agent and the second leaching agent are concentrated sulfuric acid. In other embodiments, the first leaching agent and the second leaching agent can also be hydrochloric acid, nitric acid, etc. The selection of the first leaching agent and the second leaching agent should be combined with the subsequent impurity removal process to avoid introducing additional impurities into the subsequent impurity removal process, thereby affecting the quality of the product.

[0053] In the above embodiments, the nickel-cobalt-manganese-containing material is first mixed with a first leaching agent to obtain a first mixed slurry. Then, alkali is added to adjust the pH of the first mixed slurry to 1.5-3, followed by a first solid-liquid separation to obtain a first leaching solution and a first leaching residue. The first leaching solution is then purified to obtain a salt solution containing nickel and cobalt, thus achieving the recovery of nickel and cobalt. Simultaneously, the first leaching residue is mixed with a second leaching agent to leach the nickel and cobalt in the first leaching residue a second time, resulting in a second mixed solution. Finally, the second mixed solution is purified to obtain a solid substance containing manganese concentrate and a second filtrate, thus achieving the recovery of manganese. In this method, the pH of the first mixed slurry is adjusted to 1.5-3 using alkali. This reduces the amount of carbonate additive used in the first impurity removal process of the first leaching solution, thereby reducing the amount of nickel and cobalt carried away by the precipitation of additive residue and improving the overall recovery rate of nickel and cobalt. It also reduces the pressure filtration time for the first solid-liquid separation. Furthermore, the manganese concentrate obtained from the secondary leaching only needs washing to obtain directly marketable manganese concentrate, eliminating the need for subsequent manganese extraction, reducing manganese extraction costs, and further improving economic efficiency. Therefore, the embodiments of this application reduce the recovery costs of nickel, cobalt, and manganese, and improve economic efficiency.

[0054] In an optional embodiment of this application, the first leaching process includes:

[0055] The pulping step involves mixing the nickel-cobalt-manganese-containing material with a solvent to obtain a slurry, wherein the solvent includes water and / or the second filtrate;

[0056] In the first leaching step, the slurry and the first leaching agent are mixed and subjected to a first leaching treatment to obtain a first mixed slurry.

[0057] In the above embodiments, the first leaching process includes a slurrying step and a first leaching step, that is, the nickel-cobalt-manganese-containing material is first slurried with a solvent to obtain a slurry; then the slurry is mixed with a first leaching agent to perform a first leaching treatment to obtain a first mixed slurry; wherein, the solvent is production water and / or a second filtrate obtained after a second impurity removal process. When the second filtrate is returned to the slurrying step for recycling, on the one hand, the residual leaching agent in the second filtrate is fully utilized, which can reduce the amount of leaching agent used and inhibit the leaching of manganese in the first leaching solution.

[0058] In an optional embodiment of this application, the first leaching treatment satisfies at least one of the following conditions:

[0059] I) The endpoint pH is 0–1;

[0060] II) The first leaching temperature is 70–100℃;

[0061] Ⅲ) The first leaching time is 1h to 8h.

[0062] In an optional embodiment of this application, the second leaching treatment satisfies at least one of the following conditions:

[0063] I) The endpoint pH is -1 to 0;

[0064] II) The second leaching temperature is 70–100℃;

[0065] Ⅲ) The second leaching time is 1h to 6h.

[0066] In the above embodiments, such parameter settings ensure the leaching efficiency of the first-stage leaching and the second-stage leaching. Moreover, the high temperature and high acid of the second-stage leaching can selectively leach nickel and high-valence cobalt, which can not only improve the nickel and cobalt yield, but also effectively improve the grade of the manganese-containing concentrate in the second impurity removal process.

[0067] In an optional embodiment of this application, during the second impurity removal process, 5 to 15 minutes before the end of the second leaching treatment, a flocculant is added to perform a second impurity removal treatment to obtain a solid containing manganese concentrate and a second filtrate.

[0068] In the above embodiments, the amount of flocculant added is 1% to 10% of the mass of the second mixture. For example, the amount of flocculant added can be controlled to any value within the range of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and 1% to 10% of the mass of the second mixture.

[0069] In the above embodiments, the flocculant can aggregate the particles in the second leaching process and then filter them, which is beneficial to the separation of solids containing manganese concentrate and the second filtrate in the subsequent second impurity removal process.

[0070] In an optional embodiment of this application, the method further includes:

[0071] In the washing process, the solid material containing manganese concentrate is washed with a washing solution to obtain manganese concentrate and a washing solution, wherein the washing solution is returned to the second leaching process.

[0072] In the above embodiments, the solid material containing manganese concentrate can be washed to obtain manganese concentrate that can be sold directly, eliminating the need for subsequent manganese extraction processes, reducing the extraction cost of manganese, and further improving economic efficiency; at the same time, the washing liquid is returned to the second leaching process for use, which can reduce the amount of the second leaching agent and recover the residual manganese concentrate in the washing liquid, thereby improving the overall yield of manganese.

[0073] The following examples use concentrated sulfuric acid as the first and second leaching agents, MHP as the nickel-cobalt-manganese-containing material, and MHP as the alkali to illustrate the content disclosed in this application in more detail. These examples are merely illustrative, as various modifications and variations within the scope of this application's disclosure will be apparent to those skilled in the art. Unless otherwise stated, all reagents and raw materials used in the examples are commercially available or synthesized using conventional methods, and the instruments and equipment used in the examples are commercially available. The detection results of the MHP raw material are shown in Table 1.

[0074] Table 1. Chemical element content (%) of MHP raw materials

[0075] element Ni Co Mn Na Fe Moisture content 40.82 3.22 6.69 0.07 0.21 52.1

[0076] Example 1

[0077] This application provides a method for recovering nickel, cobalt, and manganese from materials containing these materials, comprising the following steps:

[0078] (1) 24m 3 The solvent and 20.7t of MHP raw material are mixed, heated to 85℃, and slurried for 30min under stirring speed of 30Hz to obtain slurry (wherein, the solvent in this process is production water and second filtrate, the same below);

[0079] (2) Add concentrated sulfuric acid slowly to the slurry multiple times, control the pH value of the reaction slurry to 0.8-1, keep the reaction at 85℃ for 4 hours, and obtain the first mixed slurry;

[0080] (3) Add 1.57t of MHP raw material to the first mixed slurry to adjust the pH of the solution to 2.5-3.0, add water to make the solution concentration 128.67g / L, and then filter press to obtain approximately 4616kg of the first leaching residue and approximately 24m³ of the first leachate. 3 ;

[0081] (4) Add 150 kg of calcium powder / MNi solution to the first leachate and adjust the pH of the solution to 5-5.5. React for 10 hours to precipitate iron and aluminum elements. After pressure filtration, 500 kg / MNi (nickel element) of iron slag and iron removal liquid are produced. After testing, the iron and aluminum content in the iron removal liquid is less than 1 ppm. Then, the extraction process can be used to obtain a sulfate solution containing nickel and cobalt.

[0082] (5) Mix the first leaching residue, concentrated sulfuric acid and solvent, control the pH value of the solution to -0.4 to 0, and control the temperature to 85±5℃. The reaction time is 2h to obtain the second mixture (wherein, the solvent in this process is production water and washing liquid).

[0083] (6) Add 8 kg of flocculant PAM 10 minutes before the end of the second leaching reaction, then filter the second mixture by pressure. After 8-10 hours of pressure filtration, approximately 1648 kg of manganese concentrate and approximately 15 ml of the second filtrate are obtained. 3 The second filtrate obtained is returned to the solvent circulation in step (1);

[0084] (7) The solid material containing manganese concentrate was mixed with production water and washed multiple times to obtain approximately 1374 kg of manganese concentrate and approximately 25 ml of washing liquid. 3 After washing, the liquid is returned to the (5) internal circulation.

[0085] The extracts from Example 1 were analyzed, and the results are shown in Table 2.

[0086] Table 2 shows the detection and analysis results of each leachate in Example 1.

[0087] Serial Number Ni Co Mn Na Fe First leachate / concentration g / L 128.67 8.76 11.86 0.27 0.94 Second mixture / concentration g / L 53.73 6.59 3.82 0.08 0.24 Manganese concentrate composition (dry basis) % 0.51 0.28 35.35 0.01 0.00 First leaching residue leaching rate of metal A1 (%) 82.29 68.92 46.26 88.88 95.57 The leaching rate of metal A2 in the second leaching slag test is %. 90.56 84.22 8.58 95.08 99.97 Metal A3 leaching rate % in washing residue 92.78 79.88 4.31 100 100 Total leaching rate % 98.34 95.13 50.90 99.45 100.00

[0088] The leaching rate in Table 2 is the total leaching rate of the entire process, for example, total leaching rate % = (A1 + (1 - A1 / 100) * A2 + (1 - A1 / 100 - (1 - A1 / 100) * A2 / 100) * A3 / 100)%, where A1 = 1 - Z1 / Y. The results filled in the table in subsequent embodiments are the same. A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag; A2 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the second leaching slag; A3 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the washing slag; Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag; Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed + the content of nickel, cobalt, manganese, sodium and iron in the return feed. For example, the total leaching rate of Ni is % = (82.29 + (1 - 82.29 / 100) * 90.56) + (1 - 0.8229 - (1 - 82.29 / 100) * 90.56 / 100) * 92.78 / 100)% = 98.34%.

[0089] Example 2

[0090] (1) 23.6m 3 The solvent and 19.9t of MHP raw material were mixed, heated to 85±5℃, and slurried for 30min under stirring speed of 30Hz to obtain slurry;

[0091] (2) Add concentrated sulfuric acid slowly to the slurry multiple times, control the pH value of the reaction slurry to 0.4-0.6, keep the reaction at 85℃ for 4 hours to obtain the first mixed slurry;

[0092] (3) Add 1.4t of MHP raw material to the first mixed slurry to adjust the solution pH to 2-2.5, add water to make the solution concentration 125.62g / L, and then filter press to obtain approximately 4445kg of the first leaching residue and approximately 24ml of the first leachate. 3 ;

[0093] (4) Add 150 kg of calcium powder / MNi solution to the first leachate and adjust the pH of the solution to 5-5.5. React for 10 hours to precipitate iron and aluminum elements. After pressure filtration, 500 kg / MNi of iron slag and iron removal liquid are produced. After testing, the iron and aluminum content in the iron removal liquid is less than 1 ppm. Then, the extraction process can be used to obtain a sulfate solution containing nickel and cobalt.

[0094] (5) Mix the first leaching residue, concentrated sulfuric acid and solvent, control the pH value of the solution to -0.6 to -0.4, and control the temperature to 85±5℃. The reaction time is 2h to obtain the second mixture.

[0095] (6) Add 8 kg of flocculant PAM 10 minutes before the end of the second leaching reaction, then filter the second mixture by pressure. After 8-10 hours of pressure filtration, approximately 1587 kg of manganese concentrate and approximately 15 ml of the second filtrate are obtained. 3 The second filtrate obtained is returned to the solvent circulation in step (1);

[0096] (7) Washing process: The solid material containing manganese concentrate is mixed with production water and washed multiple times to obtain approximately 1323 kg of manganese concentrate and approximately 25 ml of washing liquid. 3 After washing, the liquid is returned to the internal circulation of step (5).

[0097] The extracts from Example 1 were analyzed, and the results are shown in Table 3.

[0098] Table 3. Detection and analysis results of each leachate in Example 2.

[0099] Serial Number Ni Co Mn Na Fe First leachate / concentration g / L 125.62 8.56 11.26 0.26 0.36 Second mixture / concentration g / L 60.22 7.18 3.87 0.05 0.05 Manganese concentrate composition (dry basis) % 0.48 0.31 36.65 0.01 0.00 First leaching residue leaching rate of metal A1 % 84.02 73.10 47.24 93.39 97.87 The leaching rate of metal A2 in the second leaching slag test is %. 93.95 90.94 9.58 92.94 99.98 Metal A3 leaching rate % in washing residue 89.89 61.66 2.03 100 89.89 Total leaching rate % 99.04 97.58 52.30 99.53 100.00

[0100] The leaching rate in Table 3 is the total leaching rate of the entire process, for example, total leaching rate % = (A1 + (1 - A1 / 100) * A2 + (1 - A1 / 100 - (1 - A1 / 100) * A2 / 100) * A3 / 100)%, where A1 = 1 - Z1 / Y. The results filled in the table in subsequent embodiments are the same. A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag; A2 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the second leaching slag; A3 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the washing slag; Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag; Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed + the content of nickel, cobalt, manganese, sodium and iron in the return feed. For example, the total leaching rate of Ni is % = (84.02 + (1 - 84.02 / 100) * 93.95) + (1 - 0.8402 - (1 - 84.02 / 100) * 93.95 / 100) * 89.89 / 100)% = 99.04%.

[0101] Example 3

[0102] (1) 24.2m 3 The solvent and 19.8t of MHP raw material were mixed, heated to 85℃, and slurried for 30min under stirring speed of 30Hz to obtain slurry;

[0103] (2) Add concentrated sulfuric acid slowly to the slurry multiple times, control the pH value of the reaction slurry to 0-0.2, keep the reaction at 85℃ for 4 hours, and obtain the first mixed slurry;

[0104] (3) Add 1.3t of MHP raw material to the first mixed slurry to adjust the pH of the solution to 1.5-2.0, add water to make the solution concentration 126.12g / L, and then filter press to obtain about 4400kg of the first leaching residue and about 24ml of the first leachate. 3 ;

[0105] (4) Add 150 kg of calcium powder / MNi solution to the first leachate and adjust the pH of the solution to 5-5.5. React for 10 hours to precipitate iron and aluminum elements. After pressure filtration, 500 kg / MNi of iron slag and iron removal liquid are produced. After testing, the iron and aluminum content in the iron removal liquid is less than 1 ppm. Then, the extraction process can be used to obtain a sulfate solution containing nickel and cobalt.

[0106] (5) Mix the first leaching residue, concentrated sulfuric acid and solvent, control the pH value of the solution to -0.1 to -0.6, and control the temperature to 85±5℃. The reaction time is 2h to obtain the second mixture.

[0107] (6) Add 8 kg of flocculant PAM 10 minutes before the end of the second leaching reaction, then filter the second mixture by pressure. After 8-10 hours of filtration, approximately 1571 kg of manganese concentrate and approximately 23.8 ml of the second filtrate are obtained. 3 The second filtrate obtained is returned to the solvent circulation in step (1);

[0108] (7) The solids containing manganese concentrate were mixed with production water and washed multiple times to obtain approximately 1310 kg of manganese concentrate and 24.8 m³ of washing liquid. 3 After washing, the liquid is returned to the internal circulation of step (5).

[0109] The extracts from Example 1 were analyzed, and the results are shown in Table 4.

[0110] Table 4. Detection and analysis results of each leachate in Example 3.

[0111]

[0112]

[0113] The leaching rate in Table 4 is the total leaching rate of the entire process, for example, total leaching rate % = (A1 + (1 - A1 / 100) * A2 + (1 - A1 / 100 - (1 - A1 / 100) * A2 / 100) * A3 / 100)%, where A1 = 1 - Z1 / Y. The results filled in the table in subsequent embodiments are the same. A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag; A2 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the second leaching slag; A3 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the washing slag; Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag; Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed + the content of nickel, cobalt, manganese, sodium and iron in the return feed. For example, the total leaching rate of Ni is % = (84.72 + (1 - 84.72 / 100) * 94.42) + (1 - 0.8472 - (1 - 84.72 / 100) * 94.42 / 100) * 88.98 / 100)% = 99.15%.

[0114] Comparative Example 1

[0115] The results are basically the same as those in Example 1, except that a reducing agent was added in step (2), and steps (5) and (7) were not included in Comparative Example 1. The reducing agent is one of hydrogen peroxide, sodium metabisulfite, or sulfur dioxide. Comparative Example 1 takes the addition of sodium metabisulfite as an example, and the results are shown in Table 5.

[0116] Table 5 shows the detection and analysis results of each leachate in Comparative Example 1.

[0117] Serial Number Ni Co Mn Na Fe First leachate / concentration g / L 132.62 10.86 20.28 1.67 0.72 Manganese slag composition (dry basis) % 20.86 2.42 15.82 0.18 0.09 First leaching residue leaching rate of metal A1 (%) 97.40 95.82 88.89 98.10 97.99

[0118] In Table 5, the leaching rate is the total leaching rate of the entire process. For example, the total leaching rate % = A1%, where A1 = 1 - Z1 / Y, A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag, Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag, and Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed plus the content of nickel, cobalt, manganese, sodium and iron in the return feed.

[0119] As can be seen from the comparison between Example 1 and Comparative Example 1, in Comparative Example 1, after the reducing agent is added to the reaction in step (2), the leaching rates of manganese and cobalt both reach over 95%, and the slag rate of the filter press is less than 5%. However, due to the high concentration of cobalt and manganese in the solution, the extraction and separation cost is high, and sodium ions are introduced, which will have an adverse effect on subsequent extraction and crystallization. In contrast, the direct leaching adopted in Example 1 can achieve a nickel-cobalt leaching rate of over 80% after step (2). Then, through selective leaching in the high-acid step (5), the total leaching rate of nickel also reaches over 99%. Moreover, the second filtrate in step (5) can be returned to step (2) for recycling, saving the cost of auxiliary materials. In addition, due to the selective leaching in step (5), the total leaching rate of manganese is less than 55%, thereby saving the cost of acid and alkali consumption for extracting manganese.

[0120] Comparative Example 2

[0121] The results are basically the same as those in Example 2, except that an oxidant is added in step (2). The oxidant can be oxygen, ozone, or persulfate. In Comparative Example 2, sodium persulfate was used as an example. The amount of sodium persulfate was 1400±50kg. The results are shown in Table 6.

[0122] Table 6. Leaching Detection and Analysis Results of Comparative Example 2

[0123] Serial Number Ni Co Mn Na Fe First leachate / concentration g / L 124.12 8.51 2.82 5.86 0.71 Second mixture / concentration g / L 62.86 9.66 1.52 7.26 0.16 Manganese concentrate composition (dry basis) % 0.62 0.72 42.78 0.24 0.00 First leaching residue leaching rate of metal A1 % 83.52 51.91 6.67 76.70 86.81 The leaching rate of metal A2 in the second leaching slag test is %. 88.54 85.93 1.78 99.93 96.91 Metal A3 leaching rate (%) in washing residue 93.58 68.53 13.25 100.00 92.023 Total leaching rate % 98.13 93.28 8.45 99.06 99.60

[0124] The leaching rate in Table 6 is the total leaching rate of the entire process, for example, total leaching rate % = (A1 + (1 - A1 / 100) * A2 + (1 - A1 / 100 - (1 - A1 / 100) * A2 / 100) * A3 / 100)%, where A1 = 1 - Z1 / Y. The results filled in the table in subsequent embodiments are the same. A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag, A2 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the second leaching slag, A3 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the washing slag, Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag, and Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed + the content of nickel, cobalt, manganese, sodium and iron in the return feed. For example, the total leaching rate of Ni is % = (83.52 + (1 - 83.52 / 100) * 88.54) + (1 - 0.8352 - (1 - 83.52 / 100) * 88.54 / 100) * 93.58 / 100)% = 98.13%.

[0125] A comparison of Example 2 and Comparative Example 2 shows that after adding the oxidant, the manganese leaching rate decreased from 50% to less than 10%. Although this saved on manganese extraction costs, it slowed down the filtration speed in step (5), increased the overall filter residue, and led to increased nickel and cobalt losses in the filter residue. In addition, it increased the cost of the oxidant and introduced sodium ions, increasing the difficulty of sodium extraction and crystallization separation. Therefore, the direct leaching process used in Example 2 is simpler, lower in cost, and can also save some of the manganese extraction costs, making it more suitable for actual production.

[0126] Comparative Example 3

[0127] The process is basically the same as in Example 3, except that MHP raw material was not added in step (3) to adjust the pH value of the first mixed slurry. The results are shown in Table 7. The specific steps are as follows:

[0128] (1) 23.8m 3 20.1t of production water and MHP raw material were mixed, heated to 85°C, and slurried for 30 minutes at a stirring speed of 30 Hz to obtain slurry;

[0129] (2) Add concentrated sulfuric acid to the obtained slurry, control the pH value of the slurry to 0-1, and keep it at 85℃ for 4 hours. Add water to make the solution concentration 125.89 g / L, and then filter it to obtain the first leachate and the first leach residue.

[0130] (3) Take the first leachate and add 300 kg of calcium powder / MNi solution to adjust the pH of the solution to 5-5.5. After reacting for about 24 hours, elements such as iron and aluminum will precipitate. After filtration, 700 kg / MNi of iron slag and iron-removed liquid are produced. The iron and aluminum content in the iron-removed liquid is less than 1 ppm. The test results are shown in Table 7. Then, the extraction process is carried out to obtain a sulfate solution containing nickel and cobalt.

[0131] Table 7. Leaching Detection and Analysis Results of Comparative Example 3

[0132] Serial Number Ni Co Mn Na Fe First leachate / concentration g / L 125.89 8.56 11.34 0.27 0.92 First leaching residue leaching rate of metal A1 (%) 84.36 71.60 46.52 93.73 95.29

[0133] In Table 7, the leaching rate is the total leaching rate of the entire process. For example, the total leaching rate % = A1%, where A1 = 1 - Z1 / Y, A1 represents the leaching rate of nickel, cobalt, manganese, sodium and iron in the first leaching slag, Z1 represents the content of nickel, cobalt, manganese, sodium and iron in the first leaching slag, and Y represents the content of nickel, cobalt, manganese, sodium and iron in the first feed plus the content of nickel, cobalt, manganese, sodium and iron in the return feed.

[0134] The comparison between Example 3 and Comparative Example 3 shows that the nickel leaching rate in Example 3 is 84%. After adjusting the pH value with MHP raw material, iron removal is carried out. The amount of calcium powder used is only 150 kg calcium powder / MNi, and the reaction time is about 11 hours. Compared with Comparative Example 3, the iron removal process in Example 3 has a shorter reaction cycle and lower cost.

[0135] The above provides a detailed description of a method for recovering nickel, cobalt, and manganese from nickel-cobalt-manganese-containing materials. Specific examples have been used to illustrate the principles and implementation methods of this application; the descriptions of these embodiments are merely for the purpose of helping to understand the core ideas of this application. It should be noted that those skilled in the art can make various improvements and modifications to this application without departing from its principles, and these improvements and modifications also fall within the protection scope of the claims of this application.

Claims

1. Process for the recovery of nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, characterized in that, The method includes the following steps: In the first leaching step, the nickel-cobalt-manganese-containing material is mixed with a first leaching agent and subjected to a first leaching treatment to obtain a first mixed slurry. In the first leaching step, no oxidant or reducing agent is added. The nickel-cobalt-manganese-containing material includes a mixture of nickel-cobalt hydroxide. In the pH adjustment step, alkali is added to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3, thereby obtaining a first mixed solution. The alkali includes at least one of nickel hydroxide, cobalt hydroxide, or a mixture thereof. First solid-liquid separation: The first mixture is subjected to first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt; The first impurity removal step involves subjecting the first leachate to a first impurity removal treatment to obtain a salt solution containing nickel and cobalt. In the second leaching process, the first leaching residue is mixed with the second leaching agent to leach out the nickel and cobalt in the first leaching residue, thereby obtaining a second mixture. In the second impurity removal process, before the second leaching treatment is completed, a flocculant is added to the second mixture to perform a second impurity removal treatment, resulting in a solid containing manganese concentrate and a second filtrate.

2. The method according to claim 1, characterized in that, The first leaching process includes: The pulping step involves mixing the nickel-cobalt-manganese-containing material with a solvent to obtain a slurry, wherein the solvent includes water and / or the second filtrate; In the first leaching step, the slurry and the first leaching agent are mixed and subjected to a first leaching treatment to obtain a first mixed slurry.

3. The method according to claim 1 or 2, wherein the first leaching treatment satisfies at least one of the following conditions: I) The endpoint pH is 0~1; II) The first leaching temperature is 70–100℃; Ⅲ) The first leaching time is 1h to 8h.

4. The method according to claim 1, characterized in that, The alkali comprises a nickel-cobalt hydroxide mixture, and the mass ratio of the nickel-cobalt hydroxide mixture in the alkali to the nickel-cobalt hydroxide mixture in the nickel-cobalt-manganese-containing material is (1~3):(17~19).

5. The method according to claim 1, characterized in that, The second leaching treatment satisfies at least one of the following conditions: I) The endpoint pH is -1 to 0; II) The second leaching temperature is 70–100℃; Ⅲ) The second leaching time is 1h to 6h.

6. The method according to claim 5, characterized in that, In the second impurity removal process, 5 to 15 minutes before the end of the second leaching treatment, a flocculant is added to carry out the second impurity removal treatment, resulting in a solid containing manganese concentrate and a second filtrate.

7. The method according to claim 5, characterized in that, The amount of flocculant added is 1% to 10% of the mass of the second mixture.

8. The method according to claim 1, characterized in that, The method further includes: In the washing process, the solid material containing manganese concentrate is washed with a washing solution to obtain manganese concentrate and a washing solution, wherein the washing solution is returned to the second leaching process.

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