CN109735709B - Method for recycling lithium from calcium and magnesium removing slag and preparing ternary precursor material - Google Patents
Method for recycling lithium from calcium and magnesium removing slag and preparing ternary precursor material Download PDFInfo
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- CN109735709B CN109735709B CN201811527887.4A CN201811527887A CN109735709B CN 109735709 B CN109735709 B CN 109735709B CN 201811527887 A CN201811527887 A CN 201811527887A CN 109735709 B CN109735709 B CN 109735709B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for recovering lithium and preparing a ternary precursor material by calcium and magnesium removal slag, belonging to the field of wet recovery of waste lithium ion batteries and comprising the following steps of: (1) magnesium salt transformation, (2) cobalt nickel manganese precipitation, (3) alkalization magnesium removal, (4) lithium carbonate preparation, (5) acid leaching of nickel cobalt manganese slag, (6) calcium magnesium removal, (7) extraction, (8) precursor synthesis, and (9) drying to prepare a ternary precursor material; the method has the advantages of simple process, low energy consumption, safety and stability, high separation efficiency of cobalt, nickel, manganese and lithium in the process, and high comprehensive recovery rate of each valuable metal, the main content of the lithium carbonate prepared by the method is up to 99.61 percent, the requirement of a battery level is met, the total recovery rate of nickel, cobalt, manganese and lithium in the calcium and magnesium removal slag is up to 98.5 percent, the recovery rate of lithium is up to 98.8 percent, the method is easy for industrial production, and has high economic benefit.
Description
Technical Field
The invention relates to the field of wet recovery of waste lithium batteries, in particular to a method for recovering lithium by removing calcium and magnesium residues and preparing a ternary precursor material.
Background
Lithium batteries are widely used in digital products such as mobile phones, computers, cameras, etc. because of their advantages of high energy density, high open circuit voltage, fast charge and discharge speed, long service life, etc. With the vigorous development of new energy automobile industry in China, in recent years, the lithium battery industry has explosive growth. According to GGII research data, the output of the Chinese power battery in 2017 is 44.5 GWH, which accounts for more than 50% of the total amount of the whole world, and Chinese becomes the largest lithium battery production and consumption market in the world.
After nearly thousands of charge-discharge cycles, the internal working ions of the lithium battery gradually lose activity. The increasingly widespread use of lithium batteries is bound to produce a large number of waste batteries. If the lithium ion battery is discarded at will, the environment is threatened, and metal resources are wasted, so that the lithium ion battery has very important significance for recycling of waste lithium batteries.
The waste lithium battery recovery process comprises front-end pretreatment and rear-end chemical recovery. At present, the chemical recovery of the rear end of the waste lithium battery is mainly based on a wet method. Taking a ternary material battery as an example, the wet recovery process is widely adopted: the technological process of reduction acid leaching, purification and impurity removal and extraction separation. In the purification and impurity removal process, the key point is to remove calcium and magnesium impurities in the leachate. Patent CN106505225A is a method for removing calcium and magnesium in the form of refractory calcium fluoride and magnesium fluoride by adding soluble fluoride salt. However, because the fluorides of cobalt, nickel, manganese and lithium belong to slightly soluble substances, a great amount of nickel, cobalt and manganese metal is precipitated in the form of fluorides while calcium and magnesium are removed. The calcium-removed magnesium slag contains a large amount of valuable metals such as nickel, cobalt, manganese, lithium and the like, and only relates to the recovery of lithium, so that the recovery rate of the valuable metals is greatly reduced. According to the invention, the lithium is recycled to prepare the lithium carbonate, and the valuable metals of nickel, cobalt and manganese are further recycled to prepare the ternary precursor material, so that the comprehensive utilization of resources is realized, the recovery rate of nickel, cobalt and manganese is more than 98%, and the recovery rate of lithium is more than 96%.
Disclosure of Invention
In order to solve the existing problems, the invention discloses a method for recovering lithium from calcium-magnesium-removing slag and preparing a ternary precursor material, which comprises the following steps:
(1) converting magnesium salt, namely preparing the calcium-magnesium-removed slag and magnesium salt with the magnesium ion concentration of 30-100g/L into slurry, adding inorganic acid, adjusting the pH of the system to 1.0-5.0, heating and stirring for 1-5h, and filtering to obtain a conversion liquid and calcium magnesium fluoride slag;
(2) precipitating cobalt, nickel and manganese, adding a precipitator into the transformation liquid in the step (1), controlling the system temperature to be 25-100 ℃, and separating the cobalt, nickel and manganese in the transformation liquid from lithium and magnesium in a nickel-cobalt-manganese hydroxide precipitation form to obtain nickel-cobalt-manganese slag and crude lithium liquid;
(3) acid leaching the nickel-cobalt-manganese slag, namely mixing the nickel-cobalt-manganese slag obtained in the step (2) with tap water to obtain slurry, wherein the liquid-solid mass ratio is controlled to be 2-5: 1, preparing slurry, adding inorganic acid into the slurry, adjusting the pH to 0-5, stirring and reacting for 0.5-1h to obtain pickle liquor and pickle residue;
(4) removing calcium and magnesium: adding soluble fluoride salt into the pickle liquor obtained in the step (3), controlling the system temperature to be 50-100 ℃, stirring for reaction for 0.5-2h, and filtering to obtain calcium-magnesium-removed liquor and calcium-magnesium-removed slag;
(5) and (3) extraction: extracting metal cobalt, nickel and manganese in the calcium-magnesium-removed solution by using an organic extractant, and performing back extraction to obtain a back extraction solution containing cobalt, nickel and manganese;
(6) synthesizing a precursor: adding cobalt, nickel and manganese soluble salt into the back extraction solution obtained in the step (5), adding sodium hydroxide and ammonia water, controlling the pH value of the system to 9-12, keeping the reaction temperature at 60-70 ℃, and stirring for 1-5 hours to obtain spherical nickel, cobalt and manganese hydroxide;
(7) drying: and (6) drying the spherical nickel, cobalt and manganese hydroxide at the high temperature of 100 ℃ and 500 ℃ for 2-5h to obtain the ternary precursor material.
According to the scheme, the mass percentages of cobalt, nickel, manganese and lithium in the calcium-removing magnesium slag in the step (1) are respectively 1-10%.
The preferable scheme of the invention comprises at least one of the following technical characteristics:
the liquid-solid mass ratio of the calcium-magnesium-removing slag to the magnesium salt pulping is 2-5: 1;
the heating and stirring temperature is 50-100 ℃;
the stirring speed of the heating stirring is as follows: 100-;
the magnesium salt is at least one of magnesium sulfate, magnesium nitrate and magnesium chloride;
the addition amount of the magnesium salt is 1.1-2.0 times of the theoretical mass required by the calculation of a chemical reaction equation by converting all cobalt, nickel, manganese and lithium in the calcium fluoride magnesium slag into soluble salt.
In a preferable embodiment of the present invention, in the step (2), the precipitant is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the addition amount of the precipitant is 1.0-2.0 times of the theoretical mass required by the calculation of the chemical reaction equation by converting all cobalt, nickel and manganese in the transformation liquid into hydroxide.
In a preferred embodiment of the present invention, the inorganic acid in steps (1) and (3) is at least one of sulfuric acid, nitric acid, and hydrochloric acid.
As a preferable scheme of the invention, the step (4) comprises at least one of the following technical characteristics:
the soluble fluoride salt is at least one of sodium fluoride and ammonium fluoride;
controlling the pH value of the reaction system to be 0-5;
the stirring rate was 100 and 400 rps.
In a preferred embodiment of the present invention, the pH of the calcium-magnesium removing solution in step (5) is 3.0-6.0, the organic extractant is an organic mixture of P507 and sulfonated kerosene, and the volume ratio of the organic extractant is 1:1-5, and the saponification degree is 40-70%.
As a preferable scheme of the invention, in the step (6), the required cobalt nickel manganese sulfate is added according to the molar ratio of nickel, cobalt and manganese of 8:1:1 or 6:2:2 or 5:2:3 to prepare a ternary precursor material, wherein the ternary precursor material is Ni0.8Co0.1Mn0.1(OH)2Type, or Ni0.6Co0.2Mn0.2(OH)2Type or Ni0.5Co0.2Mn0.3(OH)2And (4) molding.
As a preferable scheme of the invention, the method further comprises the following steps:
s1: alkalizing to remove magnesium, adding an alkaline agent into the crude lithium liquid obtained in the step (2), adjusting the pH value of the solution to 10.0-13.0, and filtering to obtain refined lithium liquid and magnesium hydroxide slag;
s2: and preparing lithium carbonate, adding a sodium carbonate solution into the refined lithium solution in the step S1 to precipitate lithium in the form of lithium carbonate, and washing and drying to obtain the battery-grade lithium carbonate.
In a preferred embodiment of the present invention, in step S1, the basic agent is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia water.
The working principle is that the reaction equation involved in the step (1) is as follows:
CoF2+Mg2+→MgF2↓+Co2+；
NiF2+Mg2+→MgF2↓+Ni2+；
MnF2+Mg2+→MgF2↓+Mn2+；
LiF+Mg2+→MgF2↓+Li+
the reaction equation involved in the step (2) is:
2OH-+Co2+=Co(OH)2↓；
2OH-+Ni2+=Ni(OH)2↓
2OH-+Mn2+=Mn(OH)2↓
the reaction equation involved in the step (3) is:
Mn(OH)2+2H2+=Mn2++2H2O
Co(OH)2+2H2+=Co2++2H2O
Ni (OH)2+2H2+=Ni2++2H2O
the reaction equation involved in the step (4) is:
Mg2++2F- =MgF2↓
Ca2++2F- =CaF2↓
the reaction equation involved in the step (6) is:
Co2++OH-=Co(OH)2↓
Ni2++OH-=Ni(OH)2↓
Mn2++OH-=Mn(OH)2↓
the reaction equation involved in step S1 is:
2OH-+Mg2+=Mg(OH)2↓
the reaction equation involved in step S2 is:
2Li++CO3 2-=Li2CO3↓
the invention has the beneficial effects that:
(1) the invention takes the calcium and magnesium removing slag of the leachate of the waste lithium battery as a recycling object, firstly carries out magnesium salt transformation on the calcium and magnesium removing slag to obtain a nickel-cobalt-manganese-lithium solution, carries out nickel-cobalt-manganese precipitation, acid leaching, calcium and magnesium removing, extraction, obtains spherical nickel-cobalt-manganese hydroxide through a synthesis reaction, and dries to prepare the ternary precursor material with the corresponding molar ratio of nickel, cobalt and manganese. And successively adding basic agent into the crude lithium liquid after nickel, cobalt and manganese are precipitated to separate lithium and magnesium in the crude lithium liquid, and preparing battery-grade lithium carbonate from the refined lithium liquid after alkalization.
(2) The method has the advantages of simple process, low energy consumption, safety and stability, high separation efficiency of cobalt, nickel, manganese and lithium in the process, low content of nickel and cobalt in the crude lithium liquid below 100ppm, low content of lithium in the nickel, cobalt and manganese slag below 0.1 percent, high comprehensive recovery rate of each valuable metal and high yield of nickel, cobalt and manganese of more than 95 percent; the lithium conversion yield was 95% or more. The purity of the prepared lithium carbonate is as high as 99.61%, the quality is good, and the lithium carbonate can reach the standard of battery-grade lithium carbonate.
(3) The traditional method for recovering lithium from lithium fluoride and calcium and magnesium removal slag does not involve the recovery of nickel and cobalt of valuable metals, and the method is characterized in that a nickel and cobalt precipitation process is introduced, so that the separation of nickel, cobalt and lithium is realized, the comprehensive recovery and utilization of resources are achieved, and the recovery rate of the valuable metals is up to more than 95%.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The method for recovering lithium and preparing the ternary precursor material by removing calcium and magnesium slag in the invention is further described in detail with reference to fig. 1 of the accompanying drawings.
A method for recovering lithium and preparing a ternary precursor material by removing calcium and magnesium slag is disclosed, and referring to figure 1, the process flow is as follows:
(1) converting magnesium salt, namely preparing the calcium-magnesium-removed slag and magnesium salt with the magnesium ion concentration of 30-100g/L into slurry, adding inorganic acid, adjusting the pH of the system to 1.0-5.0, heating and stirring for 1-5h, and filtering to obtain a conversion liquid and calcium magnesium fluoride slag;
the liquid-solid mass ratio of the calcium-magnesium-removing slag to the magnesium salt pulping is 2-5: 1;
the heating and stirring temperature is 50-100 ℃;
the stirring speed of the heating stirring is as follows: 100-;
the magnesium salt is at least one of magnesium sulfate, magnesium nitrate and magnesium chloride;
the addition amount of the magnesium salt is 1.1-2.0 times of the theoretical mass required by the calculation of a chemical reaction equation by converting all cobalt, nickel, manganese and lithium in the calcium fluoride magnesium slag into soluble salt.
(2) And (2) precipitating cobalt, nickel and manganese, adding a precipitator into the transformation liquid in the step (1), controlling the system temperature to be 25-100 ℃, and separating the cobalt, nickel and manganese in the transformation liquid from lithium and magnesium in a nickel-cobalt-manganese hydroxide precipitation mode to obtain nickel-cobalt-manganese slag and crude lithium liquid.
The precipitator is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the addition amount of the precipitant is 1.0-2.0 times of the theoretical mass required by the calculation of the chemical reaction equation by converting all cobalt, nickel and manganese in the transformation liquid into hydroxide.
(3) Acid leaching the nickel-cobalt-manganese slag, namely mixing the nickel-cobalt-manganese slag obtained in the step (2) with tap water to obtain slurry, wherein the liquid-solid mass ratio is controlled to be 2-5: 1, preparing slurry, adding inorganic acid into the slurry, adjusting the pH to 0-5, stirring and reacting for 0.5-1h to obtain pickle liquor and pickle residue;
(4) removing calcium and magnesium: adding soluble fluoride salt into the pickle liquor obtained in the step (3), controlling the temperature of the system to be 50-100 ℃ and the pH value of the system to be 0-5, stirring for reaction for 0.5-2h, and filtering to obtain calcium and magnesium removal liquid and calcium and magnesium removal slag;
the soluble fluoride salt is at least one of sodium fluoride and ammonium fluoride;
the stirring rate was 100 and 400 rps.
(5) And (3) extraction: extracting metal cobalt, nickel and manganese in the calcium-magnesium-removed solution by using an organic extractant, and performing back extraction to obtain a back extraction solution containing cobalt, nickel and manganese; the pH value of the calcium-magnesium removing liquid in the step is 3.0-6.0, the organic extracting agent is an organic mixture of P507 and sulfonated kerosene, and the volume ratio of the organic extracting agent to the sulfonated kerosene is 1:1-5, and the saponification degree is 40-70%.
(6) Synthesizing a precursor: adding cobalt, nickel and manganese soluble salt into the back extraction solution obtained in the step (5), adding sodium hydroxide and ammonia water, controlling the pH value of the system to 9-12, keeping the reaction temperature at 60-70 ℃, and stirring for 1-5 hours to obtain spherical nickel, cobalt and manganese hydroxide;
(7) drying: and (6) drying the spherical nickel, cobalt and manganese hydroxide at the high temperature of 100 ℃ and 500 ℃ for 2-5h to obtain the ternary precursor material.
According to the scheme, the mass percentages of cobalt, nickel, manganese and lithium in the calcium-removing magnesium slag in the step (1) are respectively 1-10%.
The inorganic acid in the steps (1) and (3) is at least one of sulfuric acid, nitric acid and hydrochloric acid.
As a preferable scheme of the invention, in the step (6), the required cobalt nickel manganese sulfate is added according to the molar ratio of nickel, cobalt and manganese of 8:1:1 or 6:2:2 or 5:2:3 to prepare a ternary precursor material, wherein the ternary precursor material is Ni0.8Co0.1Mn0.1(OH)2Type or Ni0.6Co0.2Mn0.2(OH)2Type or Ni0.5Co0.2Mn0.3(OH)2And (4) molding.
As a preferable scheme of the invention, the method further comprises the following steps:
s1: alkalizing to remove magnesium, adding an alkaline agent into the crude lithium liquid obtained in the step (2), adjusting the pH value of the solution to 10.0-13.0, and filtering to obtain refined lithium liquid and magnesium hydroxide slag;
s2: and preparing lithium carbonate, adding a sodium carbonate solution into the refined lithium solution in the step S1 to precipitate lithium in the form of lithium carbonate, and washing and drying to obtain the battery-grade lithium carbonate.
In a preferred embodiment of the present invention, in step S1, the basic agent is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia water.
Example 1
(1) Magnesium salt transformation: taking 200kg of calcium-magnesium-removed slag and a magnesium chloride solution with the magnesium ion concentration of 77 g/L at 0.54m to prepare slurry, wherein the addition amount of magnesium salt is 1.1 times of the theoretical use amount required by leaching all cobalt, nickel, manganese and lithium in the calcium-magnesium slag, and then adjusting the pH value of the system to 3.0 by using 20L of hydrochloric acid. Heating, stirring at 95 deg.C for 1 hr, filtering, and stirring at 200rps to obtain 0.52m transformation liquid. The analysis results of the main components of the transformation liquid are shown in Table 1 below:
TABLE 1 analysis results of main components of transformation liquid
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 12.80 | 29.03 | 15.06 | 28.5 | 3.2 | 13 | 0.001 | 0.002 |
(2) Depositing nickel, cobalt and manganese: and (3) carrying out dry distillation on the obtained transformation liquid at 0.52m, wherein all cobalt, nickel and manganese in the transformation liquid are converted into nickel, cobalt and manganese hydroxide, and 45kg of sodium hydroxide is added according to the formula of the chemical reaction, wherein the amount of the sodium hydroxide is 1.1 times of the theoretical mass required by calculation, so that the cobalt, nickel and manganese are separated from lithium and magnesium in the form of hydroxide. And performing replacement stirring for 0.5h, and filtering to obtain 0.46 m coarse lithium liquid and 130kg nickel cobalt manganese slag. The analysis results of the main components of the crude lithium solution are shown in Table 2 below:
TABLE 2 analysis results of main components of crude lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.01 | 0.05 | 0.08 | 32.19 | 2.9 | 13.2 | 0.001 | 0.002 |
(3) Acid leaching: 130kg of the nickel cobalt manganese slag precipitated in the step (2) and 0.4m of the nickel cobalt manganese slag are added into a reaction kettle3Was made into a slurry, and the pH of the slurry was adjusted to 1.0 with 51kg of concentrated hydrochloric acid. Stirring for 0.5h and filtering to obtain 0.42 m3And (4) acid leaching solution.
(4) Removing calcium and magnesium: adding 17.8kg of sodium fluoride into the pickle liquor obtained in the step (3), and controllingStirring the system at 90 ℃ for 2h, reacting, and filtering, wherein the stirring speed is 300rps, and the obtained product is 0.4m3Calcium and magnesium removing liquid. The calcium content in the calcium-removing magnesium liquid is 0.0002g/L and the magnesium content is 0.0005 g/L.
(5) And (3) extraction: and (3) adjusting the pH value of the calcium-magnesium removing solution in the step (4) to 3.0, carrying out 8-stage countercurrent extraction on the organic extractant with the saponification degree of 65% in P507/sulfonated kerosene (volume ratio of 1:3) and carrying out 5-stage back extraction to obtain a back extract liquid for carrying out thin film epitaxy at 0.32m, wherein the results of the components are shown in Table 4.
TABLE 4 analysis results of major components in the stripping solution
| Element(s) | Co | Ni | Mn | Ca | Mg | Fe | Al |
| content/(g/L) | 20.38 | 45.99 | 23.49 | 0.001 | 0.0015 | Not detected out | 0.0002 |
(6) Synthesizing a precursor: the designed molar ratio of nickel, cobalt and manganese is 5:2: 3. Adding nickel sulfate and manganese sulfate into the strip liquor obtained in the step (7). Adding sodium hydroxide and ammonia water into a reaction kettle, controlling the pH value of the system to 11.5, keeping the reaction temperature at 65 ℃, and stirring for 4 hours to obtain the spherical nickel cobalt manganese hydroxide.
(7) Drying: drying the spherical nickel cobalt manganese hydroxide prepared by the embodiment at a high temperature of 150 ℃ for 5 hours to obtain Ni0.5Co0.2Mn0.3(OH)251.02Kg of type ternary precursor, and the total recovery rate of nickel, cobalt and manganese from the recovery to the finished product is 97 percent. Wherein the recovery rate of cobalt is as follows: 98.0 percent; the recovery rate of nickel is as follows: 97.5 percent; the recovery rate of manganese is as follows: 96.0 percent.
Example 2
The embodiment is further optimized on the basis of embodiment 1, and specifically comprises the following steps:
s1: alkalization and magnesium removal: and (3) adding 32wt% sodium hydroxide solution to the crude lithium liquid obtained from step (2) under 0.46 m, and adjusting the pH value to 12.0. Stirring for 1h, and filtering to obtain refined lithium liquid at 0.52 m. The analysis results of the main components of the refined lithium liquid are shown in Table 3 below:
TABLE 3 analysis results of main components of refined lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.0001 | Not detected out | 0.0005 | 28.47 | 0.12 | 0.0001 | 0.0005 | 0.0002 |
S2: preparing lithium carbonate: and (3) heating the refined lithium liquid to 95 ℃, then slowly adding 300g/L sodium carbonate solution for 0.37 m to carry out flowering, stirring for 0.5h, and filtering at the stirring speed of 250 rps. And washing and drying the filter residue to obtain 75.77kg of lithium carbonate product. The technical indexes of the lithium carbonate product in the embodiment are shown in tables 13 and 14.
Example 3
(1) Magnesium salt transformation: taking 200kg of calcium-magnesium-removed slag and a magnesium sulfate solution with the magnesium ion concentration of 61 g/L at 0.6m to prepare slurry, wherein the addition amount of magnesium salt is 1.2 times of the theoretical amount required by leaching all cobalt, nickel, manganese and lithium in the calcium-magnesium slag, and then adjusting the pH value of the system to 1.0 by using 20L of concentrated sulfuric acid. Heating, stirring at 95 deg.C for 1 hr, filtering, and stirring at 200rps to obtain transformation liquid of 0.63 m. The analysis results of the main components of the transformation liquid are shown in Table 5 below:
TABLE 5 analysis results of main components of transformation liquid
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 6.3 | 14.6 | 3.2 | 22.1 | 1.1 | 8.5 | 0.002 | 0.001 |
(2) And (3) cobalt, nickel and manganese precipitation: and (3) carrying out heavy planting according to 0.63 m in the step (1), wherein all cobalt, nickel and manganese in the transformation liquid are transformed into nickel, cobalt and manganese hydroxide, and 23kg of sodium hydroxide is added according to the chemical reaction equation, wherein the amount of the sodium hydroxide is 1.1 times of the theoretical amount of the nickel, cobalt and manganese, so that the cobalt, nickel and manganese are separated from lithium and magnesium in the form of hydroxide. And performing replacement stirring for 0.5h, and filtering to obtain 0.59m coarse lithium liquid and 80kg nickel cobalt manganese slag. The analysis results of the main components of the crude lithium-transformed liquid are shown in Table 6 below:
TABLE 6 analysis results of main components of crude lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.02 | 0.02 | 0.44 | 23.13 | 1.05 | 16.38 | 0.001 | 0.002 |
(3) Acid leaching: adding 80kg of the nickel, cobalt and manganese slag precipitated in the step (2) into a reaction kettle0.3m3The tap water was made into a slurry, and the pH of the slurry was adjusted to 2.0 with 25kg of concentrated sulfuric acid. Stirring for 0.5h, filtering, stirring at 250 rps to obtain 0.35m3And (4) acid leaching solution.
(4) Removing calcium and magnesium: adding 5.6kg of sodium fluoride into the pickle liquor obtained in the step (3), controlling the temperature of the system at 90 ℃, stirring for reaction for 2h, and filtering, wherein the stirring speed is 300rps, so as to obtain 0.32m3Removing calcium and magnesium. The determination shows that the calcium content in the calcium-magnesium-removed liquid is 0.0003g/L, and the magnesium content is 0.0004 g/L.
(5) And (3) extraction: and (3) adjusting the pH value of the solution obtained in the step (4) after calcium and magnesium removal to 3.0, carrying out 8-stage countercurrent extraction on the organic extractant with the saponification degree of 65% in P507/sulfonated kerosene (volume ratio of 1:3) and carrying out 5-stage back extraction to obtain a back extract liquid, and carrying out thin film chromatography and thin film chromatography on the back extract liquid at 0.28 m, wherein the results of the components are shown in Table 8.
TABLE 8 analysis results of major components in the stripping solution
| Element(s) | Co | Ni | Mn | Ca | Mg | Fe | Al |
| content/(g/L) | 13.78 | 31.47 | 6.98 | 0.001 | 0.0015 | Not detected out | 0.0002 |
(6) Synthesizing a precursor: the designed molar ratio of nickel, cobalt and manganese is 8:1: 1. And (4) adding nickel sulfate and manganese sulfate into the strip liquor obtained in the step (6). Adding sodium hydroxide and ammonia water into a reaction kettle, controlling the pH value of the system to 11.5, keeping the reaction temperature at 65 ℃, and stirring for 4 hours at the stirring speed of 150rps to obtain the spherical nickel-cobalt-manganese hydroxide.
(7) Drying: the spherical nickel cobalt manganese hydroxide prepared by the embodiment is dried for 5 hours at a high temperature of 150 ℃ to obtain 60.26Kg of 5:3:2 type ternary precursor, and the total recovery rate of the nickel cobalt manganese from the recovery to the finished product is 97%. Wherein the recovery rate of cobalt is as follows: 97.2 percent; the recovery rate of nickel is as follows: 95.8 percent; the recovery rate of manganese is as follows: 97.0 percent.
Example 4
The embodiment is further optimized on the basis of embodiment 3, and specifically includes:
s1: alkalization and magnesium removal: and (3) adding a 32% sodium hydroxide solution obtained by carrying out labor Strength reduction on the crude lithium liquid obtained by carrying out labor Strength reduction on the fruit powder at 0.59m in the step (2), and adjusting the pH value of the solution to 12.0. Stirring for 1h, filtering, and carrying out high speed 200rps to obtain the refined lithium liquid obtained by carrying out high speed flash distillation on the seeds at 0.56 m. The analysis results of the main components of the crude lithium-transformed liquid are shown in Table 7 below:
TABLE 7 analysis results of main components of refined lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.0004 | 0.0001 | 0.0008 | 23.88 | 0.08 | 0.0001 | 0.0004 | 0.0003 |
S2: preparing lithium carbonate: and heating the qualified lithium liquid to 90 ℃, then slowly adding 220g/L sodium carbonate solution for 0.46 m and carrying out heavy planting, stirring for 0.5h and filtering, wherein the stirring speed is 200rps, and washing and drying filter residues to obtain 71.29kg of lithium carbonate product. The technical indexes of the lithium carbonate product in the embodiment are shown in tables 13 and 14.
Example 5
(1) Magnesium salt transformation: taking 200kg of calcium-magnesium-removed slag and 82.12 g/L magnesium nitrate solution with magnesium ion concentration of 0.5m to prepare slurry, wherein the addition amount of magnesium salt is 1.2 times of the theoretical amount required by leaching all cobalt, nickel, manganese and lithium in the calcium-magnesium slag, and then adjusting the pH value of the system to 4.0 by using 15L of concentrated sulfuric acid. Heating, stirring at 85 deg.C for 1 hr, and filtering to obtain a transformation liquid of 0.54m with stirring speed of 400 rps. The analysis results of the main components of the transformation liquid are shown in Table 9 below:
TABLE 9 analysis results of main components of transformation liquid
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 11.2 | 21.03 | 9.63 | 26.6 | 0.75 | 12.03 | 0.004 | 0.003 |
(2) And (3) cobalt, nickel and manganese precipitation: and (2) carrying out heavy harvest according to 0.54m in the step (1) to convert all cobalt, nickel and manganese in the transformation liquid into nickel, cobalt and manganese hydroxide, and adding 45.95kg of potassium hydroxide which is 1.05 times of the theoretical dosage calculated according to the chemical reaction equation so as to separate the cobalt, nickel and manganese from lithium and magnesium in the form of hydroxide. Stirring at 25 deg.C for 0.5h, filtering, and stirring at 350rps to obtain 0.52m coarse Li solution and 115kg Ni-Co-Mn residue. The analysis results of the main components of the crude lithium solution are shown in Table 10 below:
TABLE 10 analysis results of main components of crude lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | 0.08 | 0.07 | 0.21 | 27.07 | 0.56 | 14.08 | 0.003 | 0.002 |
(3) Acid leaching: adding 115kg of nickel cobalt manganese slag precipitated in the step (2) and 0.4m into a reaction kettle3Was slurried with 18kg nitric acid to adjust the pH of the slurry to 1.5. Stirring for 0.5h, filtering, stirring at 200rps to obtain 0.43 m3And (4) acid leaching solution.
(4) Removing calcium and magnesium: adding 7.8kg of sodium fluoride into the pickle liquor obtained in the step (3), controlling the temperature of the system to be 85 ℃, stirring for reaction for 2h, and filtering, wherein the stirring speed is 200rps, so as to obtain 0.41m3Removing calcium and magnesium. The determination shows that the calcium content in the calcium-magnesium-removed liquid is 0.0002g/L, and the magnesium content is 0.0001 g/L.
(5) And (3) extraction: and (3) adjusting the pH value of the solution obtained in the step (4) after calcium and magnesium removal to 4.0, carrying out 8-stage countercurrent extraction on the organic extractant with the saponification degree of 70% in P507/sulfonated kerosene (volume ratio of 1:3) and carrying out 5-stage back extraction to obtain a back extract liquid, and carrying out thin film chromatography on the back extract liquid to obtain the thin film chromatography-mass spectrometry-based material for the dry mass spectrometry of 0.22 m, wherein the results of all.
TABLE 12 analysis results of major components in the stripping solution
| Element(s) | Co | Ni | Mn | Ca | Mg | Fe | Al |
| content/(g/L) | 27.08 | 50.99 | 23.14 | 0.002 | 0.002 | Not detected out | 0.0004 |
(6) Synthesizing a precursor: the designed molar ratio of nickel, cobalt and manganese is 6:2: 2. And (4) adding nickel sulfate and manganese sulfate into the strip liquor obtained in the step (6). Adding sodium hydroxide and ammonia water into a reaction kettle, controlling the pH value of the system to 11.0, keeping the reaction temperature at 70 ℃, and stirring for 4 hours at the stirring speed of 200rps to obtain the spherical nickel-cobalt-manganese hydroxide.
(7) Drying: the spherical nickel cobalt manganese hydroxide prepared by the embodiment is dried for 5 hours at the high temperature of 150 ℃ to obtain 46.51Kg of 6:2:2 type ternary precursor, and the total recovery rate of the nickel cobalt manganese hydroxide from recovery to the finished product is 98%. Wherein the recovery rate of cobalt is as follows: 98.5 percent; the recovery rate of nickel is as follows: 98.8 percent; the recovery rate of manganese is as follows: 97.9 percent.
Example 6
The embodiment is further optimized on the basis of embodiment 5, and specifically includes:
s1: alkalization and magnesium removal: and (3) adding 32% sodium hydroxide solution for ethanol 0.08m into the crude lithium liquid obtained by ethanol 0.59m from step (2), and adjusting the pH value of the solution to 12.5. Stirring for 1h, filtering, and carrying out high speed 150rps to obtain the refined lithium liquid obtained by the high speed thin film chromatography method under the condition of 0.53 m. The analysis results of the main components of the refined lithium liquid are shown in Table 11 below:
TABLE 11 analysis results of main components of refined lithium solution
| Element(s) | Co | Ni | Mn | Li | Ca | Mg | Fe | Al |
| Content g/L | Not detected out | Not detected out | 0.0002 | 26.56 | 0.22 | 0.0003 | 0.0001 | 0.0003 |
S2: preparing lithium carbonate: heating the refined lithium liquid to 95 ℃, then slowly adding 240g/L sodium carbonate solution for 0.49 m and carrying out filtration with stirring for 0.5h at the stirring speed of 200rps, and washing and drying filter residues to obtain 73.55kg of lithium carbonate product. The technical indexes of the lithium carbonate product in the embodiment are shown in tables 13 and 14.
The recovery values for nickel, cobalt, manganese, lithium according to examples 2, 4, 6 are given in table 13 below:
TABLE 13 recovery of nickel, cobalt, manganese, lithium from examples 2, 4, 6
The chemical composition analysis of lithium carbonate of examples 1, 3 and 5 of the present invention is shown in table 14:
TABLE 14 technical indices of cell-grade lithium carbonate product
As can be seen from tables 13 and 14, the lithium carbonates prepared in examples 1, 3 and 5 all have a main content higher than 99% and meet the requirements of YS/T582-2006 battery level standard, wherein the lithium carbonate prepared in example 1 has a main content as high as 99.61% and high quality; the recovery rate values of the examples 2, 4 and 6 on nickel, cobalt, manganese and lithium are all higher than 95%, and the total recovery rate is higher than 97%, wherein in the example 6: the total recovery rate is as high as 98.5%, the recovery rate of nickel is as high as 98.80%, and experimental tests show that the nickel and cobalt contents in the crude lithium liquid are all below 100ppm, and the lithium contents in the nickel-cobalt-manganese slag are all below 0.1%; the traditional lithium fluoride and calcium and magnesium removal slag for recovering lithium do not relate to the recovery of valuable metal nickel and cobalt, and the invention realizes the separation of nickel, cobalt and lithium by introducing a nickel and cobalt precipitation process, thereby achieving the comprehensive recovery and utilization of resources and high recovery rate of valuable metals.
Claims (9)
1. A method for recovering lithium and preparing a ternary precursor material by calcium and magnesium removal slag is characterized by comprising the following steps: the method comprises the following steps:
(1) converting magnesium salt, namely preparing the calcium-magnesium-removed slag and a magnesium salt solution with the magnesium ion concentration of 30-100g/L into slurry, adding inorganic acid, adjusting the pH of the system to 1.0-5.0, heating and stirring for 1-5h, and filtering to obtain a conversion liquid and calcium magnesium fluoride slag;
(2) precipitating cobalt, nickel and manganese, adding a precipitator into the transformation liquid in the step (1), controlling the system temperature to be 25-100 ℃, and separating the cobalt, nickel and manganese in the transformation liquid from lithium and magnesium in a nickel-cobalt-manganese hydroxide precipitation form to obtain nickel-cobalt-manganese slag and crude lithium liquid;
(3) acid leaching the nickel-cobalt-manganese slag, namely mixing the nickel-cobalt-manganese slag obtained in the step (2) with tap water to obtain slurry, wherein the liquid-solid mass ratio is controlled to be 2-5: 1, preparing slurry, adding inorganic acid into the slurry, adjusting the pH to 0-5, stirring and reacting for 0.5-1h to obtain pickle liquor and pickle residue;
(4) removing calcium and magnesium: adding soluble fluoride salt into the pickle liquor obtained in the step (3), controlling the system temperature to be 50-100 ℃, stirring for reaction for 0.5-2h, and filtering to obtain calcium-magnesium-removed liquor and calcium-magnesium-removed slag;
(5) and (3) extraction: extracting metal cobalt, nickel and manganese in the calcium-magnesium-removed solution by using an organic extractant, and performing back extraction to obtain a back extraction solution containing cobalt, nickel and manganese;
(6) synthesizing a precursor: adding cobalt, nickel and manganese soluble salt into the back extraction solution obtained in the step (5), adding sodium hydroxide and ammonia water, controlling the pH value of the system to 9-12, keeping the reaction temperature at 60-70 ℃, and stirring for 1-5 hours to obtain spherical nickel, cobalt and manganese hydroxide;
(7) drying: drying the spherical nickel, cobalt and manganese hydroxide in the step (6) at the high temperature of 100 ℃ and 500 ℃ for 2-5h to obtain a ternary precursor material;
the calcium and magnesium removal slag in the step (1) is calcium and magnesium removal slag of the waste lithium battery leachate, wherein the mass percentages of cobalt, nickel, manganese and lithium are respectively 1-10%.
2. The method for recovering lithium and preparing a ternary precursor material from calcium and magnesium removal slag according to claim 1, which is characterized in that: the step (1) comprises at least one of the following technical characteristics:
the liquid-solid mass ratio of the calcium-magnesium-removing slag to the magnesium salt pulping is 2-5: 1;
the heating and stirring temperature is 50-100 ℃;
the stirring speed of the heating stirring is as follows: 100-;
the magnesium salt is at least one of magnesium sulfate, magnesium nitrate and magnesium chloride;
the addition amount of the magnesium salt is 1.1-2.0 times of the theoretical mass required by the calculation of a chemical reaction equation by converting all cobalt, nickel, manganese and lithium in the calcium fluoride magnesium slag into soluble salt.
3. The method for recovering lithium and preparing a ternary precursor material from calcium and magnesium removal slag according to claim 2, characterized by comprising the following steps: in the step (2), the precipitant is at least one of sodium hydroxide, potassium hydroxide and ammonia water; the addition amount of the precipitant is 1.0-2.0 times of the theoretical mass required by the calculation of the chemical reaction equation by converting all cobalt, nickel and manganese in the transformation liquid into hydroxide.
4. The method for recovering lithium and preparing a ternary precursor material from the calcium and magnesium removing slag according to claim 3, which is characterized in that: the inorganic acid in the steps (1) and (3) is at least one of sulfuric acid, nitric acid and hydrochloric acid.
5. The method for recovering lithium and preparing a ternary precursor material from calcium and magnesium removal slag according to claim 4, characterized by comprising the following steps: the step (4) comprises at least one of the following technical characteristics:
the soluble fluoride salt is at least one of sodium fluoride and ammonium fluoride;
controlling the pH value of the reaction system to be 0-5;
the stirring rate was 100 and 400 rps.
6. The method for recovering lithium and preparing a ternary precursor material from the calcium and magnesium removing slag according to claim 5, wherein the method comprises the following steps: the pH value of the calcium-magnesium removing liquid in the step (5) is 3.0-6.0, the organic extracting agent is an organic mixture of P507 and sulfonated kerosene, the volume ratio of the organic extracting agent to the sulfonated kerosene is 1:1-5, and the saponification degree is 40% -70%.
7. The method for recovering lithium and preparing a ternary precursor material from the calcium and magnesium removing slag according to claim 6, which is characterized in that: in the step (6), required cobalt nickel manganese sulfate is added according to the molar ratio of nickel, cobalt and manganese of 8:1:1 or 6:2:2 or 5:2:3 to prepare a ternary precursor material, wherein the ternary precursor material is prepared by the methodThe ternary precursor material is Ni0.8Co0.1Mn0.1(OH)2Type or Ni0.6Co0.2Mn0.2(OH)2Type or Ni0.5Co0.2Mn0.3(OH)2And (4) molding.
8. The method for recovering lithium and preparing a ternary precursor material from calcium and magnesium removal slag according to claim 1 or 2, characterized by comprising the following steps: further comprising the steps of:
s1: alkalizing to remove magnesium, adding an alkaline agent into the crude lithium liquid obtained in the step (2), adjusting the pH value of the solution to 10.0-13.0, and filtering to obtain refined lithium liquid and magnesium hydroxide slag;
s2: and (4) preparing lithium carbonate, adding a sodium carbonate solution into the refined lithium solution prepared in the step S1 to precipitate lithium in the form of lithium carbonate, and washing and drying to obtain the battery-grade lithium carbonate.
9. The method for recovering lithium and preparing a ternary precursor material from the calcium and magnesium removing slag according to claim 8, wherein the method comprises the following steps: in the step S1, the alkali agent is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia water.
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| CN111092273B (en) * | 2019-09-14 | 2022-11-18 | 湖南金源新材料股份有限公司 | Novel method for comprehensively recovering cobalt, nickel, manganese and lithium elements from ternary battery waste |
| JP7216945B2 (en) * | 2019-09-14 | 2023-02-02 | 湖南金源新材料股▲ふん▼有限公司 | Manganese-lithium separation and pre-extraction solution preparation process in comprehensive recovery of ternary battery waste and method for comprehensive recovery of cobalt-nickel-manganese-lithium elements from ternary battery waste |
| CN111041217A (en) * | 2019-12-28 | 2020-04-21 | 湖南金源新材料股份有限公司 | Method for preparing pre-extraction solution in comprehensive recovery of ternary battery waste |
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| CN111994925A (en) * | 2020-08-28 | 2020-11-27 | 贵州大龙汇成新材料有限公司 | Comprehensive utilization method of valuable resources in waste lithium batteries |
| CN112795773B (en) * | 2020-12-18 | 2022-10-14 | 南方锰业集团有限责任公司大新锰矿分公司 | Method for removing Ca and Mg in electrolytic manganese metal anode mud |
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