CN110817908A - System and method for preparing high-purity lithium carbonate by using lithium-containing waste material - Google Patents
System and method for preparing high-purity lithium carbonate by using lithium-containing waste material Download PDFInfo
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Abstract
The invention belongs to the field of waste resource utilization, and relates to a method for preparing high-purity lithium carbonate by recycling lithium-containing waste materials, so that high added value utilization of lithium resources is realized. The lithium-containing waste material is subjected to a series of technologies such as an extraction technology, a falling film evaporator technology, an ultrafiltration membrane technology, an ion exchange technology, a supergravity machine technology, a pulse control technology, a lithium precipitation crystallization control technology and the like, so that high-purity lithium carbonate is obtained, the technological process is continuous and controllable, the extraction yield is high, the production cost is low, the resource utilization degree is high, the industrialization is easy, the purposes of environmental protection, energy conservation, emission reduction and circular economy are realized, and the unification of environmental benefits and economic benefits is finally achieved.
Description
Technical Field
The invention relates to a method for preparing high-purity lithium carbonate by recycling lithium-containing waste materials, which is mainly applied to resource recycling of waste lithium ion batteries, such as lithium iron phosphate, lithium cobaltate, lithium nickelate, lithium manganate, lithium iron manganese phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary, nickel-cobalt-aluminum ternary batteries and the like.
Background
Due to the rapid development of new energy automobiles, the market scale of the Chinese lithium battery in 2017 reaches 92.8GWH, and is increased by 37.5% on a par, and the market scale is expected to exceed 200GWH and reach 216GWH in 2020. With the rapid rise of the new energy automobile industry, the power battery becomes the strongest growth point of the lithium battery industry, the market scale is 52.6GWH in 2017, the permeability reaches 56.7%, and the permeability is predicted to reach 69.9% in 2020. Since 2014, the new energy automobile industry in China is rapidly developed, the power battery can be retired after 5-6 years, and the power battery of the commercial vehicle can be retired after 2-3 years, so that the commercial vehicle enters a retired period in 2018, and the national retired amount is expected to reach 20GWH in 2020. The lithium iron phosphate battery is expected to be retired at a high speed for a long time in 2018, the retirement amount is expected to reach 20GWH by 2021, and the recycling amount is expected to exceed 6 ten thousand tons. The ternary power battery becomes the main retired stream in 2023 years, the retired amount exceeds 20GWH, and the recycling amount of the ternary lithium battery exceeds 8 ten thousand tons in 2023 years.
With the rapid development of the new energy automobile market, the scrappage of the lithium ion power battery is greatly increased. The waste lithium battery is recycled to be a renewable resource, and the lithium ion power battery mainly comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. Typical lithium ion power batteries contain valuable metals such as cobalt, lithium, copper, aluminum, nickel, iron and the like, wherein the copper, the lithium, the cobalt and the nickel mainly exist in a positive electrode material, waste lithium batteries in the market are generated in tens of millions of tons every year, and the recovery treatment of the waste lithium batteries has extremely high commercial value. At present, a large number of waste lithium batteries are available, including lithium iron phosphate batteries, lithium cobaltate batteries, lithium manganate batteries, lithium mobile phones, 18650 lithium batteries, electric vehicle lithium batteries and other large numbers of waste lithium batteries. If the waste lithium ion power battery is improperly recycled, the recycling rate of metal resources is not high, which causes waste of resources, and also causes environmental pollution, wherein the recycling of waste lithium ion batteries becomes one of the key technologies for recycling electronic wastes. CN1019425695 discloses a method for recovering lithium from waste lithium ion batteries and waste pole pieces, which is to obtain a lithium fluoride product by disassembling, crushing, alkali dissolution, acid leaching, chemical impurity removal, and fluoride salt precipitation leaching lithium, but has the problems of low product quality, low total lithium yield and the like.
The waste lithium battery can be recycled to produce nickel, cobalt, manganese and lithium salt, as well as ternary cathode materials and precursors, and the method can be directly used for manufacturing lithium battery cells, has great significance for constructing an industrial chain closed loop, can effectively recover the cost of the lithium battery, and has strong economy.
Disclosure of Invention
Aiming at the problems of high recovery and treatment cost, longer process flow, unstable product quality, low lithium resource recovery rate and the like in the prior art, the invention aims to provide a method for preparing high-purity lithium carbonate by recycling lithium-containing waste materials.
Therefore, the following technical scheme is adopted: the system for preparing high-purity lithium carbonate by using lithium-containing waste materials is characterized by comprising the following steps of:
an extraction and leaching unit, which is used for leaching the lithium-containing waste material and an extracting agent to obtain an extraction liquid and separating lithium ions from other nickel, cobalt and manganese ions;
a lithium precipitation reaction unit, adding the enriched lithium liquid from the extraction leaching unit into a sodium carbonate solution to generate a lithium carbonate precipitate, and filtering and separating to obtain a crude lithium carbonate product;
a hydrogenation reaction unit, preparing the crude product from the lithium precipitation reaction unit and water into slurry, and introducing carbon dioxide gas to obtain a lithium bicarbonate clarified liquid;
the ion exchange unit is used for carrying out ion exchange on the lithium bicarbonate clarified liquid from the hydrogenation reaction unit to realize the advanced treatment of anions and cations;
a purification and refining unit, which is used for refining the purified solution by adding a complexing agent and a membrane separation technology into the solution from the ion exchange unit;
and a spray drying unit for spray drying the purified liquid from the purification and purification unit to obtain high-purity lithium carbonate.
According to the invention, selective lithium extraction is realized by an extracting agent, a lithium precipitation reaction is enhanced by a super-gravity machine, advanced treatment of anions and cations is realized by ion exchange resin, impurity removal by a complexing agent is carried out, purification liquid refining is carried out by an ultrafiltration membrane, and a high-purity lithium carbonate product is obtained by spray drying.
The lithium-containing waste material is obtained by mechanically crushing and sorting waste batteries.
Further, the extraction leaching unit comprises an extraction kettle; the lithium precipitation reaction unit comprises a supergravity machine; the ion exchange unit comprises one or more stages of ion exchange columns; the refining unit comprises an ultrafiltration membrane separator; the spray drying unit comprises a spray dryer.
The invention also provides a method for preparing high-purity lithium carbonate by using the lithium-containing waste material, which comprises the following steps:
step I, adding lithium-containing waste materials and an extracting agent in an extraction kettle according to a certain proportion, controlling the temperature to be 20-60 ℃, carrying out heat preservation stirring reaction for 10-120 min, obtaining an extract after the reaction is finished, and enriching and separating lithium ions;
step II, adding the extraction liquid obtained in the step I into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse form, keeping the temperature, stirring uniformly, reacting for 0.5-2 hours, adding seed crystals to promote crystallization of lithium carbonate to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product;
step III, adding a certain proportion of water into the crude lithium carbonate product obtained in the step II to prepare lithium carbonate slurry, introducing carbon dioxide gas at a certain rate until the solution is turbid to clear, and finishing the reaction to obtain a lithium bicarbonate solution;
step IV, enabling the lithium bicarbonate solution in the step III to pass through one or more stages of ion exchange columns loaded with cation exchange resin, anion exchange resin and/or chelating resin at a certain flow rate, and respectively removing trace ion impurities in the solution;
v, adding a complexing agent into the solution obtained in the step IV, complexing trace calcium, magnesium and iron ions in the filtrate into complex ions with larger volume, and separating lithium ions with smaller volume through an ultrafiltration membrane to obtain a refined lithium-rich solution;
and VI, spray drying the refined lithium-rich solution in the step V to obtain high-purity lithium carbonate.
Further, in the step I, the extraction temperature is 20-80 ℃, preferably 30-50 ℃, the extraction time is 15-120 min, and the extracting agent is one or a mixture of pyrrole hexafluorophosphate ionic liquid, imidazole hexafluorophosphate ionic liquid, pyridine hexafluorophosphate ionic liquid, piperidine hexafluorophosphate ionic liquid, N-N, dimethylformamide, tributyl phosphate, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and N' N-bis (2-ethylhexyl) acrylamide.
Further, in the step II, the pulse frequency of the saturated sodium carbonate solution is 10-100 KHz, preferably 20-30 KHz.
Further, in the step II, the seed crystal is lithium carbonate, the particle size can be various particle sizes of nanometer grade and hundreds of micrometers, and the shape can be one or more of spherical, rod-shaped, flower-shaped, sheet-shaped and hollow spheres.
Further, in the step III, the ratio of the crude lithium carbonate to water is 2: 1-1: 50, the flow rate of the carbon dioxide gas is 0.5-5L/min.
Further, in the step IV, the cation exchange resin is selected from one or more of styrene, acrylic acid and phenolic aldehyde; the anion exchange resin is selected from one or more of styrene, acrylic acid and epoxy; the chelating resin is selected from one or more of D110, D113, D152, D401, D403, D418 and D564.
Further, in step IV, the flow rate of the concentrate through the ion exchange column is 5 to 50BV/h, preferably 8 to 20 BV/h.
Further, in the step V, the complexing agent is one or more of EDTA, crown ether, nitrilotriacetic acid, citric acid, tartaric acid, oleic acid, gluconic acid and diethylenetriamine pentaacetic acid.
Furthermore, in the step V, the ultrafiltration membrane is made of ceramics, polysulfone, polyetheretherketone, polyvinylidene fluoride or polytetrafluoroethylene, the filtration precision of the ultrafiltration membrane is 10-100nm, the component mode of the ultrafiltration membrane is hollow fiber, roll type, plate type or tube type, and the filtration mode of the ultrafiltration membrane is cross-flow or counter-flow filtration.
Further, the waste lithium ion battery comprises one or a mixture of lithium iron phosphate, lithium cobaltate, lithium nickelate, lithium manganate, lithium iron manganese phosphate, nickel-cobalt binary, nickel-manganese binary, cobalt-manganese binary, nickel-cobalt-manganese ternary and nickel-cobalt-aluminum ternary batteries.
The invention obtains high-purity lithium carbonate by extracting technology, falling film evaporator technology, ultrafiltration membrane technology, ion exchange technology, hypergravity machine technology, pulse control technology, lithium deposition crystallization control technology and other series technologies to the lithium-containing waste, the process is continuous and controllable, the extraction yield is high, the production cost is low, the waste resource utilization degree is high, the industrialization is easy, the purposes of environmental protection, energy conservation, emission reduction and recycling economy are realized, and the unification of environmental benefit and economic benefit is finally achieved.
Drawings
Fig. 1 is a schematic flow chart of preparing high-purity lithium carbonate by using lithium-containing waste materials in the embodiment of the invention.
Detailed Description
The invention is further described in detail with reference to the following drawings and specific examples.
Example (b): referring to fig. 1, the system for preparing high-purity lithium carbonate by using lithium-containing waste materials operates as follows:
adding the lithium-containing waste material and an extracting agent in an extraction kettle according to a certain proportion, controlling the temperature at 20-60 ℃, preserving heat, stirring and reacting for 10-120 min, obtaining an extract after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse form, keeping the temperature, stirring uniformly, reacting for 0.5-2 h, adding seed crystals to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; adding water in a certain proportion into the crude lithium carbonate product to prepare lithium carbonate slurry, introducing carbon dioxide gas at a certain rate until the solution is turbid to clear, and finishing the reaction to obtain a lithium bicarbonate solution; the solution passes through one or more stages of ion exchange columns loaded with cation exchange resin, anion exchange resin and/or chelating resin at a certain flow rate to respectively remove trace ion impurities in the solution; adding a complexing agent into the solution, complexing trace calcium, magnesium and iron ions in the filtrate into complex ions with larger volume, and separating lithium ions with smaller volume through an ultrafiltration membrane to obtain a refined lithium-rich solution; and spray drying to obtain the high-purity lithium carbonate.
Example 1
The lithium-containing waste liquid generated in the process of recovering the anode material of the waste lithium ion battery is mainly Li-containing+、Na+、H+And SO4 2-The pH of the aqueous solution of (1) is 4 to 5, and the concentration of lithium ions is 7 g/L.
Adding lithium-containing waste materials and a 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid extracting agent in a ratio of 1:3 into an extraction kettle, controlling the temperature at 40 ℃, keeping the temperature, stirring and reacting for 15min, obtaining an extraction liquid after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 18KHz, uniformly stirring for reacting for 1.5h, adding rod-shaped lithium carbonate seed crystals to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: 5, preparing lithium carbonate slurry, introducing carbon dioxide gas at the rate of 1.0L/min until the solution is turbid to clear, and finishing the reaction to obtain a lithium bicarbonate solution; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 12BV/h to respectively remove trace ion impurities in the solution; EDTA is added into the solution, trace impurity ions in the filtrate are complexed to form complex ions with larger volume, and lithium ions with smaller volume are separated by using an ultrafiltration membrane made of polysulfone to obtain refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.993%, and the product meets the quality standard of YS/T546-.
Example 2
The lithium-containing waste liquid generated in the recovery process of the waste nickel-cobalt-manganese ternary lithium ion battery is mainly Li-containing+、Na+、H+And SO4 2-The pH of the aqueous solution of (1) is 2 to 4, and the lithium ion concentration of the aqueous solution is 8.6 g/L.
Adding lithium-containing waste materials and an octyl pyrrole hexafluorophosphate ionic liquid extracting agent in a ratio of 1:8 into an extraction kettle, controlling the temperature at 50 ℃, keeping the temperature, stirring and reacting for 15min, obtaining an extract after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 20KHz, uniformly stirring for reacting for 1.5h, adding a hollow lithium carbonate seed crystal to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 10, introducing carbon dioxide gas at the rate of 1.6L/min until the solution is clear from turbid, and obtaining a lithium bicarbonate solution after the reaction is finished; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 16BV/h to respectively remove trace ion impurities in the solution; adding nitrilotriacetic acid into the solution, complexing trace impurity ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of ceramics to obtain a refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.996%, and the product meets the quality standard of YS/T546-.
Example 3
The lithium-containing waste liquid generated in the recovery process of the waste lithium manganate battery is mainly Li-containing+、Na+、H+And SO4 2-The pH of the aqueous solution of (1) is 4 to 6, and the lithium ion concentration of the aqueous solution is 6.4 g/L.
Adding lithium-containing waste materials and an ethyl piperidine hexafluorophosphate ionic liquid extracting agent in a ratio of 1:3 into an extraction kettle, controlling the temperature at 55 ℃, keeping the temperature, stirring and reacting for 30min, obtaining extract liquid after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 24KHz, uniformly stirring for 1 hour while keeping the temperature, adding micron-sized lithium carbonate crystal seeds to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 18, introducing carbon dioxide gas at the speed of 2.2L/min until the solution is clear from turbid, and obtaining a lithium bicarbonate solution after the reaction is finished; the solution passes through a first-stage ion exchange column loaded with cation exchange resin at the flow rate of 20BV/h to respectively remove trace ion impurities in the solution; adding citric acid into the solution, complexing trace impurity ions in the filtrate to form complex ions with a larger volume, and separating lithium ions with a smaller volume by using an ultrafiltration membrane made of polytetrafluoroethylene to obtain a refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.991%, and the product meets the quality standard of YS/T546-.
Example 4
The lithium-containing waste liquid generated in the recovery process of the waste lithium cobaltate battery is mainly Li-containing+、Na+、H+And SO4 2-The pH of the aqueous solution of (1) is 3 to 4, and the concentration of lithium ions is 4 g/L.
In an extraction kettle, lithium-containing waste materials and octyl pyrrole hexafluorophosphate ionic liquid: adding tributyl phosphate (6: 4) extractant at a ratio of 1:15, controlling the temperature at 48 ℃, keeping the temperature, stirring and reacting for 60min to obtain extract liquid after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 20KHz, uniformly stirring for reacting for 1.2h, adding flower-shaped lithium carbonate crystal seeds to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 10, introducing carbon dioxide gas at the rate of 3.0L/min until the solution is clear from turbid, and obtaining a lithium bicarbonate solution after the reaction is finished; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 18BV/h to respectively remove trace ion impurities in the solution; adding diethylenetriaminepentaacetic acid into the solution, complexing trace ions such as calcium, magnesium and iron in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polysulfone to obtain a refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.998%, and the product meets the quality standard of YS/T546-.
Example 5
The lithium-containing waste liquid generated in the recovery process of the waste cobalt-manganese binary lithium ion battery is mainly Li-containing+、Na+、H+And SO4 2-The aqueous solution of (1) has a pH of 1.3 to 3.2, and has a lithium ion concentration of 3.5 g/L.
In an extraction kettle, lithium-containing waste and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid: adding tributyl phosphate (4: 6) extractant at a ratio of 1:4, controlling the temperature at 56 ℃, keeping the temperature, stirring and reacting for 45min to obtain extract liquid after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 28KHz, uniformly stirring for reacting for 1.5h, adding flower-shaped lithium carbonate crystal seeds to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 25, introducing carbon dioxide gas at the rate of 2.2L/min until the solution is clear from turbid, and obtaining a lithium bicarbonate solution after the reaction is finished; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 8BV/h to respectively remove trace ion impurities in the solution; EDTA is added into the solution, trace impurity ions in the filtrate are complexed to form complex ions with larger volume, and lithium ions with smaller volume are separated by using an ultrafiltration membrane made of polyvinylidene fluoride to obtain refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.996%, and the product meets the quality standard of YS/T546-.
Example 6
The lithium-containing waste liquid generated in the recovery process of the waste lithium iron phosphate battery is mainly Li-containing+、Na+、H+And SO4 2-The aqueous solution of (1), wherein the pH of the solution is 3.5 to 4.8, and the concentration of lithium ions is 3.5 g/L.
In an extraction kettle, lithium-containing waste and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid: adding an N-N dimethylformamide (8: 2) extractant according to a ratio of 1:7, controlling the temperature at 52 ℃, keeping the temperature, stirring and reacting for 60min to obtain an extract after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 25KHz, uniformly stirring for reacting for 1.6h, adding nano-scale lithium carbonate crystal seeds to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 12, introducing carbon dioxide gas at the rate of 0.8L/min until the solution is turbid to clear, and finishing the reaction to obtain a lithium bicarbonate solution; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 10BV/h to remove trace ion impurities in the solution; EDTA is added into the solution, trace impurity ions in the filtrate are complexed to form complex ions with larger volume, and lithium ions with smaller volume are separated by using an ultrafiltration membrane made of polyvinylidene fluoride to obtain refined lithium-rich solution; and spray drying to obtain the high-purity lithium carbonate with the purity of 99.995 percent, wherein the product meets the quality standard of YS/T546-.
Example 7
The lithium-containing waste liquid generated in the recovery process of the waste nickel-manganese binary lithium ion battery is mainly Li-containing+、Na+、H+And SO4 2-The aqueous solution of (1), wherein the pH of the solution is 2.3 to 3.2, and the concentration of lithium ions is 2.8 g/L.
In an extraction kettle, lithium-containing waste and 1-ethyl-3-butyl pyrrole hexafluorophosphate salt ionic liquid: adding 2-ethylhexyl phosphate mono-2-ethylhexyl ester (7: 3) extractant according to a ratio of 1:10, controlling the temperature at 43 ℃, keeping the temperature, stirring, reacting for 36min, obtaining extract after the reaction is finished, and enriching and separating lithium ions; adding the extract into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse mode, keeping the pulse frequency at 30KHz, uniformly stirring for reacting for 2.0 hours while keeping the temperature, adding micron-sized lithium carbonate crystal seeds to promote crystallization to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product; mixing the lithium carbonate crude product and water according to the proportion of 1: preparing lithium carbonate slurry according to the proportion of 30, introducing carbon dioxide gas at the rate of 1.5L/min until the solution is turbid to clear, and finishing the reaction to obtain a lithium bicarbonate solution; the solution passes through two stages of ion exchange columns loaded with cation exchange resin and anion exchange resin at the flow rate of 13BV/h to remove trace ion impurities in the solution; adding gluconic acid into the solution, complexing trace impurity ions in the filtrate to form complex ions with larger volume, and separating lithium ions with smaller volume by using an ultrafiltration membrane made of polyether-ether-ketone to obtain a refined lithium-rich solution; the high-purity lithium carbonate is obtained through spray drying, the purity is 99.992%, and the product meets the quality standard of YS/T546-.
The method for preparing high-purity lithium carbonate by recycling the lithium-containing waste materials provided by the invention obtains the high-purity lithium carbonate by a series of technologies such as an extraction technology, a falling film evaporator technology, an ultrafiltration membrane technology, an ion exchange technology, a supergravity machine technology, a pulse control technology, a lithium deposition crystallization control technology and the like on the lithium-containing waste materials, has the advantages of continuous and controllable process, high extraction yield, low production cost, high resource utilization degree, easiness in industrialization, realization of the purposes of environmental protection, energy conservation, emission reduction and recycling economy, and finally achieves the unification of environmental benefits and economic benefits.
Claims (10)
1. A system for preparing high-purity lithium carbonate by using lithium-containing waste materials is characterized by comprising the following steps:
an extraction and leaching unit, which is used for leaching the lithium-containing waste material and an extracting agent to obtain an extraction liquid and separating lithium ions from other nickel, cobalt and manganese ions;
a lithium precipitation reaction unit, adding the enriched lithium liquid from the extraction leaching unit into a sodium carbonate solution to generate a lithium carbonate precipitate, and filtering and separating to obtain a crude lithium carbonate product;
a hydrogenation reaction unit, preparing the crude product from the lithium precipitation reaction unit and water into slurry, and introducing carbon dioxide gas to obtain a lithium bicarbonate clarified liquid;
the ion exchange unit is used for carrying out ion exchange on the lithium bicarbonate clarified liquid from the hydrogenation reaction unit to realize the advanced treatment of anions and cations;
a purification and refining unit, which is used for refining the purified solution by adding a complexing agent and a membrane separation technology into the solution from the ion exchange unit;
and a spray drying unit for spray drying the purified liquid from the purification and purification unit to obtain high-purity lithium carbonate.
2. A method for preparing high-purity lithium carbonate by using lithium-containing waste materials is characterized by comprising the following steps:
step I, adding lithium-containing waste and an extracting agent into an extraction kettle in proportion, controlling the temperature to be 20-60 ℃, carrying out heat preservation and stirring reaction for 10-120 min, obtaining an extraction liquid after the reaction is finished, and enriching and separating lithium ions;
step II, adding the extraction liquid obtained in the step I into a reaction kettle, heating to 90-95 ℃, adding a saturated sodium carbonate solution in a pulse form, keeping the temperature, stirring uniformly, reacting for 0.5-2 hours, adding seed crystals to promote crystallization of lithium carbonate to form lithium carbonate slurry, and filtering and separating to obtain a crude lithium carbonate product;
step III, adding water into the crude lithium carbonate product obtained in the step II to prepare lithium carbonate slurry, introducing carbon dioxide gas until the solution is clear from turbid, and obtaining a lithium bicarbonate solution after the reaction is finished;
step IV, passing the lithium bicarbonate solution obtained in the step III through one-stage or multi-stage ion exchange columns loaded with cation exchange resin, anion exchange resin and/or chelating resin to respectively remove trace ion impurities in the solution;
v, adding a complexing agent into the solution obtained in the step IV, complexing trace calcium, magnesium and iron ions in the filtrate into complex ions with larger volume, and separating lithium ions with smaller volume through an ultrafiltration membrane to obtain a refined lithium-rich solution;
and VI, spray drying the refined lithium-rich solution in the step V to obtain high-purity lithium carbonate.
3. The method according to claim 2, wherein in the step I, the extraction temperature is 20-80 ℃, the extraction time is 15-120 min, and the extracting agent is one or a mixture of several of pyrrole hexafluorophosphate ionic liquid, imidazole hexafluorophosphate ionic liquid, pyridine hexafluorophosphate ionic liquid, piperidine hexafluorophosphate ionic liquid, N-N, dimethylformamide, tributyl phosphate, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and N' N-bis (2-ethylhexyl) acrylamide.
4. The method of claim 2, wherein: and in the step II, adding a saturated sodium carbonate solution with the pulse frequency of 10-100 KHz.
5. The method of claim 2, wherein: in the step II, the seed crystal is lithium carbonate with the particle size of nano-scale and various particle sizes of hundreds of microns, and the shape of the seed crystal is one or more of spherical, rod-shaped, flower-shaped, sheet-shaped and hollow spheres.
6. The method of claim 2, wherein: in the step III, the ratio of the lithium carbonate crude product to the water is 1: 5-1: 50, the flow rate of the carbon dioxide gas is 0.5-5L/min.
7. The method according to claim 2, wherein in step IV, the cation exchange resin is selected from one or more of styrene, acrylic acid and phenolic aldehyde; the anion exchange resin is selected from one or more of styrene, acrylic acid and epoxy; the chelating resin is selected from one or more of D110, D113, D152, D401, D403, D418 and D564.
8. The process according to claim 2, wherein in step IV, the flow rate of the concentrate through the ion exchange column is 5 to 50 BV/h.
9. The method of claim 2, wherein: in the step V, the complexing agent is one or more of EDTA, crown ether, nitrilotriacetic acid, citric acid, tartaric acid, oleic acid, gluconic acid and diethylenetriaminepentaacetic acid.
10. The processing method according to claim 2, characterized in that: in the step V, the ultrafiltration membrane is made of ceramics, polysulfone, polyether ether ketone, polyvinylidene fluoride or polytetrafluoroethylene, the filtration precision of the ultrafiltration membrane is 10-100nm, the component mode of the ultrafiltration membrane is hollow fiber, roll type, plate type or tube type, and the filtration mode of the ultrafiltration membrane is cross flow or counter flow filtration.
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| CN111960444A (en) * | 2020-08-28 | 2020-11-20 | 贵州大龙汇成新材料有限公司 | Method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution |
| CN112408437A (en) * | 2020-11-19 | 2021-02-26 | 江西天新药业股份有限公司 | Method for recovering lithium salt |
| CN115010098A (en) * | 2022-07-27 | 2022-09-06 | 季华实验室 | Method for efficiently preparing ultra-clean high-purity sulfuric acid |
| CN115417434A (en) * | 2022-09-02 | 2022-12-02 | 安徽格派锂电循环科技有限公司 | Method for recovering valuable metals in black powder of waste lithium ion battery and preparing lithium carbonate product in carbothermic reduction mode |
| CN117105336A (en) * | 2023-10-13 | 2023-11-24 | 山东金泽水业科技有限公司 | Method for treating lithium-containing wastewater and co-producing lithium carbonate |
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