CN109279665B - Treatment method of nickel cobalt lithium manganate ternary waste - Google Patents

Treatment method of nickel cobalt lithium manganate ternary waste Download PDF

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CN109279665B
CN109279665B CN201811066427.6A CN201811066427A CN109279665B CN 109279665 B CN109279665 B CN 109279665B CN 201811066427 A CN201811066427 A CN 201811066427A CN 109279665 B CN109279665 B CN 109279665B
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郑忆依
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China Combustion Energy Environmental Energy (Shandong) Co.,Ltd.
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Abstract

The invention discloses a method for treating nickel cobalt lithium manganate ternary waste. The method comprises the steps of dissolving ternary waste by adding alkali, dissolving amphoteric metal aluminum and the like into a solution, separating aluminum from other components, reducing the solid after aluminum separation in a reduction furnace, adding pure water into the reduced substance for washing, dissolving lithium oxide in hot pure water to obtain lithium hydroxide, separating lithium from nickel, cobalt and manganese, and controlling the addition amount of sulfuric acid and the pH value of the final process and the final end point to separate metal manganese with strong activity from metals such as nickel, cobalt and the like. The method has the advantages of short flow, less waste water generation amount, high material recovery rate, battery grade of the obtained product and high added value of the product.

Description

Treatment method of nickel cobalt lithium manganate ternary waste
Technical Field
The invention relates to a method for treating nickel cobalt lithium manganate ternary waste, and belongs to the field of waste recycling.
Background
With the adjustment of national policies and the improvement of the requirement of vehicle enterprises on endurance mileage, battery enterprises are in a dispute with ternary battery services. Compared with other lithium ion battery anode materials such as lithium manganate and lithium iron phosphate, the lithium nickel cobalt manganese oxide material and the lithium cobaltate are very close to each other in electrochemical performance and processing performance, so that the lithium nickel cobalt manganese oxide material becomes a new battery material to gradually replace the lithium cobaltate, and becomes a favorite of a new generation of lithium ion battery material.
In 2015, the annual sales volume of new energy electric automobiles exceeds 33.11 thousands, and in 2016, the production and sales volume of new energy electric automobiles exceeds 50.7 thousands, and the increase of the year-on-year rate is about 50%. The service life of the lithium ion battery is generally 3-5 years, a large amount of waste lithium ion batteries are inevitably generated along with the production and consumption of the lithium ion battery, if the waste lithium ion batteries are not treated, the waste of resources which is not negligible is inevitably caused, and a large amount of harmful substances are generated. The concrete expression is as follows:
the waste lithium ion battery contains various valuable metals such as cobalt, nickel, aluminum, lithium and the like. For the cobalt aspect, 95% of the cobalt in China is imported from foreign countries, the global cobalt yield is 15 ten thousand tons, and 80% of the 15 ten thousand tons are obtained by recycling;
secondly, various heavy metals (such as cobalt, nickel and the like) and electrolyte (lithium hexafluorophosphate and the like) contained in the waste lithium ion battery can cause great harm to the natural environment and the human health;
and thirdly, the diaphragms, the shells and the like in the waste lithium ion batteries belong to non-degradable wastes, and if the diaphragms, the shells and the like are stacked randomly without effective treatment, a large amount of solid waste pollution and serious air pollution are inevitably brought to the environment.
In summary, the recovery of the waste lithium ion battery is very necessary, and for the recovery of the ternary lithium battery, the positive electrode material contains valuable metals such as lithium, cobalt, nickel and the like, so that the recovery value is great, and therefore attention is paid to the recovery.
Aiming at the treatment of the nickel cobalt lithium manganate ternary waste, the conventional process generally comprises the steps of adding sulfuric acid and a reducing agent for dissolution, then extracting and separating elements such as manganese, zinc and the like through P204, obtaining nickel salt and cobalt salt through P507, and recovering lithium in raffinate through precipitation.
Disclosure of Invention
In view of the above, the invention provides a method for treating nickel cobalt lithium manganate ternary waste, which has the advantages of short flow, less wastewater generation amount and high material recovery rate, and the obtained products are battery grade and can be returned as raw materials of ternary lithium battery anode materials.
The invention solves the technical problems by the following technical means:
the invention relates to a method for treating nickel cobalt lithium manganate ternary waste, which comprises the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 4-6 hours at the soaking temperature of 50-65 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 330-450 ℃ for 6-9 hours, cooling, and discharging to obtain a cooling material;
(2) adding the cooling material into hot pure water, stirring, maintaining the temperature of 90-95 ℃ in the stirring process, stirring for 3-4 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing solution with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1-2mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.9-0.95: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 20-50mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt-nickel washing slag for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting at the temperature of 60-80 ℃ for 3-4 hours, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.8-2.5, then introducing chlorine at the temperature of 140-;
(5) adding an ammonium bicarbonate solution into the lithium-containing filtrate, adjusting the pH of the solution to 7.2-7.5, and the reaction temperature to 35-45 ℃, and then filtering to obtain battery-grade lithium carbonate;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
And (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9-10, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 3-5 mol/L.
The mass ratio of the cooling material to the hot pure water in the step (2) is 1: 4-5, and adopting four-stage countercurrent washing for washing.
The concentration of the hydrochloric acid solution in the step (4) is 1.5-2 mol/L.
And (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2-3mol/L, the time for adding the ammonium bicarbonate solution is 1.5-2 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
And (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 49-51, then cooling the solution at the rate of 2-3 ℃/h to 10-15 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
The reducing agent adopted in the reduction in the step (1) is at least one of hydrogen, methane, carbon monoxide and water gas.
The method for treating the nickel cobalt lithium manganate ternary waste material comprises the steps of firstly dissolving amphoteric metal aluminum and the like in a solution by adopting alkali, then separating solid from liquid to realize the separation of aluminum and other components, and then reducing the solid after aluminum separation in a reduction furnace.
Adding sulfuric acid into the separated slag to perform the following reaction:
Mn+H2SO4----MnSO4+H2
M+H2SO4----MSO4+H2(M is Ni/Co)
Mn+MSO4----M+MnSO4(M is Ni/Co)
The separation of metal manganese with strong activity from metals such as nickel and cobalt is realized by controlling the addition of sulfuric acid and the pH value of the final process and the terminal, wherein a dissolution reaction and a replacement reaction are carried out, the obtained manganese solution is concentrated and crystallized to obtain battery-grade manganese sulfate, the mother liquor after the concentration and crystallization is returned for use after the nickel and cobalt are removed by hydrogen sulfide, and a small amount of impurity-removed slag is returned for reduction.
The method comprises the steps of pulping residues after manganese separation, performing electromagnetic separation, separating metal powder such as magnetic nickel cobalt and the like from other impurities such as copper, lead and the like which are not magnetic, adding hydrochloric acid for dissolution, introducing chlorine gas into the obtained nickel cobalt solution at a certain temperature and under a certain pressure, oxidizing and hydrolyzing cobalt ions into trivalent cobalt precipitates, wherein nickel cannot be oxidized under the pH value, so that the separation of nickel and cobalt is realized, concentrating and crystallizing the obtained nickel solution to obtain battery-grade nickel chloride crystals, adding a sulfuric acid solution and a reducing agent into the obtained cobalt precipitates, dissolving to obtain a cobalt sulfate solution, and concentrating and crystallizing to obtain the battery-grade cobalt sulfate.
Adding ammonium bicarbonate into the obtained lithium hydroxide, precipitating to obtain battery-grade lithium carbonate, concentrating and crystallizing the mother liquor to obtain an ammonium fertilizer, discharging wastewater generated by aluminum recovery in the whole process, basically generating no wastewater in other places, condensing and recovering steam generated in the concentration and crystallization process to obtain pure water, returning the pure water for use, reducing the generation amount of wastewater, and realizing the recovery of all components such as aluminum, nickel, cobalt, manganese and lithium.
Compared with other processes, the process is short in flow, high in component recovery rate and less in generated solid waste, battery-grade lithium carbonate, cobalt sulfate, nickel chloride and manganese sulfate are obtained, and the battery-grade lithium nickel manganese carbonate can be returned to prepare the nickel cobalt lithium manganate anode material again, so that the purpose of recycling is achieved.
The process flow is short, all components such as aluminum foil, phosphate, ferric salt and lithium salt can be recycled, aluminum hydroxide, iron oxide red, battery-grade lithium phosphate and hydrogen phosphate can be obtained, the recovery rate is high, the cost is low, and the added value of the product is high.
The invention has the beneficial effects that: the process is short, the waste water production amount is small, the material recovery rate is high, the obtained products are all battery grade, and the obtained products can be returned to be used as raw materials of the ternary lithium battery anode material.
Drawings
The invention is further described below with reference to the figures and examples.
FIG. 1 is an SEM of aluminum hydroxide obtained in example 1 of the present invention.
Detailed Description
The invention will be described in detail with reference to the accompanying drawings, and the method for treating nickel cobalt lithium manganate ternary waste of the embodiment comprises the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 4-6 hours at the soaking temperature of 50-65 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 330-450 ℃ for 6-9 hours, cooling, and discharging to obtain a cooling material;
(2) adding the cooling material into hot pure water, stirring, maintaining the temperature of 90-95 ℃ in the stirring process, stirring for 3-4 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing solution with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1-2mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.9-0.95: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 20-50mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt-nickel washing slag for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting at the temperature of 60-80 ℃ for 3-4 hours, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.8-2.5, then introducing chlorine at the temperature of 140-;
(5) adding an ammonium bicarbonate solution into the lithium-containing filtrate, adjusting the pH of the solution to 7.2-7.5, and the reaction temperature to 35-45 ℃, and then filtering to obtain battery-grade lithium carbonate;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
And (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9-10, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 3-5 mol/L.
The mass ratio of the cooling material to the hot pure water in the step (2) is 1: 4-5, and adopting four-stage countercurrent washing for washing.
The concentration of the hydrochloric acid solution in the step (4) is 1.5-2 mol/L.
And (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2-3mol/L, the time for adding the ammonium bicarbonate solution is 1.5-2 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
And (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 49-51, then cooling the solution at the rate of 2-3 ℃/h to 10-15 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
The reducing agent adopted in the reduction in the step (1) is at least one of hydrogen, methane, carbon monoxide and water gas.
Example 1
A treatment method of nickel cobalt lithium manganate ternary waste material comprises the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 5 hours at the soaking temperature of 59 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 420 ℃ for 8 hours, cooling, and discharging to obtain a cooling material;
(2) adding the cooling material into hot pure water, stirring, keeping the temperature of the stirring process at 93 ℃, stirring for 3.5 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing liquid with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1.5mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.93: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 30mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt and nickel washing residues for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting for 3.5 hours at the temperature of 70 ℃, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.95, then introducing chlorine at the temperature of 155 ℃ so that the pressure is 1.8 atm, reacting for 4.5 hours under the atmospheric pressure, then cooling, relieving pressure and filtering to obtain cobalt precipitate and a nickel solution, concentrating and crystallizing the nickel solution to obtain battery-grade nickel chloride, adding a sulfuric acid solution into the cobalt precipitate, adding a reducing agent into the cobalt precipitate, completely dissolving to obtain a cobalt sulfate solution, and performing condensation and crystallization to obtain a battery-grade cobalt sulfate crystal;
(5) adding the lithium-containing filtrate into an ammonium bicarbonate solution, adjusting the pH of the solution to 7.3, and filtering to obtain battery-grade lithium carbonate, wherein the reaction temperature is 42 ℃;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
And (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9.5, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 4.2 mol/L.
The mass ratio of the cooling material to the hot pure water in the step (2) is 1: and 4.5, adopting four-stage countercurrent washing for washing.
The concentration of the hydrochloric acid solution in the step (4) is 1.8 mol/L.
And (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2.3mol/L, the time for adding the ammonium bicarbonate solution is 1.8 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
And (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 49.5, then cooling the solution at the rate of 2.5 ℃/h to the temperature of 13 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
The reducing agent adopted in the reduction in the step (1) is hydrogen.
The final recovery rate of lithium was 99.3%, the recovery rate of cobalt was 98.9%, the recovery rate of nickel was 99.1%, the recovery rate of manganese was 99.3%, the recovery rate of aluminum was 99.4%,
as shown in fig. 1, the obtained aluminum hydroxide has a flocculent agglomerated structure, a large specific surface area and a small primary particle size, and the finally obtained detection data of the aluminum hydroxide are as follows:
Figure BDA0001798424920000061
the obtained detection data of the battery grade cobalt sulfate are as follows:
index (I) Principal content Fe Mn Zn Ca Mg Na
Numerical value 99.63％ 2.5ppm 21ppm 4ppm 31ppm 21ppm 25ppm
K Pb Ni As Cu Cd Water insoluble substance Cl
12ppm 2ppm 39ppm 0.2ppm 1.5ppm 2.3ppm 45ppm 12ppm
The obtained detection data of battery grade nickel chloride are as follows:
index (I) Principal content Fe Mn Zn Ca Mg Na
Numerical value 99.51％ 2.5ppm 24ppm 2ppm 21ppm 13ppm 21ppm
K Pb Co As Cu Cd Water insoluble substance pH
12ppm 1ppm 42ppm 0.3ppm 2.1ppm 2.1ppm 35ppm 4.6
The detection data of the battery-grade manganese sulfate are as follows:
Figure BDA0001798424920000062
Figure BDA0001798424920000071
the detection data of the battery-grade lithium carbonate are as follows:
Figure BDA0001798424920000072
example 2
A treatment method of nickel cobalt lithium manganate ternary waste material comprises the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 4.5 hours at the soaking temperature of 58 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 415 ℃ for 8 hours, cooling and discharging to obtain a cooling material;
(2) adding the cooling material into hot pure water, stirring, keeping the temperature of the stirring process at 93 ℃, stirring for 3.5 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing liquid with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1.5mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.93: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 35mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt and nickel washing residues for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting for 3.5 hours at the temperature of 75 ℃, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.95, then introducing chlorine at the temperature of 155 ℃ so that the pressure is 1.8 atm, reacting for 4.5 hours under the atmospheric pressure, then cooling, relieving pressure and filtering to obtain cobalt precipitate and a nickel solution, concentrating and crystallizing the nickel solution to obtain battery-grade nickel chloride, adding a sulfuric acid solution into the cobalt precipitate, adding a reducing agent into the cobalt precipitate, completely dissolving to obtain a cobalt sulfate solution, and performing condensation and crystallization to obtain a battery-grade cobalt sulfate crystal;
(5) adding an ammonium bicarbonate solution into the lithium-containing filtrate, adjusting the pH of the solution to 7.42, controlling the reaction temperature to 39 ℃, and then filtering to obtain battery-grade lithium carbonate;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
And (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9.5, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 4.5 mol/L.
The mass ratio of the cooling material to the hot pure water in the step (2) is 1: 4.3, four-stage countercurrent washing is adopted in the washing.
The concentration of the hydrochloric acid solution in the step (4) is 1.8 mol/L.
And (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2.6mol/L, the time for adding the ammonium bicarbonate solution is 1.8 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
And (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 50.3, then cooling the solution at the speed of 2.4 ℃/h to the temperature of 13 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
The reducing agent adopted in the reduction in the step (1) is hydrogen.
The final recovery rate of lithium was 99.3%, the recovery rate of cobalt was 98.7%, the recovery rate of nickel was 99.1%, the recovery rate of manganese was 99.3%, the recovery rate of aluminum was 99.4%,
the final aluminum hydroxide detection data were as follows:
Figure BDA0001798424920000081
the obtained detection data of the battery grade cobalt sulfate are as follows:
index (I) Principal content Fe Mn Zn Ca Mg Na
Numerical value 99.61％ 4ppm 18ppm 3ppm 25ppm 20ppm 21ppm
K Pb Ni As Cu Cd Water insoluble substance Cl
8ppm 2ppm 35ppm 0.2ppm 1.5ppm 2.1ppm 41ppm 11ppm
The obtained detection data of battery grade nickel chloride are as follows:
index (I) Principal content Fe Mn Zn Ca Mg Na
Numerical value 99.54％ 2.9ppm 32ppm 2ppm 22ppm 11ppm 21ppm
K Pb Co As Cu Cd Water insoluble substance pH
11ppm 1ppm 41ppm 0.3ppm 2.4ppm 2.6ppm 39ppm 4.5
The detection data of the battery-grade manganese sulfate are as follows:
index (I) Mn Fe Ni Zn Ca Mg Na
Numerical value 32.2％ 4ppm 23ppm 1ppm 13ppm 15ppm 21ppm
K Pb Co As Cu Cd Water insoluble substance pH
11ppm 0.2ppm 21ppm 0.2ppm 2ppm 2.1ppm 41ppm 5.8
The detection data of the battery-grade lithium carbonate are as follows:
Figure BDA0001798424920000091
example 3
A treatment method of nickel cobalt lithium manganate ternary waste material comprises the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 4.8 hours at the soaking temperature of 63 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 425 ℃ for 8 hours, cooling, and discharging to obtain a cooled material;
(2) adding the cooling material into hot pure water, stirring, keeping the temperature of the stirring process at 93 ℃, stirring for 3.5 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing liquid with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1.7mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.93: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 30mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt and nickel washing residues for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting for 3.5 hours at the temperature of 69 ℃, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.9, then introducing chlorine at the temperature of 155 ℃ so that the pressure is 1.8 atm, reacting for 4.5 hours under the atmospheric pressure, then cooling, relieving pressure and filtering to obtain cobalt precipitate and a nickel solution, concentrating and crystallizing the nickel solution to obtain battery-grade nickel chloride, adding a sulfuric acid solution into the cobalt precipitate, adding a reducing agent into the cobalt precipitate, completely dissolving to obtain a cobalt sulfate solution, and performing condensation and crystallization to obtain a battery-grade cobalt sulfate crystal;
(5) adding an ammonium bicarbonate solution into the lithium-containing filtrate, adjusting the pH of the solution to 7.4, and filtering at the reaction temperature of 44 ℃ to obtain battery-grade lithium carbonate;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
And (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9.7, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 4.5 mol/L.
The mass ratio of the cooling material to the hot pure water in the step (2) is 1: and 4.7, adopting four-stage countercurrent washing for washing.
The concentration of the hydrochloric acid solution in the step (4) is 1.8 mol/L.
And (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2.7mol/L, the time for adding the ammonium bicarbonate solution is 1.7 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
And (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 50.5, then cooling the solution at the rate of 2.5 ℃/h to the temperature of 13 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
The reducing agent adopted in the reduction in the step (1) is methane.
The final recovery rate of lithium was 99.2%, the recovery rate of cobalt was 99.1%, the recovery rate of nickel was 99.3%, the recovery rate of manganese was 99.2%, the recovery rate of aluminum was 99.3%,
the final aluminum hydroxide detection data were as follows:
Figure BDA0001798424920000101
the obtained detection data of the battery grade cobalt sulfate are as follows:
index (I) Principal content Fe Mn Zn Ca Mg Na
Numerical value 99.61％ 2ppm 23ppm 4ppm 21ppm 26ppm 23ppm
K Pb Ni As Cu Cd Water insoluble substance Cl
21ppm 1ppm 34ppm 0.3ppm 1.4ppm 2.1ppm 43ppm 12ppm
The obtained detection data of battery grade nickel chloride are as follows:
Figure BDA0001798424920000102
Figure BDA0001798424920000111
the detection data of the battery-grade manganese sulfate are as follows:
index (I) Mn Fe Ni Zn Ca Mg Na
Numerical value 32.3％ 4ppm 20ppm 1ppm 8ppm 11ppm 27ppm
K Pb Co As Cu Cd Water insoluble substance pH
12ppm 0.2ppm 33ppm 0.3ppm 2.7ppm 2.1ppm 49ppm 5.8
The detection data of the battery-grade lithium carbonate are as follows:
Figure BDA0001798424920000112
from the test data, the prepared aluminum hydroxide can be used as a flame retardant filler, and other materials such as lithium carbonate, nickel chloride, cobalt sulfate and manganese sulfate are battery grade materials.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (7)

1. A method for treating nickel cobalt lithium manganate ternary waste is characterized by comprising the following steps:
(1) adding the nickel cobalt lithium manganate ternary waste into an alkali solution, soaking for 4-6 hours at the soaking temperature of 50-65 ℃, filtering to obtain an aluminum-containing solution and filter residues, washing the filter residues, drying and screening, reducing undersize products in a reducing furnace at the reducing temperature of 330-450 ℃ for 6-9 hours, cooling, and discharging to obtain a cooling material;
(2) adding the cooling material into hot pure water, stirring, maintaining the temperature of 90-95 ℃ in the stirring process, stirring for 3-4 hours, carrying out solid-liquid separation to obtain lithium-containing filtrate and filter residue, washing the filter residue, and mixing the washing solution with the lithium-containing filtrate;
(3) adding a sulfuric acid solution into the washed filter residue obtained in the step (2) for slurrying, wherein the concentration of the sulfuric acid solution is 1-2mol/L, and the molar ratio of the added sulfuric acid to the manganese in the washed filter residue is 0.9-0.95: 1, when the pH value of the solution is more than 6.5, continuously adding sulfuric acid to maintain the pH value of the reaction to be 6-6.5, stirring the solution at the pH value for reaction, stopping the reaction when the cobalt content in the solution is 20-50mg/L, filtering the solution to obtain a manganese-containing solution and cobalt-nickel slag, washing the cobalt-nickel slag to obtain cobalt-nickel washing slag, and mixing a washing solution with the manganese-containing solution;
(4) adding water into cobalt-nickel washing slag for slurrying, performing electromagnetic separation to obtain a magnetic separation material, adding a hydrochloric acid solution into the magnetic separation material, stirring and reacting at the temperature of 60-80 ℃ for 3-4 hours, then filtering to obtain a first filtrate and a first filter residue, adding the first filtrate into a reaction kettle, adjusting the pH to 1.8-2.5, then introducing chlorine at the temperature of 140-;
(5) adding an ammonium bicarbonate solution into the lithium-containing filtrate, adjusting the pH of the solution to 7.2-7.5, and the reaction temperature to 35-45 ℃, and then filtering to obtain battery-grade lithium carbonate;
(6) and concentrating and crystallizing the manganese-containing solution to obtain battery-grade manganese sulfate, introducing hydrogen sulfide gas into the crystallized mother solution, reducing the nickel-cobalt content to below 10ppm, filtering, returning filter residues to a reduction furnace, and returning the filtrate to be mixed with the manganese-containing solution.
2. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: and (2) introducing carbon dioxide into the aluminum-containing solution, adjusting the pH of the solution to 9-10, and filtering and washing to obtain the aluminum hydroxide, wherein the concentration of the alkali solution in the step (1) is 3-5 mol/L.
3. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: the mass ratio of the cooling material to the hot pure water in the step (2) is 1: 4-5, and adopting four-stage countercurrent washing for washing.
4. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: the concentration of the hydrochloric acid solution in the step (4) is 1.5-2 mol/L.
5. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: and (3) the concentration of the ammonium bicarbonate solution in the step (5) is 2-3mol/L, the time for adding the ammonium bicarbonate solution is 1.5-2 hours, and the filtrate obtained after filtration is concentrated and crystallized to obtain the ammonium fertilizer.
6. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: and (3) concentrating the solution in the step (6) during concentration and crystallization until the Baume degree of the solution is 49-51, then cooling the solution at the rate of 2-3 ℃/h to 10-15 ℃, and carrying out centrifugal separation by adopting a horizontal screw centrifuge.
7. The method for treating the nickel cobalt lithium manganate ternary waste material as claimed in claim 1, characterized in that: the reducing agent adopted in the reduction in the step (1) is at least one of hydrogen, methane, carbon monoxide and water gas.
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CN111118311B (en) * 2019-12-28 2021-10-22 湖南金源新材料股份有限公司 Manganese-lithium separation method in comprehensive recovery of ternary battery waste
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835228B1 (en) * 2003-11-14 2004-12-28 Industrial Technology Research Institute Process of recovering valuable metals from waste secondary batteries
CN101006190A (en) * 2004-06-28 2007-07-25 斯凯资源有限公司 Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching
CN101871048A (en) * 2010-06-25 2010-10-27 浙江华友钴业股份有限公司 Method for recovering cobalt, nickel and manganese from waste lithium cells
CN103014346A (en) * 2012-12-03 2013-04-03 河池市津泰资源再生有限公司 Process method for separating zinc, iron and cobalt and nickel ore concentrates from cobalt and nickel slag
CN103361483A (en) * 2013-07-26 2013-10-23 浙江钛合仪器有限公司 Technology for removing cobalt by dynamic wave chlorine oxidation
JP5636688B2 (en) * 2010-02-23 2014-12-10 住友大阪セメント株式会社 Method for producing electrode material and method for recovering lithium phosphate
CN107151739A (en) * 2017-07-07 2017-09-12 金川集团股份有限公司 A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel
CN107653378A (en) * 2017-08-25 2018-02-02 金川集团股份有限公司 The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery
CN108265178A (en) * 2018-03-08 2018-07-10 蒋央芳 A kind of processing method of cobalt metallurgy of nickel waste water slag

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835228B1 (en) * 2003-11-14 2004-12-28 Industrial Technology Research Institute Process of recovering valuable metals from waste secondary batteries
CN101006190A (en) * 2004-06-28 2007-07-25 斯凯资源有限公司 Method for nickel and cobalt recovery from laterite ores by reaction with concentrated acid and water leaching
JP5636688B2 (en) * 2010-02-23 2014-12-10 住友大阪セメント株式会社 Method for producing electrode material and method for recovering lithium phosphate
CN101871048A (en) * 2010-06-25 2010-10-27 浙江华友钴业股份有限公司 Method for recovering cobalt, nickel and manganese from waste lithium cells
CN103014346A (en) * 2012-12-03 2013-04-03 河池市津泰资源再生有限公司 Process method for separating zinc, iron and cobalt and nickel ore concentrates from cobalt and nickel slag
CN103361483A (en) * 2013-07-26 2013-10-23 浙江钛合仪器有限公司 Technology for removing cobalt by dynamic wave chlorine oxidation
CN107151739A (en) * 2017-07-07 2017-09-12 金川集团股份有限公司 A kind of full leaching method of nitric acid of the high iron alloy powder of low nickel
CN107653378A (en) * 2017-08-25 2018-02-02 金川集团股份有限公司 The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery
CN108265178A (en) * 2018-03-08 2018-07-10 蒋央芳 A kind of processing method of cobalt metallurgy of nickel waste water slag

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