CN111268747B

CN111268747B - Recycling method and system of waste ternary battery positive electrode material based on hydrochloric acid regeneration cycle

Info

Publication number: CN111268747B
Application number: CN202010223777.XA
Authority: CN
Inventors: 杨刚; 王云山; 安学斌
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2020-03-26
Filing date: 2020-03-26
Publication date: 2021-04-27
Anticipated expiration: 2040-03-26
Also published as: CN111268747A

Abstract

The invention relates to a resource recovery method and a resource recovery system of a waste ternary battery anode material based on hydrochloric acid regeneration cycle, wherein the method comprises the steps of activating and screening the waste ternary battery anode material to obtain ternary material powder, then carrying out hydrochloric acid pickling and decoppering to obtain a solution containing nickel chloride, cobalt chloride, manganese chloride and lithium chloride, supplementing part of ternary chloride to enable the content of the substances in the solution to meet the requirement of a ternary precursor material, carrying out thermal decomposition to obtain mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl, absorbing the HCl to obtain hydrochloric acid for cyclic utilization, carrying out water leaching on the mixed oxides to obtain an oxide filter cake and a lithium chloride solution, and calcining the oxide filter cake to obtain a ternary precursor oxide; the method of the invention utilizes the characteristic that nickel chloride, cobalt chloride and manganese chloride are easy to pyrolyze, realizes the separation of nickel, cobalt, manganese and lithium, simultaneously realizes the cyclic utilization of hydrochloric acid, and has no secondary pollution.

Description

Recycling method and system of waste ternary battery positive electrode material based on hydrochloric acid regeneration cycle

Technical Field

The invention belongs to the field of waste lithium battery recovery, and relates to a method and a system for recycling a waste ternary battery anode material based on hydrochloric acid regeneration cycle.

Background

The lithium ion battery has higher working voltage and energy density, stable discharge voltage, no memory effect, light weight and small volume, and is widely applied to the fields of mobile electronic equipment, electric automobiles, reserve power supplies and the like. The lithium battery anode material mainly comprises lithium cobaltate, lithium iron phosphate and a ternary composite material, wherein the ternary battery has the advantages of high energy density, high voltage, good cycle performance and safe operation, is particularly suitable for the power demand of new energy automobiles, is widely applied and greatly promotes the development of the new energy automobiles. With the rapid development of new energy automobiles, on one hand, the use amounts of lithium, nickel, cobalt, manganese and the like are greatly increased, and on the other hand, a large amount of waste lithium ion batteries are eliminated subsequently, so that not only is the resource waste caused, but also the environment is polluted.

Metals such as nickel, cobalt, manganese and the like are used as important materials for national economy and national defense construction, the application range is gradually expanded, and the demand is increased year by year. With the increasing shortage of nickel cobalt mineral resources and environmental protectionThe increasing protection level has made it increasingly important to recover valuable metals such as nickel and cobalt from waste materials such as magnetic materials, waste catalysts, nickel waste residues, and waste batteries. The mass fraction of cobalt in the anode material of the ternary lithium ion battery is 5-20%, the mass fraction of lithium is 5-7%, and the mass fraction of nickel is 5-50%, wherein the mass fraction of cobalt is far higher than that of cobalt ore with the average grade of only 0.3%, and the ternary lithium ion battery has high recovery value. The nickel, cobalt and other valuable components in the anode of the waste ternary battery are higher than those in the original ore, the source is complex, and the impurities are different, so the treatment methods are different; the method mainly adopts wet methods, such as a sulfuric acid dissolving method, a chlorine hydrochloric acid dissolving method, a mixed acid dissolving method, a fire-wet combination method and the like, and has the advantages of simple wet recovery process, small investment and more H used in the reaction process₂SO₄、HCl、HNO₃NaOH and H₂O₂And the like. If ions such as sulfate radicals, chloride ions, sodium ions, nitrate radicals and the like which are put into the waste water or solid waste cannot enter the product, the ions generally enter the waste water or the solid waste to generate a large amount of salt-containing waste water and solid waste, and the secondary pollution to the environment is very easy to cause due to carelessness.

CN106319228A discloses a method for synchronously recovering nickel, cobalt and manganese from a sulfuric acid leaching solution containing nickel, cobalt and manganese waste residues, which comprises (1) sulfuric acid leaching; (2) removing iron and aluminum; (3) extracting copper; (4) extracting zinc; (5) synchronously extracting nickel, cobalt and manganese, then washing the organic phase containing nickel, cobalt and manganese by using dilute sulfuric acid to remove calcium and magnesium impurities carried in the organic phase, and performing countercurrent back extraction by using sulfuric acid to obtain the sulfate of nickel, cobalt and manganese.

CN108539309A discloses a method for recycling a waste nickel cobalt lithium manganate positive electrode material, which comprises the steps of disassembling a waste nickel cobalt lithium manganate battery, crushing a positive electrode plate, sieving the crushed material, and then putting the crushed material into a reduction furnace for hydrogen reduction; washing the obtained reducing material with hot pure water to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, calcining the aluminum hydroxide to obtain superfine aluminum oxide, and performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate; adding a hydrazine hydrate solution into washing slag, adding sodium hydroxide, stirring, reacting, filtering to obtain a second filtrate and a second filter residue, putting the second filter residue into a vacuum drying oven for vacuum drying, and screening and magnetically separating the dried material to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain a nickel-cobalt-manganese ternary mixed solution.

Therefore, the development of a recovery technology which has short process flow and can recycle the medium still has important significance.

Disclosure of Invention

The invention aims to provide a resource recovery method and a resource recovery system for a waste ternary battery anode material based on hydrochloric acid regeneration cycle, wherein the method comprises the steps of activating and screening the waste ternary battery anode material to obtain ternary material powder, then carrying out hydrochloric acid leaching, copper removal and desilication to obtain a solution containing nickel chloride, cobalt chloride, manganese chloride and lithium chloride, supplementing part of ternary chloride to enable the content of substances in the solution to meet the requirement of a ternary precursor material, carrying out thermal decomposition to obtain a mixed oxide of nickel oxide, cobalt oxide and manganese oxide and flue gas containing HCl, absorbing the HCl to obtain hydrochloric acid for cyclic utilization, carrying out water leaching on the mixed oxide to obtain an oxide filter cake and a lithium chloride solution, and calcining the oxide filter cake to obtain a ternary precursor oxide; the method of the invention utilizes the characteristic that nickel chloride, cobalt chloride and manganese chloride are easy to pyrolyze, realizes the separation of nickel, cobalt, manganese and lithium, simultaneously realizes the cyclic utilization of hydrochloric acid, and has no secondary pollution.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a resource recycling method of a waste ternary battery positive electrode material based on hydrochloric acid regeneration cycle, which comprises the following steps:

(1) activating the anode material of the waste ternary battery, and then screening to obtain a current collector and ternary material powder;

(2) carrying out hydrochloric acid leaching on the ternary material powder obtained in the step (1), and carrying out solid-liquid separation to obtain a first chloride solution; then, copper removal, desiliconization and solid-liquid separation are carried out to obtain a second chloride solution;

(3) adding nickel chloride, cobalt chloride and manganese chloride into the second chloride solution obtained in the step (2) to obtain a third chloride solution, wherein the adding amount of the nickel chloride, the cobalt chloride and the manganese chloride enables the molar ratio of nickel, cobalt and manganese in the obtained third chloride solution to meet the requirement of a nickel-cobalt-manganese ternary precursor material; then carrying out thermal decomposition on the third chloride solution to obtain mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl, absorbing the HCl to obtain hydrochloric acid, and circulating the hydrochloric acid to the step (2) to be mixed with supplementary hydrochloric acid for hydrochloric acid leaching;

(4) and (4) carrying out water leaching on the mixed oxide of the nickel oxide, the cobalt oxide and the manganese oxide in the step (3), carrying out solid-liquid separation to obtain a lithium chloride solution and an oxide filter cake, and calcining the oxide filter cake to obtain a ternary precursor oxide.

Removing a current collector (an aluminum foil, a copper wire and the like) and a binder and the like in a ternary material by adopting an activation treatment mode, decomposing organic matters, screening to obtain the aluminum foil, the copper foil and the copper wire, and simultaneously obtaining ternary material powder, wherein the nickel, cobalt, manganese and the like in the ternary material powder enter a liquid phase after the ternary material powder is subjected to hydrochloric acid leaching, and then removing copper and silicon to remove impurities such as Cu, silicon and the like in the solution and supplement partial nickel chloride, cobalt chloride and manganese chloride to the solution, so that the content of the nickel chloride, the cobalt chloride and the manganese chloride in the solution meets the requirement of a nickel-cobalt-manganese ternary precursor material; meanwhile, the method utilizes the characteristic that nickel chloride, cobalt chloride and manganese chloride are easily decomposed into mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl under the condition of heating, and lithium chloride is not decomposed, so that the separation of nickel, cobalt, manganese and lithium is realized, hydrochloric acid is obtained through the absorption of HCl in pyrolysis flue gas, the cyclic utilization of hydrochloric acid is realized, no secondary pollution is generated, the mixed oxides contain lithium chloride, a lithium chloride solution and an oxide filter cake are obtained after the mixed oxides are soaked in water, and a ternary precursor oxide is obtained after the oxide filter cake is calcined; the method realizes the recovery of valuable components in the anode material of the waste ternary battery, and has no environmental risk.

Preferably, the temperature of the activation in step (1) is 500-.

In the method, the activation temperature is in the range, which is beneficial to the decomposition of organic matters such as the binder and the like in the anode material of the waste ternary battery, so that the current collector and the ternary material powder can be separated conveniently by screening, when the activation temperature is less than 500 ℃, the binder and the like in the anode material are difficult to be completely decomposed, when the activation temperature is more than 600 ℃, the energy consumption is increased, and simultaneously, the activity of the material is easy to lose, which is not beneficial to the subsequent acid leaching operation.

Preferably, the activation time in step (1) is 60-90min, such as 65min, 70min, 75min, 80min or 85 min.

Preferably, the step (2) further comprises crushing the ternary material powder before the hydrochloric acid leaching.

Preferably, the terminal point of the pulverization is to a particle mesh number of 200 mesh or more, for example, 300 mesh, 400 mesh, 500 mesh, 600 mesh, 700 mesh, or the like.

The ternary material powder obtained in the method is further crushed before hydrochloric acid leaching treatment, so that the granularity of the ternary material powder reaches the specific range, the leaching of nickel, cobalt and manganese in the ternary material powder in the subsequent hydrochloric acid leaching process is facilitated, and the recovery rate of valuable components is improved.

Preferably, the hydrochloric acid used in the hydrochloric acid leaching in the step (2) has a mass concentration of 18-21%, such as 18.5%, 19%, 19.5%, 20% or 20.5%.

The hydrochloric acid with the concentration range is adopted in the process of hydrochloric acid leaching, so that the method is beneficial to the complete leaching of nickel, cobalt and manganese in the ternary material powder, when the mass concentration of the hydrochloric acid is less than 18%, the solution concentration is low, the energy consumption of subsequent chloride decomposition is increased, the constant boiling point of the hydrochloric acid is about 20.5% under normal pressure, the process difficulty is high when the constant boiling point exceeds 21%, and the concentration of the hydrochloric acid generated after the hydrochloric acid is absorbed after the subsequent chloride decomposition is 18-21%.

Preferably, the temperature of the hydrochloric acid leaching in step (2) is 75-85 ℃, such as 78 ℃, 80 ℃ or 83 ℃ and the like.

The method of the invention carries out hydrochloric acid leaching in the temperature range, which is beneficial to the complete leaching of nickel, cobalt and manganese in the ternary material powder; when the temperature is lower than 75 ℃, the yield of nickel, cobalt and manganese after acid leaching is reduced by more than 20 percent, and when the temperature is higher than 85 ℃, the solution generates a large amount of acid-containing steam, so that the energy consumption is high, and the operation is not facilitated.

Preferably, the hydrochloric acid leaching in the step (2) is used for converting nickel, cobalt and manganese in the ternary material powder into nickel chloride, cobalt chloride and manganese chloride, and the amount of the hydrochloric acid used in the hydrochloric acid leaching process is 10-20%, such as 12%, 14%, 16% or 18%, and the like.

The use amount of the hydrochloric acid is controlled to be 10-20% in the acid leaching process of the hydrochloric acid, which is beneficial to the complete leaching of nickel, cobalt and manganese in the ternary material powder.

Preferably, low-pressure steam heating is adopted in the hydrochloric acid leaching process in the step (2).

Preferably, the low pressure steam has a temperature of 140-150 deg.C, such as 142 deg.C, 144 deg.C, 146 deg.C or 148 deg.C, etc., and a pressure of 0.4-0.5MPa, such as 0.42MPa, 0.44MPa, 0.46MPa or 0.48MPa, etc.

Preferably, the decoppering method in the step (2) is reduction decoppering.

Preferably, the decoppering method in step (2) comprises adding iron powder to the first chloride solution.

Preferably, the iron powder is added in an amount such that the pH of the solution is 1-1.6, e.g. 1.1, 1.2, 1.3, 1.4 or 1.5 etc.

According to the method, the solution obtained after acid leaching contains nickel chloride, cobalt chloride, manganese chloride and lithium chloride, metals such as an organic silicon diaphragm and a copper or aluminum shell exist in the battery, and the solution contains Cu, Al, Si and the like after acid leaching, and the pH is adjusted to be 1-1.6 by adding iron powder, so that free hydrochloric acid is eliminated on one hand, and copper is reduced and removed on the other hand.

Preferably, the desilication in step (2) is precipitation desilication.

Preferably, the desiliconization method in the step (2) comprises adding ammonia water into the decoppered solution.

Preferably, the ammonia is added in an amount such that the pH of the solution is 3-4, e.g. 3.2, 3.4, 3.6 or 3.8 etc.

In the method, the solution obtained after reduction and copper removal contains iron, Al, silicon and the like, ammonia water is added to adjust the pH to 3-4, iron-aluminum hydroxide precipitate is generated, and the silicon in the removed solution is further removed.

Preferably, the nickel-cobalt-manganese ternary precursor material in the step (3) comprises any one of type 333, type 523 and type 811.

Preferably, the temperature of the thermal decomposition in step (3) is 450-.

The temperature of the thermal decomposition in the method is in the range, so that the nickel chloride, the cobalt chloride and the manganese chloride are decomposed to generate nickel oxide, cobalt oxide and manganese oxide mixed oxide and HCl, and the lithium chloride is not thermally decomposed at the temperature, so that the separation of the nickel, the cobalt and the manganese from the lithium is realized, the cyclic utilization of the hydrochloric acid is realized, and no secondary pollution is generated.

Preferably, the flue gas in the step (3) further comprises dust removal and temperature reduction before absorption.

Preferably, the temperature of the water immersion in step (4) is 80-95 ℃, such as 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃ or 94 ℃ and the like.

The temperature in the water leaching process is controlled within the range, the lithium chloride in the mixed oxide can be completely leached, when the temperature is lower than 80 ℃, the leaching speed is slow, the leaching rate is greatly reduced by more than 20%, when the temperature is higher than 95 ℃, a large amount of steam is generated, and the energy consumption is greatly increased.

Preferably, the ratio of the mass of water to the mass of the mixed oxide of nickel oxide, cobalt oxide and manganese oxide in the water leaching process of step (4) is (7-12):1, such as 8:1, 9:1, 10:1 or 11: 1.

Preferably, the heating medium used in the water leaching in the step (4) is low-pressure steam, the temperature of the low-pressure steam is 140-150 ℃, such as 142 ℃, 144 ℃, 146 ℃ or 148 ℃, and the like, and the pressure is 0.4-0.5MPa, such as 0.42MPa, 0.44MPa, 0.46MPa or 0.48MPa, and the like.

Preferably, the mass concentration of the lithium chloride solution in the step (4) is 10-15%, such as 11%, 12%, 13%, 14% or the like.

Preferably, the temperature of the calcination in step (4) is 500-600 ℃, such as 520 ℃, 540 ℃, 560 ℃, 580 ℃, and the like.

Preferably, the calcination time in step (4) is 60-90min, such as 65min, 70min, 75min, 80min or 85 min.

Preferably, the method further comprises the steps of adding soluble sulfide into the lithium chloride solution in the step (4) to remove impurities, then carrying out solid-liquid separation, adding a sodium carbonate solution, carrying out solid-liquid separation, and drying to obtain lithium carbonate.

The lithium chloride solution also contains nickel, cobalt and manganese ions, and before the lithium carbonate is prepared, sulfide is added into the solution for precipitation and impurity removal, so that the lithium chloride solution is crystallized, and the purity of the lithium carbonate prepared subsequently is improved.

Preferably, the soluble sulphide comprises sodium sulphide and/or ammonium sulphide.

Preferably, the soluble sulfide is added in an amount such that the nickel, cobalt and manganese in the lithium chloride solution are completely precipitated.

Preferably, the ratio of the molar amount of the soluble sulfide to the sum of the molar amounts of nickel, cobalt and manganese in the lithium chloride solution is (1.05-1.2):1, e.g. 1.1:1 or 1.15:1, etc.

Preferably, the sodium carbonate solution has a mass concentration of 20-25%, such as 21%, 22%, 23%, 24%, or the like.

Preferably, the drying temperature of the lithium carbonate is 150-.

As a preferable technical scheme, the resource recycling method of the waste ternary battery anode material based on the hydrochloric acid regeneration cycle comprises the following steps:

(1) activating the anode material of the waste ternary battery at the temperature of 500-600 ℃, and then screening to obtain a current collector and ternary material powder;

(2) crushing the ternary material powder obtained in the step (1) to powder with the mesh number not less than 200 meshes, then carrying out hydrochloric acid leaching in hydrochloric acid solution with the mass concentration of 18-21%, wherein the temperature of the hydrochloric acid leaching is 75-85 ℃, and carrying out solid-liquid separation to obtain first chloride solution; adding iron powder into the first chloride solution to adjust the pH value to 1-1.6, adding ammonia water to adjust the pH value to 3-4, and carrying out solid-liquid separation to obtain a second chloride solution;

(3) adding nickel chloride, cobalt chloride and manganese chloride into the second chloride solution obtained in the step (2) to obtain a third chloride solution, wherein the adding amount of the nickel chloride, the cobalt chloride and the manganese chloride enables the molar ratio of nickel, cobalt and manganese in the obtained third chloride solution to meet the requirement of a nickel-cobalt-manganese ternary precursor material; then, carrying out thermal decomposition on the third chloride solution at the temperature of 450-550 ℃ to obtain a mixed oxide of nickel oxide, cobalt oxide and manganese oxide and HCl-containing flue gas, wherein HCl in the flue gas is absorbed by water to obtain hydrochloric acid with the mass concentration of 18-21%, and circulating the hydrochloric acid to the step (2) to be mixed with supplemented hydrochloric acid for hydrochloric acid leaching;

(4) carrying out water leaching on the mixed oxide of the nickel oxide, the cobalt oxide and the manganese oxide in the step (3), wherein the ratio of the mass of water to the mass of the mixed oxide in the water leaching process is (7-12) 1, the water leaching temperature is 80-95 ℃, solid-liquid separation is carried out to obtain a lithium chloride solution with the mass concentration of 10-15% and an oxide filter cake, and the oxide filter cake is calcined at 500-600 ℃ for 60-90min to obtain a ternary precursor oxide;

(5) and (3) adding sodium sulfide into the lithium chloride solution obtained in the step (4), wherein the ratio of the molar weight of the sodium sulfide to the sum of the molar weights of nickel, cobalt and manganese in the lithium chloride solution is (1.05-1.2):1, carrying out solid-liquid separation, then adding a sodium carbonate solution with the mass concentration of 20-25% into the filtrate, carrying out solid-liquid separation, and drying at the temperature of 150-180 ℃ to obtain the lithium carbonate.

In a second aspect, the invention provides a recycling system of waste ternary battery anode materials based on hydrochloric acid regeneration cycle, which comprises a high-temperature furnace, a sieving machine, a ball mill, a hydrochloric acid pickling kettle, an acid pickling residue filter press, a solution adjusting tank, a purification filter press, a chloride preparation tank, a ternary pyrolysis furnace, a cyclone separator, a preconcentrator, a hydrochloric acid absorption tower, a water leaching kettle, an oxide filter press and a ternary calcining furnace, wherein an outlet of the high-temperature furnace is connected with an inlet of the sieving machine, an outlet of the sieving machine is connected with an inlet of the ball mill, an outlet of the ball mill is connected with an inlet of the hydrochloric acid pickling kettle, an outlet of the hydrochloric acid pickling kettle is connected with an inlet of the acid pickling residue filter press, a liquid outlet of the acid pickling residue filter press is connected with an inlet of the solution adjusting tank, an outlet of the solution adjusting tank is connected with an inlet of, the liquid outlet of the purification filter press is connected with the inlet of the chloride preparation tank, the outlet of the chloride preparation tank is connected with the liquid inlet of the preconcentrator, the liquid outlet of the preconcentrator is connected with the inlet of the ternary pyrolysis furnace, the gas outlet of the ternary pyrolysis furnace is connected with the inlet of the cyclone separator, the gas outlet of the cyclone separator is connected with the gas inlet of the preconcentrator, the gas outlet of the preconcentrator is connected with the gas inlet of the hydrochloric acid absorption tower, and the liquid outlet of the hydrochloric acid absorption tower is connected with the liquid inlet of the hydrochloric acid leaching kettle; and a solid outlet of the ternary pyrolysis furnace is connected with an inlet of the water leaching kettle, an outlet of the water leaching kettle is connected with an inlet of the oxide filter press, and a solid outlet of the oxide filter press is connected with an inlet of the ternary calcining furnace.

The high-temperature furnace in the resource recovery system is used for activating the anode material of the waste ternary battery to decompose organic matters such as a binder and the like, then the high-temperature furnace is connected with a sieving machine to separate a current collector and ternary material powder, the current collector is recovered, the ternary material powder is sent to a hydrochloric acid pickling kettle to be pickled with hydrochloric acid, a hydrochloric acid inlet is arranged on the hydrochloric acid pickling kettle, a product after pickling with hydrochloric acid is sent to an acid pickling residue filter press to remove waste residues to obtain a filtrate (namely the first chloride solution in the first aspect), then the filtrate is sent to a solution regulating tank to be subjected to decoppering and desiliconization, then the filtrate is sent to a purification filter press to remove precipitates to obtain a filtrate (namely the second chloride solution in the first aspect), then the filtrate is sent to a chloride preparation tank, partial nickel chloride, cobalt chloride and manganese chloride solutions are added to obtain a mixed solution (namely the third chloride solution in the first aspect), the chloride preparation tank is provided with a nickel chloride, cobalt chloride and manganese chloride solution inlet, then the chloride preparation tank is conveyed into a preconcentrator for preconcentration, the mixture flows out from a liquid outlet of the preconcentrator and is conveyed into a ternary pyrolysis furnace for pyrolysis to obtain a mixed oxide containing nickel chloride, cobalt chloride and manganese chloride and flue gas containing HCl, then the flue gas passes through a cyclone separator, the gas enters the preconcentrator for preconcentration of a third chloride solution, then enters a hydrochloric acid absorption tower for absorption to obtain hydrochloric acid, the hydrochloric acid is circulated to a hydrochloric acid pickling kettle, a solid product of the cyclone separator enters the ternary pyrolysis furnace and then enters a water leaching kettle for water leaching, the water leaching product is separated by an oxide filter press to obtain a lithium chloride solution and an oxide filter cake, and the oxide filter cake enters a ternary calciner for calcination to obtain a ternary precursor oxide; the resource recovery system realizes the recovery of nickel, cobalt, manganese and lithium in the anode material of the waste ternary battery, realizes the cyclic utilization of hydrochloric acid by utilizing the characteristics that nickel chloride, cobalt chloride and manganese chloride are easily decomposed by heating to generate mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl, realizes the separation of the mixed oxides of nickel, cobalt and manganese and lithium by combining a water leaching method, and obtains a ternary precursor oxide by calcining; simultaneously through the setting of solution adjustment tank, eliminate impurity such as free hydrochloric acid, copper and silicon in the hydrochloric acid pickling back solution, and then be favorable to improving product purity, the setting of the chloride preparation tank in the system makes can obtain required nickel cobalt manganese ternary precursor material through the pyrolysis, makes the solution that gets into the ternary pyrolysis oven obtain preconcentration simultaneously through the setting of preconcentrator on the one hand, and on the other hand, the flue gas that flows out by the exhanst gas outlet of ternary pyrolysis oven is behind cyclone, and the gas entry that gets into the preconcentrator realizes the flue gas cooling, the absorption of the follow-up HCl of being convenient for to realize the cyclic utilization of hydrochloric acid.

Preferably, a spiral conveyor is arranged between the outlet of the ball mill and the inlet of the hydrochloric acid pickling kettle, and the inlet and the outlet of the spiral conveyor are respectively connected with the outlet of the ball mill and the inlet of the hydrochloric acid pickling kettle.

A spiral conveyor is arranged between the ball mill and the hydrochloric acid leaching kettle, and is convenient for conveying the ball-milled powder to the hydrochloric acid leaching kettle.

Preferably, an acid leaching kettle discharge pump is arranged between the outlet of the hydrochloric acid leaching kettle and the inlet of the acid leaching residue filter press, and the inlet and the outlet of the acid leaching kettle discharge pump are respectively connected with the outlet of the hydrochloric acid leaching kettle and the inlet of the acid leaching residue filter press.

The discharge pump of the acid leaching kettle is arranged for conveying the acid leached product to the acid leaching residue filter press.

Preferably, the solution adjusting tank is provided with an iron powder feeding port and an ammonia water feeding port.

The iron powder inlet is used for adding iron powder, so that free hydrochloric acid in liquid after hydrochloric acid pickling is eliminated, Cu in the solution is reduced, and the purpose of reduction and copper removal is achieved.

Preferably, a regulating tank discharging pump is arranged between the outlet of the solution regulating tank and the inlet of the purifying filter press, and the inlet and the outlet of the regulating tank discharging pump are respectively connected with the outlet of the solution regulating tank and the inlet of the purifying filter press.

The discharge pump of the regulating tank is used for conveying the regulated liquid in the solution regulating tank to a purifying filter press to remove precipitates.

Preferably, the system further comprises a chloride dissolving tank, an outlet of the chloride dissolving tank is connected with an inlet of the chloride preparation tank.

Here, a chloride dissolution tank is provided for dissolving nickel chloride, cobalt chloride and manganese chloride to obtain a solution of the above chloride, which is then transferred to a chloride preparation tank.

Preferably, a precise filter is arranged between the outlet of the chloride dissolving tank and the inlet of the chloride preparation tank, and the inlet and the outlet of the precise filter are respectively connected with the outlet of the chloride dissolving tank and the inlet of the chloride preparation tank.

The fine filter is used for further removing tiny impurities contained in the solution.

Preferably, a dissolving tank discharge pump is arranged between the outlet of the chloride dissolving tank and the inlet of the precision filter, and the inlet and the outlet of the dissolving tank discharge pump are respectively connected with the outlet of the chloride dissolving tank and the inlet of the precision filter.

The discharge pump of the dissolving tank is arranged for outputting the solution in the chloride dissolving tank.

Preferably, a chloride preparation pump is arranged between the outlet of the chloride preparation tank and the inlet of the pre-concentrator, and the inlet and the outlet of the chloride preparation pump are respectively connected with the outlet of the chloride preparation tank and the inlet of the pre-concentrator.

Here a chloride make-up pump is used to deliver the liquid from the chloride make-up tank to the preconcentrator.

Preferably, a pre-concentrator circulating pump is arranged between the liquid outlet of the pre-concentrator and the inlet of the ternary pyrolysis furnace, the liquid outlet of the pre-concentrator is connected with the inlet of the pre-concentrator circulating pump, and the outlet of the pre-concentrator circulating pump is connected with the inlet of the ternary pyrolysis furnace and the top inlet of the pre-concentrator.

The arrangement of the pre-concentrator circulating pump facilitates the liquid in the pre-concentrator to be conveyed into the ternary pyrolysis furnace, meanwhile, partial backflow is arranged at the position, the preferable backflow amount is about 10 times of the spray decomposition amount, the dust in high-temperature flue gas can be thoroughly removed, meanwhile, the solution is evaporated and concentrated, the temperature of the flue gas is reduced, the flow requirement is high, and otherwise, the functions of dust removal, concentration and cooling cannot be realized.

Preferably, a spray pyrolysis pump is arranged between the outlet of the pre-concentrator circulating pump and the inlet of the ternary pyrolysis furnace, and the inlet and the outlet of the spray pyrolysis pump are respectively connected with the outlet of the pre-concentrator circulating pump and the inlet of the ternary pyrolysis furnace.

The arrangement of the spray pyrolysis pump is used for realizing spray pyrolysis and improving the effect of the pyrolysis.

Preferably, a hydrochloric acid pump is arranged between a liquid outlet of the hydrochloric acid absorption tower and a liquid inlet of the hydrochloric acid leaching kettle, and an inlet and an outlet of the hydrochloric acid pump are respectively connected with the liquid outlet of the hydrochloric acid absorption tower and the liquid inlet of the hydrochloric acid leaching kettle.

Here a hydrochloric acid pump is provided for delivering hydrochloric acid.

Preferably, a powder collector is arranged between the solid outlet of the ternary pyrolysis furnace and the inlet of the water leaching kettle; and the inlet and the outlet of the powder collector are respectively connected with the solid outlet of the ternary pyrolysis furnace and the inlet of the water leaching kettle.

The powder collector is arranged to collect the solid product of the ternary pyrolysis furnace and convey the solid product to the water leaching kettle.

Preferably, the system further comprises a tail gas purification tower, and the gas outlet of the hydrochloric acid absorption tower is connected with the gas inlet of the tail gas purification tower.

Here the tail gas cleaning column is arranged to further remove HCl from the tail gas.

Preferably, an acid-resistant tail gas fan is arranged between the gas outlet of the hydrochloric acid absorption tower and the gas inlet of the tail gas purification tower, and the inlet and the outlet of the acid-resistant tail gas fan are respectively connected with the gas outlet of the hydrochloric acid absorption tower and the gas inlet of the tail gas purification tower.

The arrangement of the acid-proof tail gas fan is used for gas transmission between the hydrochloric acid absorption tower and the tail gas purification tower.

Preferably, a liquid outlet of the tail gas purification tower is provided with a purification tower circulating pump, an inlet of the purification tower circulating pump is connected with the liquid outlet of the tail gas purification tower, and an outlet of the purification tower circulating pump is connected with the liquid inlet of the tail gas purification tower and the liquid inlet of the hydrochloric acid absorption tower.

The liquid part at the outlet of the tail gas purification tower is used for absorbing agent of the hydrochloric acid absorption tower and partially reflows, the function of the tail gas purification tower is to remove HCl in the tail gas, a large amount of water is needed for cyclic removal, and the solution absorbing HCl is used as absorption liquid of the hydrochloric acid absorption tower to realize water balance.

Preferably, the system still includes lithium chloride purification cauldron, sulphide filter, the synthetic cauldron of lithium carbonate, lithium carbonate filter and lithium carbonate desiccator, the entry linkage of lithium chloride purification cauldron the liquid export of oxide filter press, the exit linkage of lithium chloride purification cauldron the entry of sulphide filter, the liquid exit linkage of sulphide filter the entry of the synthetic cauldron of lithium carbonate, the exit linkage of the synthetic cauldron of lithium carbonate the entry of lithium carbonate filter, the solid exit linkage of lithium carbonate filter the entry of lithium carbonate desiccator.

The lithium chloride purification kettle is used for purifying liquid at an outlet of the oxide filter press, wherein the liquid contains nickel, cobalt or manganese ions, sulfide is added into the liquid to produce sulfide precipitate, then a sulfide filter is subjected to solid-liquid separation to obtain a purified lithium chloride solution, then the purified lithium chloride solution reacts with carbonate in a lithium carbonate synthesis kettle to generate lithium carbonate, the lithium carbonate is subjected to solid-liquid separation by a lithium carbonate filter, and an obtained solid product is dried by a lithium carbonate dryer to obtain a lithium carbonate product.

Preferably, a lithium chloride purification pump is arranged between the outlet of the lithium chloride purification kettle and the inlet of the sulfide filter, and the inlet and the outlet of the lithium chloride purification pump are respectively connected with the outlet of the lithium chloride purification kettle and the inlet of the sulfide filter.

Here a lithium chloride purge pump is provided for liquid delivery.

Preferably, a synthesis kettle discharge pump is arranged between the outlet of the lithium carbonate synthesis kettle and the inlet of the lithium carbonate filter, and the inlet and the outlet of the synthesis kettle discharge pump are respectively connected with the outlet of the lithium carbonate synthesis kettle and the inlet of the lithium carbonate filter.

Preferably, the high temperature furnace is an electric heating or natural gas heating device.

Preferably, the furnace type of the high-temperature furnace is a box furnace or a rotary furnace.

Preferably, the hydrochloric acid leaching kettle is made of a hydrochloric acid resistant material.

Preferably, the lining of the hydrochloric acid leaching kettle is made of glass lining or graphite lining.

Preferably, the hydrochloric acid leaching kettle is provided with a jacket.

Preferably, the hydrochloric acid leaching kettle takes low-pressure steam as a heat source.

Preferably, the furnace type of the ternary pyrolysis furnace is a box furnace or a rotary furnace.

Preferably, the ternary pyrolysis furnace employs bottom heating.

Preferably, the ternary pyrolysis furnace adopts a bottom discharging mode.

Preferably, the ternary pyrolysis furnace is a direct heating device.

Preferably, the ternary pyrolysis furnace is built of acid and fire resistant materials.

Preferably, the ternary pyrolysis furnace is an electric heating or natural gas heating device.

Preferably, the ternary pyrolysis furnace is fueled by natural gas.

Preferably, a solid outlet of the cyclone separator is connected with the middle part of the ternary pyrolysis furnace and is used for conveying solid powder into the pyrolysis furnace.

Preferably, the water leaching vessel is used for leaching lithium chloride from a mixed oxide of nickel oxide, cobalt oxide and manganese oxide.

Preferably, the water leaching kettle is made of chloride ion resistant alloy.

Preferably, the water leaching kettle is of a jacket structure, and low-pressure steam is used as a heat source.

Preferably, the sulphide filter is a tubular or basket filter press.

Compared with the prior art, the invention has the following beneficial effects:

(1) the method realizes the separation of nickel, cobalt and manganese by utilizing the characteristics that nickel chloride, cobalt chloride and manganese chloride are easily decomposed by heating and lithium chloride is not decomposed, and the decomposition product of ternary chloride is ternary oxide, thereby realizing the short-process preparation of the ternary precursor oxide;

(2) the product decomposed by the ternary chloride in the method contains HCl, and the cyclic utilization of the hydrochloric acid is realized after the HCl is absorbed, so that no secondary pollution is caused;

(3) the method realizes resource recycling of the anode material of the waste ternary battery, and has no environmental hidden danger.

Drawings

FIG. 1 is a schematic flow chart of a resource recycling method of a waste ternary battery anode material based on a hydrochloric acid regeneration cycle, which is disclosed by the invention;

FIG. 2 is a schematic diagram of a resource recycling system for the anode materials of the waste ternary batteries based on the hydrochloric acid regeneration cycle;

1-high temperature furnace, 2-sieving machine, 3-ball mill, 4-screw conveyer, 5-hydrochloric acid leaching kettle, 6-acid leaching kettle discharge pump, 7-acid leaching residue filter press, 8-solution adjusting tank, 9-adjusting tank discharge pump, 10-purifying filter press, 11-chloride dissolving tank, 12-dissolving tank discharge pump, 13-precision filter, 14-chloride preparing tank, 15-chloride preparing pump, 16-ternary pyrolysis furnace, 17-cyclone separator, 18-preconcentrator, 19-preconcentrator circulating pump, 20-spray pyrolysis pump, 21-hydrochloric acid absorption tower, 22-hydrochloric acid pump, 23-acid resistant tail gas fan, 24-tail gas purifying tower, 25-purifying tower circulating pump, 26-powder collector, 27-water leaching kettle, 28-water leaching kettle discharge pump, 29-oxide filter press, 30-three-way calcining furnace, 31-lithium chloride purifying kettle, 32-lithium chloride purifying pump, 33-sulfide filter, 34-lithium carbonate synthesizing kettle, 35-synthesizing kettle discharge pump, 36-lithium carbonate filter and 37-lithium carbonate dryer.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The flow schematic diagram of the resource recovery method of the waste ternary battery anode material based on the hydrochloric acid regeneration cycle is shown in fig. 1, the current collector of the waste ternary battery anode material takes copper foil and aluminum foil as an example, as can be seen from fig. 1, the method comprises the following steps:

(1') high-temperature dealuminizing copper: namely activating the anode material of the waste ternary battery at the temperature of 500-600 ℃;

(2') mechanical sieving: screening the activated product in the step (1'), removing aluminum copper foil to obtain ternary material powder, and then further crushing to obtain powder with the particle size of more than or equal to 200 meshes;

(3') acid leaching with hydrochloric acid: performing hydrochloric acid leaching on the ternary material powder obtained in the step (2'), wherein the hydrochloric acid is from supplemented hydrochloric acid and circulating hydrochloric acid, and then performing solid-liquid separation to obtain a filtrate;

(4') removing impurities by reducing the solution: adding iron powder into the filtrate obtained in the step (3') to adjust the pH value, further eliminating free hydrochloric acid, and reducing and decoppering;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value, generating iron aluminum hydroxide precipitate, and removing silicon in the solution; carrying out solid-liquid separation to obtain a filtrate;

(6') preparation of ternary chloride: adding a solution of nickel chloride, cobalt chloride and manganese chloride into the filtrate obtained in the step (5'), wherein the addition amount of the solution enables the amount of the nickel chloride, the cobalt chloride and the manganese chloride in the obtained solution to meet the requirement of a nickel-cobalt-manganese ternary precursor material;

(7') decomposition of nickel cobalt manganese: carrying out thermal decomposition on the solution prepared in the step (6') to obtain mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl, carrying out dust removal on the HCl-containing flue gas by a cyclone separator and cooling by a pre-concentrator, absorbing the HCl-containing flue gas by water to obtain hydrochloric acid, and completing preparation of regenerated hydrochloric acid, wherein the obtained hydrochloric acid is circulated to the step (3') for hydrochloric acid leaching;

(8') calcination of ternary material: washing the mixed oxide powder in the step (7') by powder water to obtain an oxide filter cake and a lithium chloride solution; then calcining to obtain a ternary precursor oxide;

(9') removing impurities by vulcanization and mechanically sieving: namely, sodium sulfide is added to the lithium chloride solution in the step (8'), then solid-liquid separation is performed, sodium carbonate is added to the filtrate, and mechanical separation and drying are performed to obtain lithium carbonate.

The schematic diagram of the recycling system of the waste ternary battery anode material based on the hydrochloric acid regeneration cycle is shown in figure 2, and can be seen from figure 2, the system comprises a high-temperature furnace 1, a sieving machine 2, a ball mill 3, a screw conveyor 4, a hydrochloric acid pickling kettle 5, an acid pickling kettle discharge pump 6, an acid pickling residue filter press 7, a solution adjusting tank 8, an adjusting tank discharge pump 9, a purification filter press 10, a chloride dissolving tank 11, a dissolving tank discharge pump 12, a precision filter 13, a chloride preparing tank 14, a chloride preparing pump 15, a ternary pyrolysis furnace 16, a cyclone separator 17, a preconcentrator 18, a preconcentrator circulating pump 19, a spray pyrolysis pump 20, a hydrochloric acid absorption tower 21, a hydrochloric acid pump 22, an acid-resistant tail gas fan 23, a tail gas purification tower 24, a purification tower circulating pump 25, a powder collector 26, a water leaching kettle 27, a water leaching kettle discharge pump 28, an oxide filter press 29, a hydrochloric acid absorption tower 21, A ternary calcining furnace 30, a lithium chloride purifying kettle 31, a lithium chloride purifying pump 32, a sulfide filter 33, a lithium carbonate synthesizing kettle 34, a synthesizing kettle discharging pump 35, a lithium carbonate filter 36 and a lithium carbonate dryer 37; wherein, the outlet of the high temperature furnace 1 is connected with the inlet of the sieving machine 2, the outlet of the sieving machine 2 is connected with the inlet of the ball mill 3, the outlet of the ball mill 3 is connected with the inlet of the screw conveyer 4, the outlet of the screw conveyer 4 is connected with the inlet of the hydrochloric acid leaching kettle 5, the outlet of the bottom of the hydrochloric acid leaching kettle 5 is connected with the inlet of the acid leaching kettle discharge pump 6, the outlet of the acid leaching kettle discharge pump 6 is connected with the inlet of the acid leaching residue filter press 7, the liquid outlet of the acid leaching residue filter press 7 is connected with the inlet of the solution adjusting tank 8, the outlet of the solution adjusting tank 8 is connected with the inlet of the adjusting tank discharge pump 9, the outlet of the adjusting tank discharge pump 9 is connected with the inlet of the purifying filter press 10, and the outlet of the purifying filter press 10 is; the outlet of the chloride dissolving tank 11 is connected with the inlet of a dissolving tank discharging pump 12, the outlet of the dissolving tank discharging pump 12 is connected with the inlet of a precise filter 13, the outlet of the precise filter 13 is connected with the inlet of a chloride preparation tank 14, the outlet of the chloride preparation tank 14 is connected with the inlet of a chloride preparation pump 15, the outlet of the chloride preparation pump 15 is connected with the liquid inlet of a preconcentrator 18, the liquid outlet of the preconcentrator 18 is connected with the inlet of a preconcentrator circulating pump 19, the outlet of the preconcentrator circulating pump 19 is connected with the inlet of a spray pyrolysis pump 20 and the top inlet of the preconcentrator 18, the outlet of the spray pyrolysis pump 20 is connected with the upper liquid inlet of a ternary pyrolysis furnace 16, the top gas outlet of the ternary pyrolysis furnace 16 is connected with the inlet of a cyclone separator 17, the outlet of the cyclone separator 17 is connected with the inlet of the preconcentrator 18, the top gas outlet of the preconcentrator 18 is connected with the gas inlet of, the upper gas outlet of the hydrochloric acid absorption tower 21 is connected with the inlet of the acid-resistant tail gas fan 23, the outlet of the acid-resistant tail gas fan 23 is connected with the gas inlet of the tail gas purification tower 24, the liquid outlet of the tail gas purification tower 24 is connected with the inlet of the purification tower circulating pump 25, the outlet of the purification tower circulating pump 25 is connected with the top liquid inlet of the tail gas purification tower 24 and the upper liquid inlet of the hydrochloric acid absorption tower 21, the outlet of the hydrochloric acid pump 22 is connected with the liquid inlet of the hydrochloric acid leaching kettle 5, the lower outlet of the ternary pyrolysis furnace 16 is connected with the inlet of the powder collector 26, the outlet of the powder collector 26 is connected with the upper inlet of the water leaching kettle 27, the bottom outlet of the water leaching kettle 27 is connected with the inlet of the water leaching kettle discharge pump 28, the outlet of the water leaching kettle discharge pump 28 is connected with the inlet of the oxide filter press 29, the solid outlet of the oxide filter, the liquid outlet of the oxide filter press 29 is connected with the inlet of the lithium chloride purifying kettle 31, the outlet of the lithium chloride purifying kettle 31 is connected with the inlet of the lithium chloride purifying pump 32, the outlet of the lithium chloride purifying pump 32 is connected with the inlet of the sulfide filter 33, the outlet of the sulfide filter 33 is connected with the inlet of the lithium carbonate synthesizing kettle 34, the outlet of the lithium carbonate synthesizing kettle 34 is connected with the inlet of the synthetic kettle discharging pump 35, the outlet of the synthetic kettle discharging pump 35 is connected with the inlet of the lithium carbonate filter 36, and the outlet of the lithium carbonate filter 36 is connected with the inlet of the lithium carbonate drier 37.

The specific implementation mode of the invention partially adopts the anode material of the waste ternary battery from a certain domestic waste lithium ion battery purchasing company, and the main components of the anode material are shown in the following table;

TABLE 1

Composition of	Li	Ni	Co	Mn	Cu	Al	Fe
								Mass concentration, wt%	6.03	35.16	15.27	18.95	0.59	1.38	0.37

The purity test standard of the lithium carbonate obtained in the embodiment part of the invention is national standard GB/T of industrial lithium carbonate

11075-2013, the technical indexes of the national standard GB/T11075-2013 of industrial lithium carbonate are shown in the following table;

TABLE 2

Example 1

The resource recycling method of the anode material of the waste ternary battery comprises the following steps:

(1') high-temperature dealuminizing copper: adding the anode material of the waste ternary battery into a natural gas heating rotary high-temperature furnace for activation, wherein the activation temperature is 500 ℃, and the activation time is 90min, and in the process, removing and decomposing binders, organic matters and the like in the waste to separate lithium, nickel, cobalt, manganese and the like from an aluminum foil, a copper foil and a copper wire;

(2') mechanical sieving: recovering aluminum foil, copper foil and copper wire from the activated product obtained in the step (1') in a sieving machine to obtain solid powder containing lithium, nickel, cobalt and manganese; grinding the waste ternary battery anode material subjected to aluminum foil, copper foil and copper wire removal in a ball mill to more than 200 meshes;

(3') acid leaching with hydrochloric acid: conveying the ball-milled product in the step (2') into a hydrochloric acid leaching kettle by using a screw conveyor, wherein the hydrochloric acid leaching kettle is made of glass lining and is provided with a jacket, steam with the pressure of 0.4MPa and the temperature of 140 ℃ is used as a heat source for heating, then adding hydrochloric acid with the mass concentration of 18% into the hydrochloric acid leaching kettle, the added hydrochloric acid comprises circulating hydrochloric acid and supplementary hydrochloric acid which are generated by hydrolysis of nickel chloride, cobalt chloride and manganese chloride, the adding amount of the hydrochloric acid is 10% excessive relative to the sum of molar amounts of hydrochloric acid required by acid leaching of ions of nickel, cobalt and manganese in different valence states in the anode material of the waste ternary battery, performing acid leaching at 85 ℃, so that nickel, cobalt, manganese and lithium are all dissolved into a liquid phase to form chloride, and conveying the acid-leached material to an acid leaching residue filter press by using an acid leaching kettle discharge pump for solid-liquid separation;

(4') removing impurities by reducing the solution: the filtrate obtained in the step (3') enters a solution adjusting tank, iron powder is added into the solution adjusting tank to consume free hydrochloric acid and adjust the pH value of the system to 1.0, and meanwhile, the residual copper is further reduced and removed;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value to 3.0, precipitating iron and aluminum, removing impurities such as silicon and the like, and conveying the material to a purification filter press by using a discharge pump of an adjusting tank for solid-liquid separation to obtain filtrate;

(6') preparation of ternary chloride: sending the filtrate obtained in the step (5') into a chloride preparation tank, adding corresponding amounts of nickel chloride, cobalt chloride, manganese chloride and water into a chloride dissolving tank according to the 333 type nickel-cobalt-manganese ternary precursor material ratio to prepare a mixed solution, then sending the mixed solution into a precision filter by a pump to be filtered, and then sending the filtered solution into the chloride preparation tank to obtain a prepared solution;

(7') decomposition of nickel cobalt manganese: pumping the solution prepared in the step (6') to a pre-concentrator by using a chloride preparation pump, performing contact heat exchange with high-temperature flue gas from a cyclone separator to perform concentration, pumping the concentrated solution to a ternary pyrolysis furnace by using a spray pyrolysis pump to perform pyrolysis at 450 ℃, building the ternary pyrolysis furnace by using an acid-resistant refractory material, using natural gas as a fuel, directly heating the bottom of the ternary pyrolysis furnace, discharging the solid from the bottom of the ternary pyrolysis furnace, enabling the high-temperature flue gas and the liquid to flow upwards in a countercurrent manner, decomposing nickel chloride, cobalt chloride and manganese chloride into oxides and hydrogen chloride, dedusting the high-temperature flue gas containing HCl by using the cyclone separator, returning powder from the interior of the ternary pyrolysis furnace, enabling the gas phase to enter the pre-concentrator to perform heat exchange with the mixed solution of the chloride, absorbing the gas phase by using water in a hydrochloric acid absorption tower to obtain hydrochloric acid with the mass concentration of 18%, recycling the hydrochloric acid;

(8') calcination of ternary material: feeding the lithium chloride-containing solid obtained at the bottom of the ternary pyrolysis furnace in the step (7') into a water leaching kettle through a powder collector, adding water, heating for leaching, wherein the mass ratio of leaching water to solid is 12:1, the water leaching kettle is made of a chloride ion resistant alloy material and is provided with a jacket, steam with the pressure of 0.4MPa and the temperature of 140 ℃ is used as a heat source for heating, the leaching temperature is 80 ℃, the leaching time is 30min, a discharging pump of the water leaching kettle is used for conveying the material to an oxide filter press for solid-liquid separation, the obtained filter cake is washed by adding water, the washed filter cake is fed into an electric heating box type ternary precursor for high-temperature calcination, the calcination temperature is 600 ℃, the calcination time is 60min, and a ternary precursor oxide is obtained, and all indexes meet the requirements of a 333 type;

(9') removing impurities by vulcanization and mechanically sieving: putting the water leaching filtrate obtained by the oxide filter press in the step (8') into a chloride purification tank, adding a sodium sulfide solution, wherein the ratio of the addition amount of the sodium sulfide to the molar amount of nickel, cobalt and manganese in the chloride solution is 1.05:1, and performing vulcanization precipitation and tubular sulfur treatmentA compound filter, wherein a filter cake is washed to obtain a nickel-cobalt-manganese sulfide, a lithium chloride solution with the mass concentration of 10% enters a lithium carbonate synthesis kettle, a sodium carbonate solution with the mass concentration of 25% is slowly added into the lithium chloride solution to synthesize lithium carbonate at 95 ℃, and the lithium carbonate is subjected to solid-liquid separation by the lithium carbonate filter and drying by a lithium carbonate dryer to obtain a lithium carbonate product which meets the national standard GB/T11075-₂CO₃-an index requirement of 1.

Example 2

(1') high-temperature dealuminizing copper: adding the anode material of the waste ternary battery into an electric heating box type high-temperature furnace for activation, wherein the activation temperature is 520 ℃, and the activation time is 80min, and in the process, removing and decomposing the binder, organic matters and the like in the waste to separate lithium, nickel, cobalt, manganese and the like from an aluminum foil, a copper foil and a copper wire;

(2') mechanical sieving: recovering the aluminum foil, the copper foil and the copper wire from the activation product in the step (1') in a sieving machine to obtain solid powder containing lithium, nickel, cobalt and manganese; grinding the waste ternary battery anode material subjected to aluminum foil, copper foil and copper wire removal in a ball mill to more than 200 meshes;

(3') acid leaching with hydrochloric acid: conveying the powder obtained in the step (2') into a hydrochloric acid pickling kettle by using a screw conveyor, wherein the hydrochloric acid pickling kettle is made of a graphite lining material and is provided with a jacket, heating is carried out by using steam with the pressure of 0.5MPa and the temperature of 150 ℃ as a heat source, then adding hydrochloric acid with the mass concentration of 19% into the hydrochloric acid pickling kettle, the added hydrochloric acid comprises circulating hydrochloric acid and supplementary hydrochloric acid generated by hydrolyzing nickel chloride, cobalt chloride and manganese chloride, the adding amount of the hydrochloric acid is 12% excessive relative to the sum of the molar amounts of hydrochloric acid required by pickling nickel, cobalt and manganese ions with different valence states in the anode material of the waste ternary battery, carrying out pickling at 83 ℃, completely dissolving nickel, cobalt, manganese and lithium into a liquid phase to form chloride, conveying the pickling material to a pickling residue filter press by using a discharging pump of the pickling kettle, and carrying out solid-liquid separation to obtain filtrate;

(4') removing impurities by reducing the solution: the filtrate obtained in the step (3') enters a solution adjusting tank, iron powder is added into the solution adjusting tank to consume free hydrochloric acid and adjust the pH value of the system to 1.2, and meanwhile, the residual copper is further reduced and removed;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value to 3.2, precipitating iron and aluminum, removing impurities such as silicon and the like, and conveying the material to a purification filter press by using a discharge pump of an adjusting tank for solid-liquid separation to obtain filtrate;

(6') preparation of ternary chloride: sending the filtrate obtained in the step (5') into a chloride preparation tank; adding corresponding amounts of nickel chloride, cobalt chloride, manganese chloride and water into a chloride dissolving tank according to a 523 type ternary precursor proportion to prepare a mixed solution, then pumping the mixed solution to a precision filter for filtering, and then sending the filtered mixed solution into a chloride preparation tank to prepare the solution;

(7') decomposition of nickel cobalt manganese: pumping the solution prepared in the step (6') to a pre-concentrator, contacting with high-temperature flue gas from a cyclone separator for heat exchange and concentrating, then pumping the concentrated solution to a ternary pyrolysis furnace through a spray pyrolysis pump for pyrolysis at 470 ℃, wherein the ternary pyrolysis furnace is built by acid-resistant and refractory materials, natural gas is used as fuel, the bottom of the ternary pyrolysis furnace is directly heated, solid is discharged from the bottom, the high-temperature flue gas and liquid flow upwards in a countercurrent manner, nickel chloride, cobalt chloride and manganese chloride are decomposed into oxides and hydrogen chloride, the HCl-containing high-temperature flue gas is dedusted by the cyclone separator, powder returns from the inside of the ternary pyrolysis furnace, gas phase enters the pre-concentrator and is subjected to heat exchange with chloride mixed solution for cooling, hydrochloric acid with the mass concentration of 19% is obtained through water absorption in a hydrochloric acid absorption tower and is recycled, the tail gas is purified by a tail gas purification tower and then discharged;

(8') calcination of ternary material: feeding the lithium chloride-containing solid obtained at the bottom of the ternary pyrolysis furnace in the step (7') into a water leaching kettle through a powder collector, adding water, heating for leaching, wherein the mass ratio of leaching water to solid is 10:1, the water leaching kettle is made of a chloride ion resistant alloy material and is provided with a jacket, steam with the pressure of 0.5MPa and the temperature of 150 ℃ is used as a heat source for heating, the leaching temperature is 85 ℃, the leaching time is 25min, a discharging pump of the water leaching kettle is used for conveying the material to an oxide filter press for solid-liquid separation, the obtained filter cake is washed by adding water, the washed filter cake enters a natural gas heating rotary type ternary precursor for high-temperature calcination, the calcination temperature is 580 ℃, the calcination time is 70min, and a ternary precursor oxide is obtained, and each index meets the requirement of a 523 type ternary;

(9') removing impurities by vulcanization and mechanically sieving: and (3) putting the water leaching filtrate obtained by the oxide filter press in the step (8') into a chloride purification tank, adding a sodium sulfide solution, wherein the ratio of the addition amount of sodium sulfide to the molar amount of nickel, cobalt and manganese in the chloride solution is 1.1:1, performing vulcanization precipitation, passing through a basket type sulfide filter, washing a filter cake to obtain a nickel, cobalt and manganese sulfide, putting a lithium chloride solution with the mass concentration of 11% into a lithium carbonate synthesis kettle, slowly adding a sodium carbonate solution with the mass concentration of 24% into a lithium chloride solution, synthesizing lithium carbonate at 95 ℃, performing solid-liquid separation by a lithium carbonate filter and drying by a lithium carbonate dryer to obtain a lithium carbonate product, wherein the lithium carbonate product meets the national standard GB/T11075 and 2013 Li in Li cobalt and manganese content₂CO₃-an index requirement of 1.

Example 3

(1') high-temperature dealuminizing copper: adding the anode material of the waste ternary battery into an electric heating box type high-temperature furnace for activation, wherein the activation temperature is 540 ℃, and the activation time is 70min, and in the process, removing and decomposing the binder, organic matters and the like in the waste to separate lithium, nickel, cobalt, manganese and the like from the aluminum foil, the copper foil and the copper wire;

(3') acid leaching with hydrochloric acid: conveying the ball-milled product obtained in the step (2') into a hydrochloric acid pickling kettle by using a screw conveyor, wherein the hydrochloric acid pickling kettle is made of glass lining materials and is provided with a jacket, heating is carried out by using steam with the pressure of 0.5MPa and the temperature of 150 ℃ as a heat source, then hydrochloric acid with the mass concentration of 20% is added into the hydrochloric acid pickling kettle, the added hydrochloric acid comprises circulating hydrochloric acid and supplementary hydrochloric acid generated by hydrolyzing nickel chloride, cobalt chloride and manganese chloride, the adding amount of the hydrochloric acid is 16% excessive relative to the sum of molar amounts of hydrochloric acid required by pickling nickel, cobalt and manganese ions with different valence states in the anode material of the waste ternary battery, pickling is carried out at the temperature of 81 ℃, so that nickel, cobalt, manganese and lithium are all dissolved into a liquid phase to form chloride, and the pickling material is conveyed to a pickling residue filter press by using a discharging pump of the pickling kettle to carry out solid;

(4') removing impurities by reducing the solution: the filtrate obtained in the step (3') enters a solution adjusting tank, iron powder is added into the solution adjusting tank to consume free hydrochloric acid and adjust the pH value of the system to 1.3, and meanwhile, the residual copper is further reduced and removed;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value to 3.4, precipitating iron and aluminum, removing impurities such as silicon and the like, and conveying the material to a purification filter press by using a discharge pump of an adjusting tank for solid-liquid separation to obtain filtrate;

(6') preparation of ternary chloride: feeding the filtrate obtained in step (5') to a chloride preparation tank; adding corresponding amounts of nickel chloride, cobalt chloride, manganese chloride and water into a chloride dissolving tank according to the proportion of 811 type ternary precursor to prepare a mixed solution, then pumping the mixed solution to a precision filter for filtering, and then sending the filtered solution into a chloride preparation tank to obtain a prepared solution;

(7') decomposition of nickel cobalt manganese: pumping the solution prepared in the step (6') to a pre-concentrator by using a chloride preparation pump, performing contact heat exchange with high-temperature flue gas from a cyclone separator to perform concentration, pumping the concentrated solution to a ternary pyrolysis furnace by using a spray pyrolysis pump to perform pyrolysis at 490 ℃, building the ternary pyrolysis furnace by using an acid-resistant refractory material, using natural gas as a fuel, directly heating the bottom of the ternary pyrolysis furnace, discharging the solid from the bottom, enabling the high-temperature flue gas and the liquid to flow upwards in a countercurrent manner, decomposing nickel chloride, cobalt chloride and manganese chloride into oxides and hydrogen chloride, dedusting the high-temperature flue gas containing HCl by using the cyclone separator, returning powder from the inside of the ternary pyrolysis furnace, enabling the gas phase to enter the pre-concentrator to perform heat exchange with the mixed solution of the chloride, absorbing the gas phase by using water in a hydrochloric acid absorption tower to obtain hydrochloric acid with the mass concentration of 20%, recycling, purifying the tail gas by using a tail;

(8') calcination of ternary material: feeding the lithium chloride-containing solid obtained at the bottom of the ternary pyrolysis furnace in the step (7') into a water leaching kettle through a powder collector, adding water and heating for leaching, wherein the mass ratio of leaching water to solid is 9:1, the water leaching kettle is made of a chloride ion resistant alloy material and is provided with a jacket, steam with the pressure of 0.4MPa and the temperature of 140 ℃ is used as a heat source for heating, the leaching temperature is 90 ℃, the leaching time is 20min, a discharging pump of the water leaching kettle is used for conveying the material to an oxide filter press for solid-liquid separation, the obtained filter cake is washed by adding water, the washed filter cake enters a natural gas heating rotary type ternary calcining furnace for high-temperature calcination, the calcining temperature is 560 ℃, the calcining time is 80min, and the ternary precursor oxide is obtained, and all indexes meet the requirement of a 811 type;

(9') removing impurities by vulcanization and mechanically sieving: the water leaching filtrate obtained by the oxide filter press in the step (8') enters a chloride purification tank, a sodium sulfide solution is added, the ratio of the addition amount of the sodium sulfide to the molar amount of nickel, cobalt and manganese in the chloride solution is 1.15:1, the mixture is subjected to vulcanization precipitation and then passes through a filter press type sulfide filter, a filter cake is washed to obtain a nickel, cobalt and manganese sulfide, a lithium chloride solution with the mass concentration of 13% enters a lithium carbonate synthesis kettle, a sodium carbonate solution with the mass concentration of 22% is slowly added into a lithium chloride solution to synthesize lithium carbonate at 95 ℃, the lithium carbonate is subjected to solid-liquid separation by a lithium carbonate filter and drying by a lithium carbonate dryer to obtain a lithium carbonate product, and the lithium carbonate product meets the national standard GB/T11075 and Li 2013₂CO₃-an index requirement of 1.

Example 4

(1') high-temperature dealuminizing copper: adding the anode material of the waste ternary battery into a natural gas heating rotary high-temperature furnace for activation, wherein the activation temperature is 580 ℃, and the activation time is 60min, and in the process, the binder, organic matters and the like in the waste are removed and decomposed, so that lithium, nickel, cobalt, manganese and the like are separated from aluminum foil, copper foil and copper wire;

(2') mechanical sieving: recovering aluminum foil, copper foil and copper wire from the activated product in the step (1') in a sieving machine to obtain solid powder containing lithium, nickel, cobalt and manganese; grinding the waste ternary battery anode material subjected to aluminum foil, copper foil and copper wire removal in a ball mill to more than 200 meshes;

(3') acid leaching with hydrochloric acid: conveying the ball-milled product obtained in the step (2') into a hydrochloric acid leaching kettle by using a screw conveyor, wherein the hydrochloric acid leaching kettle is made of a stone mill lining material and is provided with a jacket, heating is carried out by using steam with the pressure of 0.4MPa and the temperature of 140 ℃ as a heat source, then hydrochloric acid with the mass concentration of 21% is added into the hydrochloric acid leaching kettle, the added hydrochloric acid comprises circulating hydrochloric acid and supplementary hydrochloric acid generated by hydrolyzing nickel chloride, cobalt chloride and manganese chloride, the adding amount of the hydrochloric acid is 18% excessive relative to the sum of molar amounts of hydrochloric acid required by acid leaching of ions of nickel, cobalt and manganese in different valence states in the anode material of the waste ternary battery, acid leaching is carried out at 77 ℃, so that nickel, cobalt, manganese and lithium are all dissolved into a liquid phase to form chloride, and the acid-leached material is conveyed to an acid leaching residue filter press by using an acid leaching kettle discharge;

(4') removing impurities by reducing the solution: the filtrate obtained in the step (3') enters a solution adjusting tank, iron powder is added into the solution adjusting tank to consume free hydrochloric acid and adjust the pH value of the system to 1.5, and meanwhile, the residual copper is further reduced and removed;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value to 3.8, precipitating iron and aluminum, removing impurities such as silicon and the like, and conveying the material to a purification filter press by using a discharge pump of an adjusting tank for solid-liquid separation to obtain filtrate;

(6') preparation of ternary chloride: sending the filtrate obtained in the step (5') into a chloride preparation tank, adding corresponding amounts of nickel chloride, cobalt chloride, manganese chloride and water into a chloride dissolving tank according to the 523 type ternary precursor proportion to prepare a mixed solution, then pumping the mixed solution to a precision filter for filtering, and then sending the filtered solution into the chloride preparation tank to obtain a prepared solution;

(7') decomposition of nickel cobalt manganese: pumping the solution prepared in the step (6') to a pre-concentrator by using a chloride preparation pump, performing contact heat exchange with high-temperature flue gas from a cyclone separator to perform concentration, pumping the concentrated solution to a ternary pyrolysis furnace by using a spray pyrolysis pump to perform pyrolysis at 530 ℃, building the ternary pyrolysis furnace by using an acid-resistant refractory material, using natural gas as a fuel, directly heating the bottom of the ternary pyrolysis furnace, discharging the solid from the bottom of the ternary pyrolysis furnace, enabling the high-temperature flue gas and the liquid to flow upwards in a countercurrent manner, decomposing nickel chloride, cobalt chloride and manganese chloride into oxides and hydrogen chloride, dedusting the high-temperature flue gas containing HCl by using the cyclone separator, returning powder from the interior of the ternary pyrolysis furnace, enabling the gas phase to enter the pre-concentrator to perform heat exchange with the mixed solution of the chloride, absorbing the gas phase by using water in a hydrochloric acid absorption tower to obtain hydrochloric acid with the mass concentration of 21%, recycling the hydrochloric acid;

(8') calcination of ternary material: feeding the lithium chloride-containing solid obtained at the bottom of the ternary pyrolysis furnace in the step (7') into a water leaching kettle through a powder collector, adding water and heating for leaching, wherein the mass ratio of leaching water to solid is 8:1, the water leaching kettle is made of a chloride ion resistant alloy material and is provided with a jacket, steam with the pressure of 0.4MPa and the temperature of 140 ℃ is used as a heat source for heating, the leaching temperature is 95 ℃, the leaching time is 20min, a discharging pump of the water leaching kettle is used for conveying the material to an oxide filter press for solid-liquid separation, the obtained filter cake is washed by adding water, the washed filter cake enters a natural gas heating rotary type ternary precursor for high-temperature calcination, the calcination temperature is 580 ℃, the calcination time is 70min, and a ternary precursor oxide is obtained, and each index meets the requirement of a 811 type ternary;

(9') removing impurities by vulcanization and mechanically sieving: the method comprises the steps of (8') enabling water leaching filtrate obtained by an oxide filter press to enter a chloride purification tank, adding a sodium sulfide solution, enabling the ratio of the addition amount of sodium sulfide to the molar amount of nickel, cobalt and manganese in the chloride solution to be 1.2:1, enabling the mixture to pass through a tubular sulfide filter after vulcanization and precipitation, washing a filter cake to obtain a nickel, cobalt and manganese sulfide, enabling a lithium chloride solution with the mass concentration of 14% to enter a lithium carbonate synthesis kettle, slowly adding a sodium carbonate solution with the mass concentration of 21% into a lithium chloride solution, synthesizing lithium carbonate at 95 ℃, performing solid-liquid separation by a lithium carbonate filter and drying by a lithium carbonate dryer to obtain a lithium carbonate product, wherein the lithium carbonate product meets the national standard GB/T11075 and 2013 for Li₂CO₃-an index requirement of 1.

Example 5

(1') high-temperature dealuminizing copper: adding the anode material of the waste ternary battery into an electric heating box type high-temperature furnace for activation, wherein the activation temperature is 600 ℃, and the activation time is 60min, and in the process, removing and decomposing the binder, organic matters and the like in the waste to separate lithium, nickel, cobalt, manganese and the like from an aluminum foil, a copper foil and a copper wire;

(3') acid leaching with hydrochloric acid: conveying the ball-milled product obtained in the step (2') into a hydrochloric acid pickling kettle by using a screw conveyor, wherein the hydrochloric acid pickling kettle is made of glass lining materials and is provided with a jacket, heating is carried out by using steam with the pressure of 0.5MPa and the temperature of 150 ℃ as a heat source, then hydrochloric acid with the mass concentration of 18% is added into the hydrochloric acid pickling kettle, the added hydrochloric acid comprises circulating hydrochloric acid and supplementary hydrochloric acid generated by hydrolyzing nickel chloride, cobalt chloride and manganese chloride, the adding amount of the hydrochloric acid is 20% excessive relative to the sum of molar amounts of hydrochloric acid required by pickling nickel, cobalt and manganese ions with different valence states in the anode material of the waste ternary battery, pickling is carried out at 75 ℃, so that nickel, cobalt, manganese and lithium are all dissolved into a liquid phase to form chloride, and the pickling material is conveyed to a pickling residue filter press by using a discharging pump of the pickling kettle to carry out solid-liquid separation;

(4') removing impurities by reducing the solution: the filtrate obtained in the step (3') enters a solution adjusting tank, iron powder is added into the solution adjusting tank to consume free hydrochloric acid and adjust the pH value of the system to 1.6, and meanwhile, the residual copper is further reduced and removed;

(5') neutralizing the solution to remove impurities: adding ammonia water into the solution obtained in the step (4') to adjust the pH value to 4.0, precipitating iron and aluminum, removing impurities such as silicon and the like, and conveying the material to a purification filter press by using a discharge pump of an adjusting tank for solid-liquid separation to obtain filtrate;

(7') decomposition of nickel cobalt manganese: pumping the solution prepared in the step (6') to a pre-concentrator by using a chloride preparation pump, performing contact heat exchange with high-temperature flue gas from a cyclone separator to perform concentration, pumping the concentrated solution to a ternary pyrolysis furnace by using a spray pyrolysis pump to perform pyrolysis at 550 ℃, building the ternary pyrolysis furnace by using an acid-resistant refractory material, using natural gas as a fuel, directly heating the bottom of the ternary pyrolysis furnace, discharging the solid from the bottom of the ternary pyrolysis furnace, enabling the high-temperature flue gas and the liquid to flow upwards in a countercurrent manner, decomposing nickel chloride, cobalt chloride and manganese chloride into oxides and hydrogen chloride, dedusting the high-temperature flue gas containing HCl by using the cyclone separator, returning powder from the interior of the ternary pyrolysis furnace, enabling the gas phase to enter the pre-concentrator to perform heat exchange with the mixed solution of the chloride, absorbing the gas phase by using water in a hydrochloric acid absorption tower to obtain hydrochloric acid with the mass concentration of 18%, recycling the hydrochloric acid;

(8') calcination of ternary material: feeding the lithium chloride-containing solid obtained at the bottom of the ternary pyrolysis furnace in the step (7') into a water leaching kettle through a powder collector, adding water, heating for leaching, wherein the mass ratio of leaching water to solid is 7:1, the water leaching kettle is made of a chloride ion resistant alloy material and is provided with a jacket, steam with the pressure of 0.5MPa and the temperature of 150 ℃ is used as a heat source for heating, the leaching temperature is 85 ℃, the leaching time is 25min, a discharging pump of the water leaching kettle is used for conveying the material to an oxide filter press for solid-liquid separation, the obtained filter cake is washed by adding water, the washed filter cake enters a natural gas heating rotary type ternary calcination furnace for high-temperature calcination, the calcination temperature is 600 ℃, the calcination time is 60min, and a ternary precursor oxide is obtained, and all indexes meet the requirements of a 523 type;

(9') removing impurities by vulcanization and mechanically sieving: the water leaching filtrate obtained by the oxide filter press in the step (8') enters a chloride purification tank, a sodium sulfide solution is added, wherein the ratio of the addition amount of sodium sulfide to the molar amount of nickel, cobalt and manganese in the chloride solution is 1.1:1, a tubular sulfide filter is used for sulfurizing and precipitating the mixture, a filter cake is washed to obtain a nickel, cobalt and manganese sulfide, a lithium chloride solution with the mass concentration of 15% enters a lithium carbonate synthesis kettle, a sodium carbonate solution with the mass concentration of 20% is slowly added into a lithium chloride solution, and the lithium carbonate solution is added into the lithium chloride solutionSynthesizing lithium carbonate at 95 ℃, and then performing solid-liquid separation by a lithium carbonate filter and drying by a lithium carbonate dryer to obtain a lithium carbonate product which meets the national standard GB/T11075-₂CO₃-an index requirement of 1.

As can be seen from the above examples 1-5, in the method for recycling the anode material of the waste ternary battery based on the hydrochloric acid regeneration cycle, valuable components (nickel, cobalt, manganese and the like) in the ball-milled ternary material powder are all dissolved in a liquid phase by high-temperature (75-85 ℃) hydrochloric acid leaching, and meanwhile, the properties that the decomposition temperature of nickel chloride, cobalt chloride and manganese chloride is low and lithium chloride is not decomposed are utilized, the cyclic utilization of hydrochloric acid is realized through the thermal decomposition process, no secondary pollution is caused, the separation of nickel, cobalt, manganese and lithium is realized by combining with water leaching, and the ternary chloride decomposition product is a ternary oxide, so that the preparation of a ternary precursor oxide in a short flow is realized, and the effects of both preparing a product and realizing the hydrochloric acid regeneration cycle are realized; the product obtained by the method comprises a current collector (aluminum foil and copper foil), a ternary precursor oxide and lithium carbonate, and the purity of the obtained lithium carbonate is high and meets the national standard GB/T11075-wall lithium 2013₂CO₃-an index requirement of 1; and further, the recycling of the anode material of the waste ternary battery is realized, and no environmental hidden danger exists.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A resource recycling method of a waste ternary battery positive electrode material based on hydrochloric acid regeneration cycle is characterized by comprising the following steps:

(3) adding nickel chloride, cobalt chloride and manganese chloride into the second chloride solution obtained in the step (2) to obtain a third chloride solution, wherein the adding amount of the nickel chloride, the cobalt chloride and the manganese chloride enables the molar ratio of nickel, cobalt and manganese in the obtained third chloride solution to meet the requirement of a nickel-cobalt-manganese ternary precursor material; then carrying out thermal decomposition on the third chloride solution, wherein the thermal decomposition temperature is 450-550 ℃, so as to obtain mixed oxides of nickel oxide, cobalt oxide and manganese oxide and HCl, the HCl is absorbed to obtain hydrochloric acid, and the hydrochloric acid is circulated to the step (2) to be mixed with supplementary hydrochloric acid for hydrochloric acid leaching;

2. The method as claimed in claim 1, wherein the temperature of the activation in step (1) is 500-600 ℃.

3. The method of claim 1, wherein the activation time of step (1) is 60-90 min.

4. The method of claim 1, wherein the step (2) further comprises pulverizing the ternary material powder prior to the hydrochloric acid pickling.

5. The method of claim 4, wherein the end point of said pulverizing is at least 200 mesh.

6. The method of claim 1, wherein the hydrochloric acid used in the hydrochloric acid leaching in step (2) has a mass concentration of 18 to 21%.

7. The process of claim 1, wherein the temperature of the hydrochloric acid leach in step (2) is from 75 ℃ to 85 ℃.

8. The method of claim 1, wherein the hydrochloric acid leaching in step (2) is used for converting nickel, cobalt and manganese in the ternary material powder into nickel chloride, cobalt chloride and manganese chloride, and the amount of hydrochloric acid used in the hydrochloric acid leaching process is 10-20% in excess.

9. The method of claim 1, wherein low pressure steam heating is used in the hydrochloric acid leaching in step (2).

10. The method as claimed in claim 9, wherein the low pressure steam has a temperature of 140 ℃ and a pressure of 0.4 to 0.5 MPa.

11. The method of claim 1, wherein the decoppering method in step (2) is reductive decoppering.

12. The method of claim 11, wherein the decoppering process of step (2) includes adding iron powder to the first chloride solution.

13. The method of claim 12 wherein the iron powder is added in an amount to provide a solution pH of 1 to 1.6.

14. The method of claim 1, wherein the desilication of step (2) is precipitation desilication.

15. The method of claim 14, wherein the desiliconization in step (2) comprises adding ammonia to the decoppered solution.

16. The method of claim 15, wherein the aqueous ammonia is added in an amount such that the pH of the solution is from 3 to 4.

17. The method of claim 1, wherein the nickel cobalt manganese ternary precursor material of step (3) comprises any one of type 333, type 523, or type 811.

18. The method of claim 1, wherein said HCl of step (3) further comprises dedusting and reducing the temperature prior to absorption.

19. The method of claim 1, wherein the water immersion temperature of step (4) is 80-95 ℃.

20. The method of claim 1, wherein the ratio of the mass of water to the mass of the mixed oxides of nickel oxide, cobalt oxide and manganese oxide in the water leaching process of step (4) is (7-12): 1.

21. The method as claimed in claim 1, wherein the heating medium used in the water immersion in the step (4) is low-pressure steam, the temperature of the low-pressure steam is 140 ℃ and 150 ℃, and the pressure is 0.4-0.5 MPa.

22. The method according to claim 1, wherein the lithium chloride solution in the step (4) has a mass concentration of 10-15%.

23. The method as claimed in claim 1, wherein the temperature of the calcination in the step (4) is 500-600 ℃.

24. The method of claim 1, wherein the calcination time in step (4) is 60-90 min.

25. The method of claim 1, further comprising adding a soluble sulfide to the lithium chloride solution in step (4) to remove impurities, then performing solid-liquid separation, adding a sodium carbonate solution, performing solid-liquid separation, and drying to obtain lithium carbonate.

26. The method of claim 25, wherein the soluble sulfide comprises sodium sulfide and/or ammonium sulfide.

27. The method of claim 25, wherein the soluble sulfide is added in an amount to completely precipitate nickel, cobalt, and manganese in the lithium chloride solution.

28. The method of claim 25, wherein the ratio of the molar amount of soluble sulfide to the sum of the molar amounts of nickel, cobalt, and manganese in the lithium chloride solution is (1.05-1.2): 1.

29. The method of claim 25, wherein the sodium carbonate solution has a mass concentration of 20-25%.

30. The method of claim 25 wherein the lithium carbonate is dried at a temperature of 150 ℃ to 180 ℃.

31. The method of claim 1, wherein the method comprises the steps of:

(3) adding nickel chloride, cobalt chloride and manganese chloride into the second chloride solution obtained in the step (2) to obtain a third chloride solution, wherein the adding amount of the nickel chloride, the cobalt chloride and the manganese chloride enables the molar ratio of nickel, cobalt and manganese in the obtained third chloride solution to meet the requirement of a nickel-cobalt-manganese ternary precursor material; then, carrying out thermal decomposition on the third chloride solution at the temperature of 450-550 ℃ to obtain mixed oxide of nickel oxide, cobalt oxide and manganese oxide and HCl, absorbing the HCl to obtain hydrochloric acid with the mass concentration of 18-21%, and circulating the hydrochloric acid to the step (2) to be mixed with supplemented hydrochloric acid for hydrochloric acid leaching;

32. A recycling system of a waste ternary battery anode material based on hydrochloric acid regeneration cycle is characterized by comprising a high-temperature furnace, a screening machine, a ball mill, a hydrochloric acid pickling kettle, a pickling slag filter press, a solution adjusting tank, a purification filter press, a chloride preparation tank, a ternary pyrolysis furnace, a cyclone separator, a preconcentrator, a hydrochloric acid absorption tower, a water leaching kettle, an oxide filter press and a ternary calcining furnace, wherein an outlet of the high-temperature furnace is connected with an inlet of the screening machine, an outlet of the screening machine is connected with an inlet of the ball mill, an outlet of the ball mill is connected with an inlet of the hydrochloric acid pickling kettle, an outlet of the hydrochloric acid pickling kettle is connected with an inlet of the pickling slag filter press, a liquid outlet of the pickling slag filter press is connected with an inlet of the solution adjusting tank, and an outlet of the solution adjusting tank is connected with an inlet of the purification filter press, the liquid outlet of the purification filter press is connected with the inlet of the chloride preparation tank, the outlet of the chloride preparation tank is connected with the liquid inlet of the preconcentrator, the liquid outlet of the preconcentrator is connected with the inlet of the ternary pyrolysis furnace, the gas outlet of the ternary pyrolysis furnace is connected with the inlet of a cyclone separator, the gas outlet of the cyclone separator is connected with the gas inlet of the preconcentrator, the gas outlet of the preconcentrator is connected with the gas inlet of the hydrochloric acid absorption tower, the liquid outlet of the hydrochloric acid absorption tower is connected with the liquid inlet of a hydrochloric acid leaching kettle, the solid outlet of the ternary pyrolysis furnace is connected with the inlet of the water leaching kettle, the outlet of the water leaching kettle is connected with the inlet of the oxide filter press, and the solid outlet of the oxide filter press is connected with the inlet of the ternary calcining furnace.

33. A resource recovery system as claimed in claim 32, wherein a screw conveyor is arranged between the outlet of the ball mill and the inlet of the hydrochloric acid leaching kettle, and the inlet and the outlet of the screw conveyor are respectively connected with the outlet of the ball mill and the inlet of the hydrochloric acid leaching kettle.

34. The resource recycling system of claim 32, wherein an acid leaching kettle discharge pump is arranged between the outlet of the hydrochloric acid leaching kettle and the inlet of the acid leaching residue filter press, and the inlet and the outlet of the acid leaching kettle discharge pump are respectively connected with the outlet of the hydrochloric acid leaching kettle and the inlet of the acid leaching residue filter press.

35. A resource recovery system as set forth in claim 32, wherein the solution adjusting tank is provided with an iron powder inlet and an aqueous ammonia inlet.

36. The resource recovery system according to claim 32, wherein a surge tank discharge pump is provided between the outlet of the solution surge tank and the inlet of the purification filter press, and the inlet and the outlet of the surge tank discharge pump are connected to the outlet of the solution surge tank and the inlet of the purification filter press, respectively.

37. A resource recovery system as claimed in claim 32, further comprising a chloride dissolving tank, the outlet of which is connected to the inlet of the chloride formulating tank.

38. A resource recovery system as claimed in claim 32, wherein a precision filter is provided between the outlet of the chloride dissolving tank and the inlet of the chloride preparation tank, and the inlet and the outlet of the precision filter are connected to the outlet of the chloride dissolving tank and the inlet of the chloride preparation tank, respectively.

39. A resource recovery system as claimed in claim 38, wherein a dissolving tank discharge pump is provided between the outlet of the chloride dissolving tank and the inlet of the precision filter, and the inlet and the outlet of the dissolving tank discharge pump are connected to the outlet of the chloride dissolving tank and the inlet of the precision filter, respectively.

40. A resource recovery system as claimed in claim 32, wherein a chloride make-up pump is provided between the outlet of the chloride make-up tank and the inlet of the pre-concentrator, the inlet and outlet of the chloride make-up pump being connected to the outlet of the chloride make-up tank and the inlet of the pre-concentrator respectively.

41. The resource recovery system of claim 32, wherein a pre-concentrator circulation pump is disposed between the liquid outlet of the pre-concentrator and the inlet of the ternary pyrolysis furnace, the liquid outlet of the pre-concentrator is connected to the inlet of the pre-concentrator circulation pump, and the outlet of the pre-concentrator circulation pump is connected to the inlet of the ternary pyrolysis furnace and the top inlet of the pre-concentrator.

42. The resource recovery system of claim 32, wherein a spray pyrolysis pump is disposed between the outlet of the preconcentrator recycle pump and the inlet of the ternary pyrolysis furnace, and the inlet and the outlet of the spray pyrolysis pump are respectively connected to the outlet of the preconcentrator recycle pump and the inlet of the ternary pyrolysis furnace.

43. The resource recovery system of claim 32, wherein a hydrochloric acid pump is disposed between the liquid outlet of the hydrochloric acid absorption tower and the liquid inlet of the hydrochloric acid leaching kettle, and the inlet and the outlet of the hydrochloric acid pump are respectively connected to the liquid outlet of the hydrochloric acid absorption tower and the liquid inlet of the hydrochloric acid leaching kettle.

44. A resource recovery system as claimed in claim 32, wherein a powder collector is disposed between the solids outlet of the tertiary pyrolysis furnace and the inlet of the water leaching tank; and the inlet and the outlet of the powder collector are respectively connected with the solid outlet of the ternary pyrolysis furnace and the inlet of the water leaching kettle.

45. The resource recovery system of claim 32, further comprising a tail gas cleanup column, wherein the gas outlet of the hydrochloric acid absorption column is connected to the gas inlet of the tail gas cleanup column.

46. The resource recovery system of claim 45, wherein an acid-resistant tail gas blower is arranged between the gas outlet of the hydrochloric acid absorption tower and the gas inlet of the tail gas purification tower, and the inlet and the outlet of the acid-resistant tail gas blower are respectively connected with the gas outlet of the hydrochloric acid absorption tower and the gas inlet of the tail gas purification tower.

47. The resource recycling system according to claim 45, wherein a liquid outlet of the off-gas purification tower is provided with a purification tower circulating pump, an inlet of the purification tower circulating pump is connected to the liquid outlet of the off-gas purification tower, and an outlet of the purification tower circulating pump is connected to the liquid inlet of the off-gas purification tower and the liquid inlet of the hydrochloric acid absorption tower.

48. The resource recovery system of claim 32, wherein the system further comprises a lithium chloride purification kettle, a sulfide filter, a lithium carbonate synthesis kettle, a lithium carbonate filter and a lithium carbonate dryer, wherein an inlet of the lithium chloride purification kettle is connected with a liquid outlet of the oxide filter press, an outlet of the lithium chloride purification kettle is connected with an inlet of the sulfide filter, a liquid outlet of the sulfide filter is connected with an inlet of the lithium carbonate synthesis kettle, an outlet of the lithium carbonate synthesis kettle is connected with an inlet of the lithium carbonate filter, and a solid outlet of the lithium carbonate filter is connected with an inlet of the lithium carbonate dryer.

49. The resource recovery system according to claim 48, wherein a lithium chloride purification pump is provided between the outlet of the lithium chloride purification kettle and the inlet of the sulfide filter, and the inlet and the outlet of the lithium chloride purification pump are connected to the outlet of the lithium chloride purification kettle and the inlet of the sulfide filter, respectively.

50. The resource recovery system of claim 48, wherein a synthesis kettle discharge pump is arranged between the outlet of the lithium carbonate synthesis kettle and the inlet of the lithium carbonate filter, and the inlet and the outlet of the synthesis kettle discharge pump are respectively connected with the outlet of the lithium carbonate synthesis kettle and the inlet of the lithium carbonate filter.

51. A resource recovery system as claimed in claim 32, wherein the high temperature furnace is an electrical or natural gas heating facility.

52. A resource recovery system as set forth in claim 32 wherein the high-temperature furnace is a box furnace or a rotary furnace.

53. The resource recovery system of claim 32, wherein the hydrochloric acid leaching kettle is made of hydrochloric acid resistant material.

54. The resource recovery system of claim 32, wherein the lining of the hydrochloric acid leaching kettle is made of glass lining or graphite lining.

55. A resource recovery system as set forth in claim 32 wherein said hydrochloric acid leach tank is jacketed.

56. The resource recovery system of claim 32, wherein the hydrochloric acid leaching tank uses low-pressure steam as a heat source.

57. The resource recovery system of claim 32, wherein the ternary pyrolysis furnace is of a box type or a rotary kiln.

58. A resource recovery system as recited in claim 32, wherein the ternary pyrolysis furnace employs bottom heating.

59. A resource recovery system as recited in claim 32, wherein the tertiary pyrolysis furnace employs a bottom discharge mode.

60. A resource recovery system as recited in claim 32, wherein the ternary pyrolysis furnace is a direct heating facility.

61. A resource recovery system as recited in claim 32, wherein the tertiary pyrolysis furnace is constructed of acid and fire resistant material.

62. A resource recovery system as claimed in claim 32, wherein the tertiary pyrolysis furnace is an electrical or natural gas heating facility.

63. A resource recovery system as recited in claim 32, wherein the tertiary pyrolysis furnace is fueled by natural gas.

64. The resource recovery system of claim 32, wherein the solids outlet of the cyclone is connected to a middle portion of the ternary pyrolysis furnace for feeding the solid pulverized material into the pyrolysis furnace.

65. A resource recovery system as claimed in claim 32, wherein the water leaching vessel is adapted to leach lithium chloride from a mixed oxide of nickel oxide, cobalt oxide and manganese oxide.

66. A resource recovery system as set forth in claim 32, wherein the water leaching tank is made of a chloride ion resistant alloy.

67. A resource recovery system as claimed in claim 32, wherein the water leaching tank is of a jacket structure and low pressure steam is used as a heat source.

68. A resource recovery system as claimed in claim 48, wherein the sulfide filter is a tubular or basket filter press.