Method for recovering nickel, cobalt and manganese from material containing nickel, cobalt and manganese

Abstract

The invention particularly discloses a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese. The method comprises the following steps of a first leaching procedure, a pH adjusting procedure, a first solid-liquid separation procedure, a first impurity removal procedure, a second leaching procedure and a second impurity removal procedure. According to the method for recycling the nickel, the cobalt and the manganese from the material containing the nickel, the cobalt and the manganese, an oxidizing agent and a reducing agent do not need to be added, the pH value of the first mixed slurry obtained in the first leaching procedure is adjusted by adding alkali, the filter pressing time of liquid-solid separation can be effectively shortened, and meanwhile the use amount of auxiliary materials in the subsequent impurity removal treatment process can be reduced; moreover, the manganese concentrate which can be directly sold can be obtained by simply washing the solid of the manganese-containing concentrate obtained by the second leaching process, so that the subsequent manganese extraction process is omitted, the manganese extraction cost is reduced, and the economic benefit is further improved. Therefore, the recovery method provided by the invention has the characteristics of low cost and good economic benefit.

Description

Technical Field

[0001] The present application belongs to the technical field of hydrometallurgy, and in particular relates to a method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese. Background Art

[0002] Nickel, cobalt and manganese-containing materials are important raw materials for preparing battery-grade nickel sulfate and battery-grade cobalt sulfate. In related technologies, the recovery of nickel, cobalt and manganese from nickel, cobalt and manganese-containing materials is generally 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, the present 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 technical problems and aims to provide a method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese, so as to reduce the cost of recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese, thereby improving economic benefits.

[0005] In order to solve the above technical problems, the present application provides a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, the method comprising the following steps:

[0006] a first leaching step, mixing the nickel-cobalt-manganese containing material with a first leaching agent and performing a first leaching treatment to obtain a first mixed slurry;

[0007] A pH adjustment step of adding alkali to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3 to obtain a first mixed solution;

[0008] first solid-liquid separation, subjecting the first mixed solution to a first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt;

[0009] a first impurity removal step, performing a first impurity removal treatment on the first leaching solution to obtain a salt solution containing nickel and cobalt;

[0010] a second leaching step, mixing the first leaching residue with a second leaching agent to leach nickel and cobalt in the first leaching residue to obtain a second mixed solution;

[0011] The second impurity removal step is to perform a second impurity removal treatment on the second mixed liquid to obtain a solid matter containing manganese concentrate and a second filtrate.

[0012] The above-mentioned method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese adopts a two-stage leaching method, and the method does not add an oxidant and a reducing agent during a leaching process, effectively improves the working environment, saves auxiliary material costs, and uses alkali to adjust the pH of the first mixed slurry to 1.5-3, which can reduce the amount of auxiliary materials used in the first impurity removal process of the first leachate, and then can reduce the nickel and cobalt taken away by the precipitation of the auxiliary material slag, improve the comprehensive recovery rate of nickel and cobalt, and reduce the filter pressing time of the first solid-liquid separation; In addition, the second mixed solution is treated by the second impurity removal process to obtain a solid containing manganese concentrate, and the solid containing manganese concentrate is washed to obtain a manganese concentrate directly sold outside, eliminating the subsequent fierce extraction process, reducing the extraction cost of manganese, and further improving the economic benefit. Therefore, the method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese provided by the present application has the characteristics of low cost and good economic benefit.

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

[0014] a slurrying step, 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 with a solvent to form a slurry, which can break up the nickel-cobalt-manganese-containing material, effectively avoid 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 end point pH is 0-1;

[0019] Ⅱ) The first leaching temperature is 70-100°C;

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

[0021] By controlling the pH of the first mixed slurry to be between 0 and 1, the leaching of nickel and cobalt in the first mixed slurry is facilitated.

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

[0023] In some embodiments, the base includes at least one of nickel hydroxide, cobalt hydroxide or a mixture thereof; further, the base includes a nickel-cobalt hydroxide mixture, and the mass ratio of the nickel-cobalt hydroxide mixture in the base to the nickel-cobalt hydroxide mixture in the nickel-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 end point pH is -1 to 0;

[0026] Ⅱ) The second leaching temperature is 70-100°C;

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

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

[0029] In some embodiments, in the second impurity removal process, 5 to 15 minutes before the end of the second leaching process, a flocculant is added to perform the second impurity removal process to obtain a solid containing manganese concentrate and a second filtrate. The flocculant is used to aggregate particles in the second leaching process for filtration, which is beneficial for separating the solid containing manganese concentrate and the second filtrate in the second impurity removal process, and the second filtrate is returned to the slurry step in the first leaching process, so that the residual leaching agent in the second filtrate is fully utilized, which not only reduces the amount of the first leaching agent, but also inhibits the leaching of manganese in the first leaching solution.

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

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

[0032] In the washing step, the solid matter containing the manganese concentrate is washed with a washing liquid to obtain a manganese concentrate and a washed liquid, wherein the washed liquid is used to return to the second leaching step. The washed liquid is returned to the second leaching step for use, which can not only reduce the amount of the second leaching agent, but also recycle the manganese concentrate remaining in the washed liquid, thereby improving the comprehensive yield of manganese.

[0033] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1 This is a flow chart of a method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese in this application. DETAILED DESCRIPTION

[0036] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0037] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0038] If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0039] If there is no special explanation, the pressure mentioned in this application is gauge pressure, which is gauge pressure = absolute pressure - standard atmospheric pressure. For example, if the evaporation decomposition pressure is 0.2 MPa, it 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] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": 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 the embodiment of the present application is to provide a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, by mixing the material containing nickel, cobalt and manganese with a first leaching agent for a first leaching treatment, then adding alkali to adjust the pH to 1.5-3, and then performing a first solid-liquid separation to obtain a first leachate and a first leaching residue, and performing a first impurity removal treatment on the first leachate to obtain a salt solution containing nickel and cobalt; then, the first leaching residue is mixed with a second leaching agent to leach nickel and cobalt in the first leaching residue to obtain a second mixed solution, and then the second mixed solution is subjected to a second impurity removal treatment to obtain a solid containing manganese concentrate and a second filtrate. In the method, no oxidant and reductant are added in the first leaching process, thereby reducing the amount of auxiliary materials, and adjusting the pH value of the first leachate can not only reduce the amount of auxiliary materials required in the subsequent first impurity removal treatment of the first leaching slurry, but also reduce the residual amount of nickel and cobalt taken away by the slag, thereby improving the comprehensive recovery rate of nickel and cobalt. Moreover, the alkali added in the first leaching slurry adjusts the pH of the first mixed slurry to 1.5-3, which is also conducive to reducing the pressure filtration time of the first solid-liquid separation and improving production efficiency. At the same time, the solid containing manganese concentrate obtained in the second impurity removal process can be obtained by simple washing to obtain manganese concentrate for direct sale, eliminating the subsequent fierce extraction process, reducing the extraction cost of manganese, and further improving economic benefits. Therefore, by the method for recovering nickel, cobalt and manganese from materials containing nickel, cobalt and manganese, the amount of auxiliary materials is saved, the recovery cost is reduced, and the comprehensive recovery rate and economic efficiency of nickel, cobalt and manganese are improved.

[0042] Based on the above general concept, reference Figure 1 As shown, the embodiment of the present application provides a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, the method comprising the following steps:

[0043] a first leaching step, mixing the nickel-cobalt-manganese containing material with a first leaching agent and performing a first leaching treatment to obtain a first mixed slurry;

[0044] A pH adjustment step of adding alkali to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3 to obtain a first mixed solution;

[0045] first solid-liquid separation, subjecting the first mixed solution to a first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt;

[0046] a first impurity removal step, performing a first impurity removal treatment on the first leaching solution to obtain a salt solution containing nickel and cobalt;

[0047] a second leaching step, mixing the first leaching residue with a second leaching agent to leach nickel and cobalt in the first leaching residue to obtain a second mixed solution;

[0048] The second impurity removal step is to perform a second impurity removal treatment on the second mixed liquid to obtain a solid matter containing manganese concentrate and a second filtrate.

[0049] It should be noted that the material containing nickel, cobalt and manganese includes a mixture of nickel hydroxide and cobalt hydroxide. Manganese concentrate refers to an ore with a manganese content of more than 30%.

[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 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): (13-19). Exemplarily, 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 can be controlled to be 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 any ratio within the range of (1-3): (13-19);

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

[0052] In the above embodiment, the first leaching agent and the second leaching agent are both concentrated sulfuric acid. In other embodiments, the first leaching agent and the second leaching agent may 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 embodiment, the nickel-cobalt-manganese-containing material is first mixed with the first leaching agent to obtain a first mixed slurry, and then an alkali is added to adjust the pH of the first mixed slurry to 1.5-3, and then a first solid-liquid separation is performed to obtain a first leachate and a first leaching residue; then the first leachate is decontaminated to obtain a salt solution containing nickel and cobalt, thereby realizing the recovery of nickel and cobalt, and at the same time, the first leaching residue is mixed with the second leaching agent to secondary leach the nickel and cobalt in the first leaching residue to obtain a second mixed solution; finally, the second mixed solution is decontaminated to obtain a solid substance containing manganese concentrate and a second filtrate, thereby realizing the recovery of manganese. In this method, the pH of the first mixed slurry is adjusted to 1.5-3 by alkali adjustment, which can reduce the amount of auxiliary carbonate used in the first impurity removal process of the first leaching solution, thereby reducing the nickel and cobalt taken away by the precipitation of auxiliary slag, improving the comprehensive recovery rate of nickel and cobalt, and reducing the filter pressing time of the first solid-liquid separation; moreover, the solid matter containing manganese concentrate obtained by the secondary leaching only needs to be washed to obtain the manganese concentrate directly sold, eliminating the subsequent fierce extraction process, reducing the extraction cost of manganese, and further improving the economic benefits. Therefore, the embodiment of the present application reduces the recovery cost of nickel, cobalt and manganese, and improves the economic benefits.

[0054] In an optional embodiment of the present application, the first leaching process comprises:

[0055] a slurrying step, 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 embodiment, 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; the slurry is then mixed with a first leaching agent to perform a first leaching treatment to obtain a first mixed slurry; wherein the solvent is produced water and / or a second filtrate obtained by a second impurity removal process, and 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 not only reduce the amount of leaching agent used, but also inhibit the leaching of manganese in the first leaching solution.

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

[0059] Ⅰ) The end point pH is 0-1;

[0060] Ⅱ) The first leaching temperature is 70-100°C;

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

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

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

[0064] Ⅱ) The second leaching temperature is 70-100°C;

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

[0066] In the above embodiment, such parameter settings ensure the leaching efficiency of the first stage leaching and the second stage leaching, and the high temperature and high acid of the second stage leaching can also selectively leach nickel and high-valent 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 the present application, in the second impurity removal step, 5 minutes 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 matter containing manganese concentrate and a second filtrate.

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

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

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

[0071] A washing step is to use a washing liquid to wash the solid matter of the manganese concentrate to obtain a manganese concentrate and a washed liquid, wherein the washed liquid is used to return to the second leaching step.

[0072] In the above embodiment, the solid matter containing manganese concentrate can be washed to obtain manganese concentrate that can be directly sold, which saves the subsequent fierce extraction process, reduces the extraction cost of manganese, and further improves the economic benefit; at the same time, the washed liquid is returned to the second leaching process for use, which can not only reduce the amount of the second leaching agent, but also can recycle the residual manganese concentrate in the washed liquid, thereby improving the comprehensive 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 more specifically describe the contents disclosed in the present application. These examples are only for illustrative purposes, because it is obvious to those skilled in the art to make various modifications and changes within the scope of the disclosure of the present application. Unless otherwise stated, all reagents and raw materials used in the examples are commercially available or synthesized according to conventional methods, and the instruments and equipment used in the examples are commercially available, wherein 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] The present invention provides a method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, comprising the following steps:

[0078] (1) 24m 3 The solvent and 20.7t of MHP raw material were mixed, the temperature was raised to 85°C, and slurry was performed for 30min at a stirring speed of 30Hz to obtain a slurry (wherein the solvent in this process is produced water and the second filtrate, the same below);

[0079] (2) slowly adding concentrated sulfuric acid to the slurry several times, controlling the pH value of the reaction slurry to 0.8-1, and reacting at 85° C. for 4 hours to obtain a first mixed slurry;

[0080] (3) 1.57 t of MHP raw material was added to the first mixed slurry to adjust the pH value of the solution to 2.5-3.0, and water was added to make the solution concentration 128.67 g / L, and then filter press was performed to obtain about 4616 kg of the first leaching residue and about 24 m of the first leaching liquid. 3 ;

[0081] (4) adding 150 kg of calcium powder / MNi solution to the first leaching solution and adjusting the solution pH to 5-5.5, reacting for 10 hours to precipitate iron and aluminum elements, and producing 500 kg / MNi (nickel element) iron slag and iron-removed liquid after filter pressing. After testing, the iron and aluminum contents in the iron-removed liquid are less than 1 ppm, and then the solution is subjected to an extraction process to obtain a sulfate solution containing nickel and cobalt;

[0082] (5) Mixing the first leaching residue, concentrated sulfuric acid and solvent, controlling the solution pH value to -0.4 to 0, and controlling the temperature to 85±5°C, the reaction time to 2h, to obtain a second mixed solution (wherein the solvent in this step is produced water and post-washing liquid);

[0083] (6) 8 kg of flocculant PAM was added 10 min before the end of the second leaching reaction, and then the second mixed solution was filtered. After 8 to 10 hours of filtering, about 1648 kg of solid matter containing manganese concentrate and about 15 m of second filtrate were obtained. 3 The obtained second filtrate is returned to the solvent cycle of step (1);

[0084] (7) The solid matter containing manganese concentrate was mixed with production water and washed several times to obtain about 1374 kg of manganese concentrate and about 25 m3 of washed liquid. 3 After washing, the liquid is returned to (5) for internal circulation.

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

[0086] Table 2 Detection and analysis results of each extract 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 mixed solution / 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 Leaching rate of metal A1 based on the first leaching residue % 82.29 68.92 46.26 88.88 95.57 Leaching rate of metal A2 in the second leaching residue % 90.56 84.22 8.58 95.08 99.97 Metal A3 leaching rate based on 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 slag leaching rate of the entire process, such as, total leaching rate % = (A1 + (1-A1 / 100) * A2 + (1-A1 / 100-(1-A1 / 100) * A2 / 100) * A3 / 100)%, wherein A1 = 1-Z1 / Y, and the results filled in the corresponding tables of the 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 input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material. For example, the total leaching rate of Ni (%) = (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, the temperature was raised to 85±5°C, and slurried for 30min at a stirring speed of 30Hz to obtain a slurry;

[0091] (2) slowly adding concentrated sulfuric acid to the slurry several times to control the pH value of the reaction slurry to 0.4-0.6, and heat-retaining the reaction at 85° C. for 4 hours to obtain a first mixed slurry;

[0092] (3) 1.4 t of MHP raw material was added to the first mixed slurry to adjust the pH value of the solution to 2-2.5, and water was added to make the solution concentration 125.62 g / L, and then filter press was performed to obtain about 4445 kg of the first leaching residue and about 24 m of the first leaching liquid. 3 ;

[0093] (4) adding 150 kg of calcium powder / MNi solution to the first leaching solution and adjusting the pH value of the solution to 5-5.5, reacting for 10 hours to precipitate iron and aluminum elements, and producing 500 kg / MNi of iron slag and iron-removed liquid after filter pressing. After testing, the iron and aluminum contents in the iron-removed liquid are less than 1 ppm, and then the solution is subjected to an extraction process to obtain a sulfate solution containing nickel and cobalt;

[0094] (5) mixing the first leaching residue, concentrated sulfuric acid and solvent, controlling the pH value of the solution to -0.6 to -0.4, and controlling the temperature to 85±5°C, and the reaction time to 2h to obtain a second mixed solution;

[0095] (6) 8 kg of flocculant PAM was added 10 min before the end of the second leaching reaction, and then the second mixed solution was filtered. After 8 to 10 hours of filtering, about 1587 kg of solid matter containing manganese concentrate and about 15 m of second filtrate were obtained. 3 The obtained second filtrate is returned to the solvent cycle of step (1);

[0096] (7) Washing process: The solid matter containing manganese concentrate is mixed with production water and washed several times to obtain about 1323 kg of manganese concentrate and about 25 m3 of washed liquid. 3 After washing, the liquid is returned to step (5) for circulation.

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

[0098] Table 3 Detection and analysis results of each extract 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 mixed solution / 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 Leaching rate of metal A1 in the first leaching residue % 84.02 73.10 47.24 93.39 97.87 Leaching rate of metal A2 in the second leaching residue % 93.95 90.94 9.58 92.94 99.98 Metal A3 leaching rate based on 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 slag leaching rate of the entire process, such as, total leaching rate % = (A1 + (1-A1 / 100) * A2 + (1-A1 / 100-(1-A1 / 100) * A2 / 100) * A3 / 100)%, wherein A1 = 1-Z1 / Y, and the results filled in the corresponding tables of the 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 input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material. For example, the total leaching rate of Ni (%) = (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 19.8 t of MHP raw material were mixed, the temperature was raised to 85°C, and slurried for 30 min at a stirring speed of 30 Hz to obtain a slurry;

[0103] (2) slowly adding concentrated sulfuric acid to the slurry several times, controlling the pH value of the reaction slurry to be 0-0.2, and reacting at 85° C. for 4 hours to obtain a first mixed slurry;

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

[0105] (4) adding 150 kg of calcium powder / MNi solution to the first leaching solution and adjusting the pH value of the solution to 5-5.5, reacting for 10 hours to precipitate iron and aluminum elements, and producing 500 kg / MNi of iron slag and iron-removed liquid after filter pressing. After testing, the iron and aluminum contents in the iron-removed liquid are less than 1 ppm, and then the solution is subjected to an extraction process to obtain a sulfate solution containing nickel and cobalt;

[0106] (5) mixing the first leaching residue, concentrated sulfuric acid and solvent, controlling the pH value of the solution to -0.1 to -0.6, and controlling the temperature to 85±5°C, and the reaction time to 2h to obtain a second mixed solution;

[0107] (6) 8 kg of flocculant PAM was added 10 min before the end of the second leaching reaction, and then the second mixed solution was filtered. After 8 to 10 hours of filtering, about 1571 kg of solid matter containing manganese concentrate and about 23.8 m of second filtrate were obtained. 3 The obtained second filtrate is returned to the solvent cycle of step (1);

[0108] (7) The solid matter containing manganese concentrate was mixed with production water and washed several times to obtain about 1310 kg of manganese concentrate and 24.8 m3 of washed liquid. 3 After washing, the liquid is returned to step (5) for circulation.

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

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

[0111]

[0112]

[0113] The leaching rate in Table 4 is the total slag leaching rate of the entire process, such as, total leaching rate % = (A1 + (1-A1 / 100) * A2 + (1-A1 / 100-(1-A1 / 100) * A2 / 100) * A3 / 100)%, wherein A1 = 1-Z1 / Y, and the results filled in the corresponding tables of the 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 input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material. For example, the total leaching rate of Ni (%) = (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 method is basically the same as Example 1, except that a reducing agent is added in step (2), and Comparative Example 1 does not have steps (5) and (7). The reducing agent is selected from one of hydrogen peroxide, sodium pyrosulfite, and sulfur dioxide. Comparative Example 1 takes the addition of sodium pyrosulfite as an example. The results are shown in Table 5.

[0116] Table 5 Detection and analysis results of each extract 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 Leaching rate of metal A1 in the first leaching residue % 97.40 95.82 88.89 98.10 97.99

[0118] The leaching rate in Table 5 is the total slag leaching rate of the entire process, such as, total leaching rate % = A1%, wherein 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 stage input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material.

[0119] From the comparison between Example 1 and Comparative Example 1, it can be seen that in Comparative Example 1, after the reducing agent is added to the reaction of step (2), the leaching rates of manganese and cobalt both reach more than 95%, and the slag rate of filter pressing 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 the introduction of sodium ions will have an adverse effect on subsequent extraction and crystallization. In contrast, in the direct leaching adopted in Example 1, the nickel and cobalt leaching rate after step (2) can reach more than 80%, and then through the selective leaching of the high acid step (5), the total leaching rate of nickel also reaches more than 99%, and the second filtrate in step (5) can be returned to step (2) for recycling, saving the cost of auxiliary material consumption. In addition, due to the selective leaching of step (5), the total leaching rate of manganese is less than 55%, thereby saving the acid and alkali consumption cost of extracting manganese.

[0120] Comparative Example 2

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

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

[0123] Serial number Ni Co Mn Na Fe First leachate / concentration g / L 124.12 8.51 2.82 5.86 0.71 Second mixed solution / 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 Leaching rate of metal A1 based on the first leaching residue % 83.52 51.91 6.67 76.70 86.81 Leaching rate of metal A2 in the second leaching residue % 88.54 85.93 1.78 99.93 96.91 Metal A3 leaching rate based on 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 slag leaching rate of the entire process, such as, total leaching rate % = (A1 + (1-A1 / 100) * A2 + (1-A1 / 100-(1-A1 / 100) * A2 / 100) * A3 / 100)%, wherein A1 = 1-Z1 / Y, and the results filled in the corresponding tables of the 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 input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material. For example, the total leaching rate of Ni (%) = (83.52 + (1-83.52 / 100) * 88.54) + (1-0.8352-(1-83.52 / 100) * 88.54 / 100) * 93.58 / 100)% = 98.13%.

[0125] From the comparison between Example 2 and Comparative Example 2, it can be seen that after adding the oxidant, the leaching rate of manganese is reduced from 50% to less than 10%. Although the cost of extracting manganese is saved, the filtration speed of step (5) is slowed down, the overall filter residue increases, resulting in increased nickel and cobalt losses in the filter residue, and the cost of the oxidant is increased. At the same time, sodium ions are introduced, which increases the difficulty of extracting and crystallizing sodium. Therefore, the direct leaching process adopted in Example 2 is simpler and has lower cost, and can also save part of the manganese extraction cost, which is more suitable for actual production.

[0126] Comparative Example 3

[0127] The method is basically the same as Example 3, except that in step (3), no MHP raw material is added 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 The produced water and 20.1 t of MHP raw material were mixed, heated to 85°C, and slurried for 30 min at a stirring speed of 30 Hz to obtain a slurry;

[0129] (2) adding concentrated sulfuric acid to the obtained slurry, controlling the pH value of the slurry to 0-1, and keeping the temperature at 85° C. for 4 h, adding water to make the solution concentration reach 125.89 g / L, and then filtering by pressure to obtain a first leachate and a first leach residue;

[0130] (3) The first leaching solution was taken and 300 kg of calcium powder / MNi solution was added to adjust the solution pH to 5-5.5. The solution was reacted for about 24 hours to precipitate elements such as iron and aluminum. After pressure filtration, 700 kg / MNi of iron slag and iron-removing liquid were produced. The solution was tested and the iron and aluminum contents in the iron-removing liquid were less than 1 ppm. The test results are shown in Table 7. Then, an extraction process was performed to obtain a sulfate solution containing nickel and cobalt.

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

[0132] Serial number Ni Co Mn Na Fe First leachate / concentration g / L 125.89 8.56 11.34 0.27 0.92 Leaching rate of metal A1 based on the first leaching residue % 84.36 71.60 46.52 93.73 95.29

[0133] The leaching rate in Table 7 is the total slag leaching rate of the entire process, such as, total leaching rate % = A1%, wherein 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 input material + the content of nickel, cobalt, manganese, sodium and iron in the callback material.

[0134] From the comparison between Example 3 and Comparative Example 3, it can be seen that the first-stage nickel leaching rate in Example 3 is 84%. After the pH value is adjusted by MHP raw material, iron removal is carried out. The amount of calcium powder used is only 150 kg calcium powder / MNi, and the reaction 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 is a detailed introduction to a method for recovering nickel, cobalt and manganese from nickel-cobalt-manganese-containing materials provided by the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application, and the description of the above embodiments is only used to help understand the core idea of ​​the present application. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present application, several improvements and modifications can be made to the present application, and these improvements and modifications also fall within the scope of protection of the claims of the present application.

Claims

1. A method for recovering nickel, cobalt and manganese from a material containing nickel, cobalt and manganese, characterized in that: The method comprises the following steps: a first leaching step, mixing the nickel-cobalt-manganese containing material with a first leaching agent and performing a first leaching treatment to obtain a first mixed slurry; A pH adjustment step of adding alkali to the first mixed slurry to adjust the pH of the first mixed slurry to 1.5-3 to obtain a first mixed solution; first solid-liquid separation, subjecting the first mixed solution to a first solid-liquid separation treatment to obtain a first leaching solution and a first leaching residue containing nickel and cobalt; a first impurity removal step of performing a first impurity removal treatment on the first leaching solution to obtain a salt solution containing nickel and cobalt; a second leaching step, mixing the first leaching residue with a second leaching agent to leach nickel and cobalt in the first leaching residue to obtain a second mixed solution; The second impurity removal step is to perform a second impurity removal treatment on the second mixed liquid to obtain a solid matter containing manganese concentrate and a second filtrate.

2. The method according to claim 1, characterized in that The first leaching step comprises: a slurrying step, 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 end point pH is 0-1; Ⅱ) The first leaching temperature is 70-100°C; III) The first leaching time is 1h to 8h.

4. The method according to claim 1, characterized in that: The nickel-cobalt-manganese-containing material comprises a mixture of nickel-cobalt hydroxide.

5. The method according to claim 4, characterized in that The base includes at least one of nickel hydroxide, cobalt hydroxide, or a mixture thereof.

6. The method according to claim 4, 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).

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

8. The method according to claim 7, characterized in that In the second impurity removal step, 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 matter containing manganese concentrate and a second filtrate.

9. The method according to claim 7, characterized in that: The added amount of the flocculant is 1% to 10% of the mass of the second mixed liquid.

10. The method according to claim 1, characterized in that The method further comprises: A washing step is to use a washing liquid to wash the solid matter of the manganese concentrate to obtain a manganese concentrate and a washed liquid, wherein the washed liquid is used to return to the second leaching step.

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