CN219017751U - Lithium ion battery electrode powder recovery system - Google Patents
Lithium ion battery electrode powder recovery system Download PDFInfo
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- CN219017751U CN219017751U CN202223219617.1U CN202223219617U CN219017751U CN 219017751 U CN219017751 U CN 219017751U CN 202223219617 U CN202223219617 U CN 202223219617U CN 219017751 U CN219017751 U CN 219017751U
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Abstract
The utility model discloses a lithium ion battery electrode powder recovery system. The system comprises a leaching unit, a purifying unit, a neutralization precipitation unit, a impurity removing device and a carbon dioxide lithium precipitation device which are sequentially connected, wherein the leaching unit, the purifying unit, the neutralization precipitation unit, the impurity removing device and the carbon dioxide lithium precipitation device are used for sequentially carrying out acid leaching on electrode powder, purifying leaching liquid, neutralizing precipitation on the purified leaching liquid by adopting a calcium-based neutralizer, carrying out cyclone separation on the discharged underflow, filtering and overflowing to obtain lithium-containing filtrate, removing impurities from the lithium-containing filtrate, and introducing carbon dioxide lithium precipitation to obtain lithium-precipitating liquid and lithium carbonate slurry; in addition, the carbon dioxide lithium precipitation device is also connected with the purification unit and used for purifying the leaching solution by adopting the lithium precipitation liquid, and is also connected with the impurity removal device and used for removing impurities from the lithium-containing filtrate by adopting the lithium carbonate slurry. The system for recycling the electrode powder can avoid the high-energy-consumption process of evaporation and crystallization, simplify the flow, reduce the energy consumption and the cost, and has high recovery rate and higher purity of each recycled product.
Description
Technical Field
The utility model relates to the technical field of lithium ion battery electrode recycling, in particular to a low-cost and short-flow lithium ion battery electrode powder recycling system.
Background
With the rapid development of new energy automobiles, the consumption of a power battery serving as a heart of the new energy automobile is also the water-rise ship height. With the rapid development of lithium batteries, the next is the rough waste lithium ion battery retirement tide. The comprehensive recovery of the waste lithium ion battery becomes an important subject which is essentially faced by the multiple pressures of resource, environmental protection and safety. In recent years, research on the process of recycling lithium batteries is under way, and some processes have been successfully applied to industrial production and have good benefits. The recovery process of the waste lithium ion battery is various and complex, but can be roughly divided into three steps: disassembling and crushing the battery, heat treating and physically sorting, and comprehensively recovering electrode powder. The recovery value of the four elements of nickel, cobalt, manganese and lithium contained in the electrode powder is extremely high, and the recovery value is heavy in the whole battery recovery link.
The more common treatment processes at present mainly comprise the following steps:
(1) synthetic methods and ion exchange methods. Firstly, fully dissolving a separated positive electrode material by adopting dilute hydrochloric acid, removing impurities, centrifugally separating, adjusting the pH value of a supernatant to be alkaline, and introducing pure oxygen to oxidize cobalt and nickel into trivalent ions; then, the solution is repeatedly passed through weak acid cation exchange resin, the cobalt and nickel are separated by eluting with ammonium sulfate solution with different concentrations, the cobalt complex is eluted by sulfuric acid, the cation exchange resin is regenerated, and finally cobalt and lithium are deposited by oxalate.
(2) Precipitation. By H 2 SO 4 +H 2 O 2 And (3) leaching the positive and negative electrode mixed active substances of the separated current collector on line, removing iron from the leached filtrate by adopting a sodium-iron-vanadium method, extracting and separating copper, hydrolyzing and precipitating to remove aluminum, adding a proper amount of nickel sulfate, manganese sulfate or cobalt sulfate, and preparing a nickel-cobalt-manganese carbonate precursor by adopting a carbonate coprecipitation method.
(3) And (5) coprecipitation. Fully dissolving the separated positive fragments by using sodium hydroxide solution, passing through P 2 O 4 Adding H after removing impurities 2 SO 4 And H is 2 O 2 Reducing the mixed solution into a solution containing nickel, cobalt and manganese, and adjusting the molar ratio of the solution to 1 by adopting nickel sulfate, manganese sulfate or cobalt sulfate: 1:1, adding a certain amount of NH 3 And preparing a ternary precursor of nickel, cobalt and manganese, and finally adding lithium carbonate into the ternary precursor, and performing high-temperature sintering to obtain the ternary positive electrode material of nickel, cobalt and lithium manganate.
Chinese application CN109593963a discloses a new method for selectively recovering valuable metals from waste lithium batteries. Firstly, leaching anode and cathode powder of a waste ternary lithium ion battery by sulfuric acid; extracting nickel sulfate and cobalt sulfate from the leaching solution by extraction, or adding sodium hydroxide to obtain cobalt nickel hydroxide precipitate; and finally adding sodium carbonate into the residual solution to precipitate lithium to obtain lithium carbonate.
Chinese application CN109666799a discloses a method for separating and recovering valuable metals from waste lithium battery materials and application thereof. Firstly, leaching a battery anode material by using sulfuric acid and a reducing agent (one or more of glucose, sucrose, vitamin C, grape seeds, sodium thiosulfate and sodium sulfite); then adding an additive into the leaching solution to adjust the pH value to 10-12, coprecipitating nickel, cobalt and manganese ions in the leaching solution, and filtering to obtain nickel-cobalt-manganese precipitate and lithium ion solution; and finally concentrating the lithium ion solution to 20-45 g/L, and adding excessive anhydrous sodium carbonate to react to obtain precipitate lithium carbonate.
Chinese application CN109721110a discloses a method for obtaining nickel cobalt manganese hydroxide from active materials recovered from waste lithium batteries. Firstly, preserving heat and stirring nickel-cobalt-manganese leaching solution obtained from waste power lithium batteries for 0.1-5 h at the temperature of-20-10 ℃, and filtering out precipitated crystalline salt to obtain nickel-cobalt-manganese sulfate solution; and then regulating the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese sulfate solution to be 1-3 mol/L, adding ammonia water until the pH value of the system is 8-10 for complex reaction, then regulating the pH value of the reaction system to be 10-12, aging after regulation, and washing and drying a filtered filter cake to obtain the nickel cobalt manganese ternary element composite hydroxide.
Chinese application CN111261967a discloses a method for recovering waste lithium batteries and a battery grade nickel-cobalt-manganese mixed crystal prepared by recovering. Firstly, separating positive electrode powder, preparing slurry, leaching, adding a precipitator (any one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium hydroxide and ammonia water) after removing impurities, and carrying out solid-liquid separation to obtain nickel-cobalt-manganese slag and lithium-containing solution.
The present inventors have found that in the prior art including the above-mentioned documents, when the neutralization precipitation method is used for the recovery treatment, the neutralization reagent is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and aqueous ammonia, and these neutralization reagents can be summarized as sodium-based reagents or ammonium-based reagents. In the sulfuric acid leaching solution system of the electrode powder, no matter the sodium-based reagent or the ammonium-based reagent is adopted for neutralization, the neutralization product can generate corresponding sulfate which is soluble in water, for example, sodium sulfate is generated when sodium hydroxide is adopted for neutralization, and ammonium sulfate is generated when ammonia water is adopted; however, these water-soluble sulfates must be removed from the system by evaporative crystallization, which is energy intensive, whether by steam multi-effect evaporation or MVR evaporation; and these reagents are also relatively expensive and the cost of the reagents in the production process is high. On the other hand, the inventor also finds that in the subsequent step of producing lithium carbonate, the traditional process adopts sodium carbonate as a lithium precipitating agent to precipitate lithium carbonate, so that sodium sulfate cannot be produced, and the part of salt-containing solution can be removed from the system through evaporation and crystallization, and the process has the defect of high energy consumption. In summary, no recovery system for recovering electrode powder has the advantages of simple structure, convenient operation, low energy consumption, low cost and high recovery rate in the prior art.
Disclosure of Invention
The utility model aims at providing a lithium ion battery electrode powder recovery system. The above object can be achieved by the following embodiments of the present utility model:
according to an embodiment of the present utility model, there is provided a lithium ion battery electrode powder recovery system including: the leaching unit, the purifying unit, the neutralization precipitation unit, the impurity removal device and the carbon dioxide lithium precipitation device are sequentially connected; the leaching unit is used for carrying out acid leaching on the electrode powder to obtain leaching liquid; the purifying unit is used for purifying the leaching solution to obtain purified leaching solution; the neutralization and precipitation unit comprises a cyclone, is provided with a calcium-based neutralizer adding port, and is used for neutralizing and precipitating the purified leaching solution by adding the calcium-based neutralizer, and separating by adopting the cyclone to obtain a lithium-containing filtrate; the impurity removing device is used for removing impurities from the lithium-containing filtrate to obtain a lithium-containing solution; the carbon dioxide lithium precipitation device is used for precipitating lithium from a lithium-containing solution by adopting carbon dioxide to obtain a lithium-precipitated solution and lithium carbonate slurry; the carbon dioxide lithium precipitation device is also connected with the purification unit and is used for purifying the leaching liquid by adopting the lithium precipitation liquid; the carbon dioxide lithium precipitation device is also connected with a impurity removal device and is used for removing impurities from the lithium-containing filtrate by adopting lithium carbonate slurry.
Optionally, the leaching unit comprises two sections of leaching devices and two sections of washing devices which are sequentially connected, wherein a filtrate outlet of the two sections of leaching devices and a washing liquid outlet of the two sections of washing devices are connected with an inlet of the first section of leaching devices, the second section of washing devices are also provided with graphite slag discharge ports, and a filtrate outlet of the first section of leaching devices is connected with the purifying unit.
Optionally, the purifying unit further comprises a two-stage washing device, wherein a washing liquid outlet of the two-stage washing device is connected with an inlet of the one-stage leaching device, and the two-stage washing device is provided with an iron aluminum slag outlet.
Optionally, in the neutralization precipitation unit, the cyclone has a underflow opening and an overflow opening; the overflow port is provided with a filtering device for filtering overflow to obtain lithium-containing filtrate and nickel-cobalt-manganese precipitate; the underflow opening is connected with a gypsum product preparation device for washing the underflow by adopting an acid solution to obtain a gypsum product, and a filtrate outlet of the gypsum product preparation device is connected with a leaching unit.
Optionally, the impurity removing device is provided with a filter residue discharging outlet for discharging carbonate products.
Optionally, the carbon dioxide lithium precipitation device comprises: the device comprises a venturi, a body and a lithium-precipitating post-liquid tank which are sequentially connected, wherein the venturi is provided with a lithium-precipitating pre-liquid inlet, a carbon dioxide inlet and a carbon dioxide return port; the lithium precipitation precursor liquid inlet is used for adding a lithium-containing solution; the body is provided with a first carbon dioxide outlet which is connected with the gas-liquid separator; the lithium-precipitation liquid tank is provided with a second carbon dioxide outlet; and the gas outlet of the gas-liquid separator and the second carbon dioxide outlet are connected with the carbon dioxide return port of the venturi tube.
Optionally, in the carbon dioxide lithium precipitation device, the body is formed by connecting an upper straight cylinder section and a lower cone cylinder section; the straight barrel section is provided with a mixed slurry inlet and a lithium-precipitation liquid outlet, the body is connected with the venturi through the mixed slurry inlet, and the body is connected with a lithium-precipitation liquid tank through the lithium-precipitation liquid outlet; the first carbon dioxide outlet is positioned in the straight cylinder section; the cone section is provided with a lithium carbonate slurry discharge outlet.
Optionally, in the carbon dioxide lithium precipitation device, the post-lithium precipitation liquid outlet of the post-lithium precipitation liquid tank is connected with the purification unit, and the post-lithium precipitation liquid outlet of the post-lithium precipitation liquid tank is also connected with the leaching unit.
Optionally, in the carbon dioxide lithium precipitation device, a lithium carbonate slurry outlet through a cone section is connected with the impurity removal device, and the lithium carbonate slurry outlet is also connected with the leaching unit.
Optionally, in the carbon dioxide lithium precipitation device, the lithium carbonate slurry outlet is further connected with a filtering device, and the filtering device is used for filtering the lithium carbonate slurry to obtain a lithium carbonate product.
The beneficial effects are that: by adopting the embodiment, the high-energy-consumption process of evaporation and crystallization is avoided, the process is simplified, the energy consumption and the cost are reduced, the recovery rate is high, and the purity of each recovered product is high.
In addition, in the preferred embodiment, the carbon dioxide utilization rate and thus the lithium precipitation efficiency can be improved by adopting a specific carbon dioxide lithium precipitation device.
Drawings
Fig. 1 is a schematic diagram of a connection structure of a lithium ion battery electrode powder recovery system according to an embodiment of the utility model.
Fig. 2 is a schematic structural diagram of a carbon dioxide precipitation apparatus used in a lithium ion battery electrode powder recovery system according to an embodiment of the present utility model.
Fig. 3 is a flowchart illustrating the operation of the electrode powder recycling system for lithium ion batteries according to an embodiment of the present utility model.
Reference numerals: the device comprises a venturi tube 1, a straight barrel section 2, a conical barrel section 3, a liquid outlet after lithium precipitation 4, a first carbon dioxide outlet 5, a gas-liquid separator 6, a lithium carbonate slurry outlet 7 and a liquid tank after lithium precipitation 8.
Detailed Description
The technical solutions of the present utility model will be clearly and completely described in conjunction with the embodiments of the present utility model, and it is apparent that the described embodiments are only some embodiments of the present utility model, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the utility model, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the utility model without making any inventive effort, are intended to be within the scope of the utility model.
As described in the background art of the present application, the present inventors have found that the recovery of lithium ion battery electrode powder requires a high-energy process of evaporative crystallization, and based on this, the recovery system of lithium ion battery electrode powder is improved, which avoids the high-energy process of evaporative crystallization and reduces the recovery processing cost. The application innovates to neutralization precipitation unit, adds the neutralizer that is low-priced and can avoid neutralization process byproduct soluble salt through setting up calcium-based neutralizer and adding the mouth to avoid this high energy consumption process of evaporation crystallization and reduce the reagent cost of production process simultaneously. The application is also innovative to the lithium deposition device, and the low-cost lithium deposition agent capable of avoiding byproduct soluble salt in the lithium deposition process is added through the venturi tube, and the recycling of carbon dioxide of the lithium deposition device is improved, so that the high-energy consumption procedure of evaporation and crystallization is avoided, and the reagent cost of the production process is reduced. The improved system is adopted to perform the procedures of neutralization, lithium precipitation and the like, so that the recovery effect of the electrode powder of the lithium ion battery is optimal.
Lithium ion batteries are novel batteries in which a lithium-containing compound is used as a positive electrode material and carbon intercalated with lithium is used as a negative electrode. The positive electrode material of the lithium ion battery comprises: lixCoO 2 、LixNiO 2 、LixMnO 4 ，Li(Ni x Co y Mn 1-x-y )O 2 Or Li (Ni) x Co y Al 1-x-y )O 2. . The electrode powder is a mixture obtained in the process of disassembling and crushing the lithium ion battery, and is a mixture of anode powder, cathode powder, a small amount of copper, iron, aluminum and the like.
Fig. 1 schematically illustrates a connection structure of a lithium ion battery electrode powder recovery system according to an embodiment of the present utility model. As shown in fig. 1, the lithium ion battery electrode powder recovery system in this embodiment includes: leaching unit, purification unit, neutralization precipitation unit, edulcoration device, carbon dioxide heavy lithium device. In addition, as shown in fig. 1, in this embodiment, the carbon dioxide lithium precipitation device is also connected to a purification unit and an impurity removal device.
Wherein, in the leaching unit, can include two sections leaching devices and two sections washing devices that link to each other in proper order, can discharge the graphite sediment of selling after two sections washing device wash, two sections leaching device's filtrate export and two sections washing device's washing liquid export all link to each other with one section leaching device's entry to carry out the reprocessing, improve treatment effeciency.
The purifying unit can comprise two sections of washing devices, the iron aluminum slag which can be sold outside is discharged after the washing of the two sections of washing devices, and the washing liquid outlets of the two sections of washing devices are connected with the inlet of the one section of leaching device so as to carry out retreatment and improve the treatment efficiency.
The neutralization precipitation unit is provided with a calcium-based neutralizing agent adding port, and neutralization precipitation is performed by adding the calcium-based neutralizing agent. The neutralization precipitation unit comprises a cyclone, and the cyclone is a hydrocyclone. The lower part of the cyclone is provided with a underflow opening for discharging the underflow, and the underflow is prepared into the saleable gypsum. The upper part of the cyclone is provided with an overflow port, and the overflow port is used for solid-liquid separation to obtain lithium-containing filtrate and nickel-cobalt-manganese precipitate which can be sold out.
The impurity removing device removes impurities from the lithium-containing filtrate obtained after filtration overflow to obtain a lithium-containing solution, and the lithium-containing solution is used as a lithium precipitation precursor solution to be sent to the carbon dioxide precipitation device for lithium precipitation, so that the recovery efficiency is ensured and the carbon dioxide utilization rate is improved.
Fig. 2 schematically shows the structure of a carbon dioxide precipitation device used in the lithium ion battery electrode powder recovery system in an embodiment.
As shown in fig. 2, the carbon dioxide lithium precipitation device comprises a venturi tube 1, a body, a lithium precipitation post-liquid tank 8 and a gas-liquid separator 6 which are sequentially connected. The venturi tube 1 is provided with a lithium precipitation front liquid inlet, a carbon dioxide return port and a mixed slurry outlet. The venturi 1 is arranged horizontally and causes the mixed slurry to enter tangentially into the straight barrel section 2 of the body. The body is formed by connecting a straight cylinder section 2 at the upper part and a conical cylinder section 3 with an inverted cone shape at the lower part. The straight section 2 is provided with a mixed slurry inlet connected with a mixed slurry outlet, the top of the straight section is provided with a first carbon dioxide outlet 5 and a lithium-precipitation rear liquid outlet 4, wherein the first carbon dioxide outlet 5 is connected to a carbon dioxide return port through a gas-liquid separator 6, the lithium-precipitation rear liquid outlet 4 is connected to a lithium-precipitation rear liquid tank 8, the top of the lithium-precipitation rear liquid tank 8 is provided with a second carbon dioxide outlet, and the second carbon dioxide outlet is connected to the carbon dioxide return port. The bottom of the cone section 3 is provided with a lithium carbonate slurry discharge outlet 7, and the lithium carbonate slurry discharge outlet 7 is respectively connected with the impurity removing device and the purifying unit and is also connected with a filtering device to obtain a lithium carbonate product. The bottom of the lithium-precipitation liquid tank 8 is provided with a lithium-precipitation liquid external discharge port which is respectively connected with the purification unit and the leaching device.
According to the embodiment, the improved carbon dioxide lithium precipitation device is adopted for precipitating lithium, so that the carbon dioxide utilization rate is improved, and the recovery efficiency of electrode powder is improved. The venturi 1 is added before the carbon dioxide lithium precipitation device, so that carbon dioxide and lithium precipitation precursor liquid are fully mixed and enter the carbon dioxide lithium precipitation device for lithium precipitation, and part of unreacted carbon dioxide in the carbon dioxide lithium precipitation device is discharged through the first carbon dioxide discharge port 5 above and is separated by the gas-liquid separator 6 and then enters the venturi 1 again; the other part of the solution and the solution after lithium precipitation enter the solution tank 8 after lithium precipitation together, are discharged through a waste gas port above the tank body, namely a second carbon dioxide discharge port, and return to the venturi tube 1, so that the high-efficiency utilization of carbon dioxide is realized. The specific principle is as follows: after the mixed slurry enters a carbon dioxide lithium precipitation device, the mixed slurry can spirally move downwards, and simultaneously the lithium precipitation precursor liquid fully contacts and reacts with carbon dioxide to generate lithium carbonate precipitation, the lithium carbonate precipitation is thrown to the cylinder wall under the action of inertial centrifugal force and is precipitated to the bottom of the conical cylinder section 3 along with the downward rotational flow to be discharged. The clear liquid becomes ascending inner layer rotational flow and is discharged from the top of the straight cylinder section 2. In the process, carbon dioxide released from slurry can form a negative pressure air column at the center of inner layer rotational flow, one part of the negative pressure air column is discharged together with clear liquid and enters the lithium-precipitating liquid tank 8, the other part of the negative pressure air column is discharged through the first carbon dioxide discharge port 5, and the negative pressure air column is separated through the gas-liquid separator 6 and then enters the venturi 1 again, and carbon dioxide entering the lithium-precipitating liquid tank 8 can be discharged from the upper part of the tank body and returns to the venturi 1 again, so that the utilization rate of the carbon dioxide is improved.
Fig. 3 schematically illustrates a specific operation procedure of the electrode powder recovery system for a lithium ion battery in an embodiment of the present utility model when electrode powder is recovered, where the procedure mainly includes three parts of leaching and purifying, precipitating nickel cobalt manganese, and precipitating lithium carbonate, and specifically includes:
firstly, acid leaching is carried out on electrode powder by adopting a leaching device, a purifying device is adopted to purify leaching liquid, and nickel-cobalt-manganese-lithium solution is obtained by filtering by a filtering device.
Sulfuric acid is used as a leaching agent, hydrogen peroxide is used as a reducing agent, and the ternary powder, namely the electrode powder, is subjected to two-stage leaching. Specifically, in the leaching unit, sulfuric acid is firstly adopted as a leaching agent, and hydrogen peroxide is added as a reducing agent to carry out one-stage leaching. The leaching solution obtained by the solid-liquid separation of the first leaching stage is sent to a purification process, the leaching residue, namely the filter cake, is sent to a second leaching stage, the rest valuable metals are continuously leached, and sulfuric acid is also used as a leaching agent in the second leaching stage, and hydrogen peroxide is also added as a reducing agent. The filtrate obtained by the solid-liquid separation of the second stage leaching is returned to the first stage leaching, the leaching slag is the filter cake which is graphite slag, after the two stages of washing is carried out by adding washing water, the graphite slag can be used as a product for sale, and meanwhile, the washing water is returned to the first stage leaching. The recovery rate of each valuable metal can be further improved by returning the filtrate and the washing liquid to be reprocessed.
The leaching solution is obtained by one-stage leaching, and the main components of the leaching solution are mixed solution of nickel sulfate, cobalt sulfate, manganese sulfate and lithium sulfate and a small amount of iron and aluminum impurities. Impurities need to be removed to the maximum extent before the next nickel cobalt manganese precipitation process is performed to improve the product purity. Specifically, in a purification unit, adding a lithium-precipitated solution and lithium carbonate slurry produced in a subsequent process to the leaching solution, and adjusting the pH value of the solution to be 2.5-4.5, so that impurity iron aluminum in the leaching solution forms a precipitate due to hydrolysis reaction, removing the iron aluminum precipitate from the solution through solid-liquid separation to obtain a nickel-cobalt-manganese-lithium solution with higher purity, wherein the content of iron and aluminum in the solution is less than 0.1g/L, and the iron-aluminum removal rate can reach about 99%. And the iron-aluminum slag obtained by solid-liquid separation is washed by washing water for two sections, the obtained iron-aluminum slag can be sold as a product, and meanwhile, the washing liquid is returned to one section for leaching, so that the recovery rate of valuable metals is improved.
Furthermore, one stage leaching: the reaction temperature is 70-80 ℃, the end point pH value is controlled to be 1.5-3.0, and the reaction time is 1.5-2.5 h. Two-stage leaching: the liquid-solid ratio is controlled to be 5-7, the reaction temperature is 75-85 ℃, the terminal acidity is controlled to be 100-150 g/L, and the reaction time is 1.5-2.5 h. By controlling the leaching parameters, the leaching efficiency is further improved, and the recovery rate of each product is higher.
And secondly, in a neutralization precipitation unit, carrying out neutralization precipitation on the nickel-cobalt-manganese-lithium solution by adopting a calcium-based neutralizer, carrying out cyclone separation, discharging underflow, and filtering overflow to obtain nickel-cobalt-manganese precipitate and lithium-containing filtrate.
And adding a calcium-based neutralizer into the purified nickel cobalt manganese lithium solution. The calcium-based neutralizer comprises one or more of calcium oxide, calcium hydroxide and calcium carbonate. In a neutralization precipitation unit, the pH value of the nickel cobalt manganese lithium solution is regulated to 9-10 by adding the calcium-based neutralizer, so as to carry out neutralization precipitation, wherein nickel ions, cobalt ions and manganese ions in the solution all generate precipitation, and Ca in the neutralizer 2+ Then with SO in solution 4 2- The reaction produces calcium sulfate precipitate.
However, the inventor further found that both calcium sulfate and generated nickel cobalt manganese precipitate are solid, and the conventional solid-liquid separation mode is adopted, so that the difference of sedimentation speeds of the calcium sulfate and the nickel cobalt manganese precipitate in a solution is utilized, the calcium sulfate and the nickel cobalt manganese precipitate are efficiently separated by adopting a hydrocyclone, underflow and overflow are discharged, wherein the underflow (gypsum slurry) can be discharged from the bottom of the hydrocyclone, the overflow is discharged from the upper part, the saleable gypsum can be prepared through filtration, after the overflow is filtered, the filter cake is nickel, cobalt and manganese precipitate and can be sold as MHP, and the filtrate is lithium-containing filtrate (containing calcium and magnesium impurities) and enters a lithium precipitation procedure to recover lithium in the lithium-containing filtrate.
In addition, the inventor of the application also found that a small amount of nickel cobalt manganese precipitate is usually entrained in the gypsum product obtained by filtering the gypsum slurry, and in order to further improve the metal recovery rate, the underflow is sent to a gypsum product preparation device, the gypsum product is firstly washed by adopting a dilute acid solution, and the pH value of the dilute acid solution can be 1.5-2.0; the gypsum product is then filtered to yield a purer gypsum product, at which point the gypsum product is at least 98% pure, and the wash liquor is returned to the leaching process, e.g., to a secondary leach.
Finally, removing impurities from the lithium-containing filtrate in an impurity removing device, and filtering to obtain a lithium-containing solution after removing the impurities; and (3) delivering the lithium-containing solution into a carbon dioxide lithium precipitation device, simultaneously introducing carbon dioxide into the lithium-containing solution, mixing and precipitating lithium to produce lithium carbonate slurry and lithium precipitation post-liquid.
The lithium-containing filtrate is filtrate after overflow filtration, the main components of the filtrate are lithium hydroxide and a small amount of calcium and magnesium ions, the impurity is removed by adopting an impurity removing device before lithium precipitation, and calcium and magnesium are removed by adopting lithium carbonate slurry produced in a subsequent process, the lithium carbonate dosage is 1.1-1.3 times of the total reaction theory amount of calcium and magnesium, at the moment, calcium and magnesium generate indissolvable carbonate precipitates to be removed from a system, the outsource carbonate such as calcium carbonate and the like can be prepared, and the lithium-containing solution after impurity removal is used as lithium precipitation precursor solution for lithium precipitation, so that the lithium precipitation efficiency is improved. The method is characterized in that carbon dioxide is introduced into a lithium-containing solution after calcium and magnesium removal, the carbon dioxide and a lithium-precipitating precursor solution are fully mixed to perform cyclone sedimentation for lithium precipitation, at this time, lithium hydroxide and carbon dioxide react to generate lithium carbonate precipitation, lithium carbonate slurry containing the lithium carbonate precipitation is discharged from the lower part, and a lithium-precipitating rear solution is collected in a lithium-precipitating rear solution tank 8.
In addition, as shown in fig. 1, the post-lithium precipitation liquid in the post-lithium precipitation liquid tank 8 can be returned to the purification unit as a pH adjustor for removing iron and aluminum. In addition, the solution after lithium deposition in the solution tank 8 after lithium deposition can be returned to the leaching unit for reprocessing. The solution after lithium deposition is returned to remove iron and aluminum and leached for a period of time, so that the system is recycled, resources are saved, and meanwhile, the unrecovered lithium element in the solution after lithium deposition is recovered again, so that the metal recovery rate is improved.
In addition, as shown in fig. 1, the lithium carbonate slurry discharged from the cone section 3 can be sent to a purification unit for removing iron and aluminum, can be sent to a impurity removal device for removing calcium and magnesium, and can be directly filtered to obtain a product for sale (the purity of the lithium carbonate product is more than or equal to 99.5%). The lithium carbonate slurry is returned to remove iron, aluminum, calcium and magnesium, so that the conventional sodium carbonate is replaced, the introduction of sodium element is avoided, the subsequent evaporation and crystallization operation is not needed, and the disposable investment and the production cost are greatly saved.
The improved carbon dioxide lithium precipitation device is adopted to carry out lithium precipitation, specifically, lithium precipitation front liquid and carbon dioxide are fully mixed in a venturi tube 1, mixed slurry enters a straight barrel section 2 for cyclone precipitation, produced lithium carbonate is precipitated into a cone bottom and finally discharged from a lithium carbonate slurry discharge outlet 7, lithium precipitation rear liquid slowly rises in the straight barrel section 2 and continuously reacts with unconsumed carbon dioxide, produced lithium carbonate is precipitated to the cone bottom of the cone barrel section 3, the lithium carbonate can be used as a product after filtration for sale, the purity can reach more than 99.5 percent, lithium precipitation rear liquid flows out from a lithium precipitation rear liquid discharge outlet 4, unreacted carbon dioxide is discharged from a first carbon dioxide discharge outlet 5 above the straight barrel section 2, gas returns to the venturi tube 1 after separation by a gas-liquid separator 6, liquid is discharged from a lower discharge outlet, lithium precipitation rear liquid is discharged from a lithium precipitation rear liquid discharge outlet 4 at the top to a lithium precipitation rear liquid tank 8, part of unreacted carbon dioxide in the lithium precipitation rear liquid tank 8 can be discharged from a second carbon dioxide discharge outlet above the lithium precipitation rear liquid tank 8 and flows back to the venturi tube 1 for utilization. By adopting the carbon dioxide lithium precipitation device to precipitate lithium, the utilization rate of carbon dioxide can reach more than 90 percent. The lithium carbonate slurry can be sold as a product after being filtered, the purity can reach more than 99.5%, lithium carbonate precipitation can be obtained by controlling the adding amount of carbon dioxide, specifically, the introducing amount of the carbon dioxide can be 1.0 times of the theoretical reaction total amount of the carbon dioxide and lithium ions, and the lithium carbonate slurry is not suitable for excessive supply, and can be controlled by a flowmeter and a valve in an interlocking way.
The following describes the operation process and detection result of the electrode powder recovery system for lithium ion battery according to the present application with reference to two specific application embodiments:
application example 1
1) The first stage leaching reaction temperature is regulated to be about 70 ℃, the final pH value is controlled to be 2.0, and the reaction time is 2.0h. The solid ratio of the leaching solution at the second stage is controlled to be about 6, the reaction temperature is 80 ℃, the terminal acidity is controlled to be 100g/L, and the reaction time is 2.0h. And (3) returning all the leaching liquid of the second stage to the first stage for leaching, washing the leaching residue of the second stage with water, and then selling the leaching residue as a graphite product, and returning washing water to the second stage for leaching. The leaching rate of nickel, cobalt, manganese and lithium can reach about 98.5 percent by two-stage leaching, and the purity of graphite products can reach more than 98 percent.
2) Adding the lithium-precipitated solution and lithium carbonate slurry produced in the subsequent process into the first-stage leaching solution, adjusting the pH value of the solution to about 3.5, carrying out hydrolysis reaction on iron and aluminum to form precipitate, and removing the precipitate by filtration. The obtained iron-aluminum slag is used as a product for sale or outsourcing treatment after being washed by water, and the washing water is returned to the second stage for leaching. The content of iron and aluminum in the purified solution is less than 0.1g/L, and the iron and aluminum removal rate can reach about 99 percent.
3) Adding CaO into the purified leaching solution to control the pH value of the end point to be 9, wherein nickel, cobalt and manganese ions in the solution all generate precipitation, and Ca in the neutralizer 2+ Then with SO in solution 4 2- The reaction produces calcium sulfate precipitate. The slurry obtained by the reaction is introduced into a hydrocyclone, the gypsum slurry is discharged from the bottom, and the overflow containing nickel cobalt manganese precipitate is discharged from the upper part. And (3) obtaining a nickel-cobalt-manganese precipitate mixture after overflow and further solid-liquid separation, and sending filtrate serving as a calcium-magnesium removing precursor liquid to a impurity removing device for impurity removing. The gypsum and the nickel cobalt manganese precipitate are separated through a hydrocyclone, the content of the gypsum entrained in the nickel cobalt manganese precipitate is less than 1%, and the content of the nickel cobalt manganese precipitate entrained in the gypsum is less than 2%, and the gypsum can be recovered through acid washing.
4) The underflow from the hydrocyclone was washed with a dilute acid solution (pH 2.0). The filtered washing liquid returns to the leaching process, the washing slag is sold as gypsum products, and the purity of the gypsum can reach 99 percent.
5) And adding lithium carbonate slurry produced in the lithium carbonate precipitation step into the calcium and magnesium removal precursor solution, wherein the addition amount of the lithium carbonate slurry is 1.1 times of the theoretical amount of the reaction between the calcium and the magnesium, at the moment, calcium and magnesium generate insoluble carbonate precipitates, the insoluble carbonate precipitates are removed from the system through filtration, and the filtrate is used as the lithium precipitation precursor solution and is sent to the lithium precipitation step for recovering lithium in the lithium precipitation precursor solution. The removal rate of calcium and magnesium can reach about 99 percent.
6) Carbon dioxide is introduced into the lithium precipitation precursor liquid and fully mixed in the venturi tube 1, mixed slurry after mixing enters the straight cylinder section 2 and the cone cylinder section 3 for cyclone precipitation, and produced lithium carbonate is precipitated into the cone bottom and discharged. The solution after lithium precipitation slowly rises in the straight barrel section 2 and continuously reacts with unconsumed carbon dioxide, the produced lithium carbonate is precipitated to the cone bottom, the solution after lithium precipitation flows out from the solution outlet 4 after lithium precipitation into the solution tank 8 after lithium precipitation, the unreacted carbon dioxide is discharged from the carbon dioxide outlet 5 of the straight barrel section 2, and the carbon dioxide discharged from the solution tank 8 after lithium precipitation flows back into the venturi tube 1 together with the carbon dioxide through the gas-liquid separator 6. Wherein, the adding amount of carbon dioxide is controlled to be 1.0 times of the theoretical reaction total amount of lithium ions, and the lithium carbonate precipitate can be obtained. The filtered lithium carbonate can be used as a lithium carbonate product for sale, and the purity of the lithium carbonate can reach more than 99.5 percent. By adopting the device provided by the utility model, the utilization rate of carbon dioxide in the lithium precipitation process can reach more than 90%.
Application example 2
1) The first stage leaching reaction temperature is about 80 ℃, the end point pH value is controlled at 2.0, and the reaction time is 2.0h. The solid ratio of the leaching solution at the second stage is controlled to be about 6, the reaction temperature is 80 ℃, the terminal acidity is controlled to be 150g/L, and the reaction time is 2.0h. And (3) returning all the leaching liquid of the second stage to the first stage for leaching, washing the leaching residue of the second stage with water, and then selling the leaching residue as a graphite product, and returning washing water to the second stage for leaching. The leaching rate of nickel, cobalt, manganese and lithium can reach about 99 percent, and the purity of graphite products can reach more than 98.5 percent through two-stage leaching.
2) Adding the lithium-precipitated solution and lithium carbonate slurry produced in the subsequent process into the first-stage leaching solution, adjusting the pH value of the solution to about 3.5, and removing the solution by filtration because of the formation of precipitate by hydrolysis reaction of iron and aluminum. The obtained iron-aluminum slag is used as a product for sale or outsourcing treatment after being washed by water, and the washing water is returned to the second stage for leaching. The content of iron and aluminum in the purified solution is less than 0.1g/L, and the iron and aluminum removal rate can reach about 99 percent.
3) Adding Ca (OH) into the purified leaching solution 2 Controlling the pH value of the end point to be 10, wherein nickel ions, cobalt ions and manganese ions in the solution all generate precipitation, and neutralizing Ca in the neutralizer 2+ Then with SO in solution 4 2- The reaction produces calcium sulfate precipitate. The slurry obtained by the reaction is introduced into a hydrocyclone, the gypsum slurry is discharged from the bottom, and the nickel-cobalt-manganese precipitate is discharged from the upper part. The overflowed liquid is further subjected to solid-liquid separation to obtain a mixture of nickel, cobalt and manganese precipitates, and the filtrate is used as a calcium and magnesium removing precursor liquid and is sent to a impurity removing procedure. Separating gypsum from nickel cobalt manganese precipitate by hydrocyclone, wherein the content of gypsum entrained in the nickel cobalt manganese precipitate is less than 1The content of nickel-cobalt-manganese precipitates carried in the gypsum is less than 1.5 percent and can be recovered by acid washing.
4) The underflow from the hydrocyclone was washed with a dilute acid solution (pH 2.0). The washing liquid after filtration returns to the leaching process, the washing slag is sold as gypsum products, and the purity of the gypsum can reach 99 percent.
5) And adding lithium carbonate produced in the process of depositing lithium carbonate into the calcium-magnesium removing precursor solution, wherein the adding amount is 1.1 times of the theoretical amount of the reaction between the lithium carbonate and the calcium-magnesium, and calcium and magnesium generate indissolvable carbonate precipitates which are removed from the system by filtration. And sending the filtrate to a lithium precipitation process as a lithium precipitation precursor solution to recover lithium in the filtrate. The removal rate of calcium and magnesium can reach about 99 percent.
6) Carbon dioxide is introduced into the lithium precipitation precursor liquid and fully mixed in the venturi tube 1, mixed slurry after mixing enters the straight cylinder section 2 and the cone cylinder section 3 for cyclone precipitation, and produced lithium carbonate is precipitated into the cone bottom and discharged. The solution after lithium precipitation slowly rises in the straight barrel section 2 and continuously reacts with unconsumed carbon dioxide, the produced lithium carbonate is precipitated to the cone bottom, the solution after lithium precipitation flows out from the solution outlet 4 after lithium precipitation into the solution tank 8 after lithium precipitation, the unreacted carbon dioxide is discharged from the carbon dioxide outlet 5 of the straight barrel section 2, and the carbon dioxide discharged from the solution tank 8 after lithium precipitation flows back into the venturi tube 1 together with the carbon dioxide through the gas-liquid separator 6. And controlling the addition amount of carbon dioxide to be 1.0 time of the theoretical reaction total amount of lithium ions, thus obtaining the lithium carbonate precipitate. The filtered lithium carbonate can be used as a lithium carbonate product for sale, and the purity of the lithium carbonate can reach more than 99.5 percent. By adopting the device provided by the utility model, the utilization rate of carbon dioxide in the lithium precipitation process can reach more than 90%.
Some embodiments of the present application also have the following benefits:
1) Adding a calcium-based neutralizing agent including but not limited to calcium oxide, calcium hydroxide, calcium carbonate and the like into the neutralization precipitation unit through a calcium-based neutralizing agent adding port, and precipitating nickel and manganese from one or more mixed solutions of nickel sulfate, cobalt sulfate and manganese sulfate; meanwhile, gypsum is produced by adopting a hydrocyclone in a neutralization precipitation unit, soluble salt is not byproduct in the reaction process, and the high-energy consumption process of evaporation and crystallization is avoided. And calcium-based reagent (CaO, ca (OH) 2 ) General sodium group (NaOH, na) 2 CO 3 ) Or amino (NH) 4 OH、(NH 4 ) 2 CO 3 ) Reagents are inexpensive, and thus the cost of reagents in the production process can be significantly reduced.
2) The improved carbon dioxide lithium deposition device is adopted to deposit lithium hydroxide, and the carbon dioxide lithium deposition does not produce soluble salt as a byproduct, so that the high energy consumption process of evaporation and crystallization is avoided. And compared with sodium carbonate, the cost of carbon dioxide is lower, and the cost of reagents in the lithium precipitation process can be obviously reduced. In addition, compare with traditional straight-through reaction unit, the carbon dioxide device that sinks lithium after this application improves has increased venturi 1, has increased carbon dioxide recovery pipeline, and carbon dioxide utilization ratio is higher, can reach more than 90%.
3) According to the method, leaching and purifying are carried out through the leaching unit and the purifying unit, calcium-based neutralizer is adopted for precipitation and cyclone separation through the neutralization precipitation unit, impurity is removed through the impurity removing device, improved rear device lithium precipitation is adopted after impurity removal, the high-energy consumption evaporation and crystallization process is avoided, the cost is reduced, the obtained lithium precipitation rear liquid can be returned to the purifying and/or leaching step for use or is treated, the obtained lithium carbonate can be filtered and then is sold as a product, and the impurity removing and purifying steps can be returned for full use. Not only solves the problems of complex recovery process and long flow of the existing electrode powder; the evaporative crystallization process is avoided, and the energy consumption level of the existing recovery process is reduced; meanwhile, the problem of higher reagent cost in the existing recovery process is solved; and the purity of each obtained product is higher, thereby realizing the purpose of high-efficiency recovery.
The description of the present utility model has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the utility model in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiments were chosen and described in order to best explain the principles of the utility model and the practical application, and to enable others of ordinary skill in the art to understand the utility model for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A lithium ion battery electrode powder recovery system, comprising: the leaching unit, the purifying unit, the neutralization precipitation unit, the impurity removal device and the carbon dioxide lithium precipitation device are sequentially connected, wherein,
the leaching unit is used for carrying out acid leaching on the electrode powder to obtain leaching liquid;
the purifying unit is used for purifying the leaching solution to obtain purified leaching solution;
the neutralization and precipitation unit comprises a cyclone, is provided with a calcium-based neutralizer adding port, and is used for neutralizing and precipitating the purified leaching solution by adding the calcium-based neutralizer, and separating by adopting the cyclone to obtain a lithium-containing filtrate;
the impurity removing device is used for removing impurities from the lithium-containing filtrate to obtain a lithium-containing solution;
the carbon dioxide lithium precipitation device is used for precipitating lithium from a lithium-containing solution by adopting carbon dioxide to obtain a lithium-precipitated solution and lithium carbonate slurry;
the carbon dioxide lithium precipitation device is also connected with the purification unit and is used for purifying the leaching liquid by adopting the lithium precipitation liquid; the carbon dioxide lithium precipitation device is also connected with a impurity removal device and is used for removing impurities from the lithium-containing filtrate by adopting lithium carbonate slurry.
2. The lithium ion battery electrode powder recovery system according to claim 1, wherein the leaching unit comprises a two-stage leaching device and a two-stage washing device which are sequentially connected, wherein a filtrate outlet of the two-stage leaching device and a washing liquid outlet of the two-stage washing device are connected with an inlet of the one-stage leaching device, the two-stage washing device is further provided with a graphite slag outlet, and a filtrate outlet of the one-stage leaching device is connected with the purifying unit.
3. The lithium ion battery electrode powder recovery system according to claim 2, further comprising a two-stage washing device in the purification unit, wherein a washing liquid outlet of the two-stage washing device is connected with an inlet of the one-stage leaching device, and the two-stage washing device is provided with an iron-aluminum slag discharge outlet.
4. The lithium ion battery electrode powder recovery system according to claim 1, wherein in the neutralization precipitation unit, the cyclone has a underflow port and an overflow port; the overflow port is provided with a filtering device for filtering overflow to obtain lithium-containing filtrate and nickel-cobalt-manganese precipitate; the underflow opening is connected with a gypsum product preparation device for washing the underflow by adopting an acid solution to obtain a gypsum product, and a filtrate outlet of the gypsum product preparation device is connected with a leaching unit.
5. The lithium ion battery electrode powder recovery system of claim 1, wherein the impurity removal device has a residue discharge outlet for discharging carbonate product.
6. The lithium ion battery electrode powder recovery system of claim 1, wherein the carbon dioxide precipitation device comprises: the device comprises a venturi, a body and a lithium-precipitating post-liquid tank which are sequentially connected, wherein the venturi is provided with a lithium-precipitating pre-liquid inlet, a carbon dioxide inlet and a carbon dioxide return port; the lithium precipitation precursor liquid inlet is used for adding a lithium-containing solution; the body is provided with a first carbon dioxide outlet which is connected with the gas-liquid separator; the lithium-precipitation liquid tank is provided with a second carbon dioxide outlet; and the gas outlet of the gas-liquid separator and the second carbon dioxide outlet are connected with the carbon dioxide return port of the venturi tube.
7. The lithium ion battery electrode powder recovery system according to claim 6, wherein in the carbon dioxide precipitation device, the body is formed by connecting an upper straight cylinder section and a lower cone cylinder section; the straight barrel section is provided with a mixed slurry inlet and a lithium-precipitation liquid outlet, the body is connected with the venturi through the mixed slurry inlet, and the body is connected with a lithium-precipitation liquid tank through the lithium-precipitation liquid outlet; the first carbon dioxide outlet is positioned in the straight cylinder section; the cone section is provided with a lithium carbonate slurry discharge outlet.
8. The lithium ion battery electrode powder recovery system according to claim 6, wherein in the carbon dioxide precipitation device, the post-precipitation liquid external discharge port of the post-precipitation liquid tank is connected with the purification unit, and the post-precipitation liquid external discharge port of the post-precipitation liquid tank is also connected with the leaching unit.
9. The lithium ion battery electrode powder recovery system according to claim 7, wherein in the carbon dioxide precipitation device, a lithium carbonate slurry discharge outlet through a cone section is connected with the impurity removal device, and the lithium carbonate slurry discharge outlet is also connected with the leaching unit.
10. The lithium ion battery electrode powder recovery system according to claim 7, wherein in the carbon dioxide precipitation device, the lithium carbonate slurry discharge outlet is further connected with a filtering device for filtering the lithium carbonate slurry to obtain a lithium carbonate product.
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