CN109402394A - A method of the comprehensively recovering valuable metal from lithium ion cell electrode waste material - Google Patents
A method of the comprehensively recovering valuable metal from lithium ion cell electrode waste material Download PDFInfo
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- CN109402394A CN109402394A CN201811200438.9A CN201811200438A CN109402394A CN 109402394 A CN109402394 A CN 109402394A CN 201811200438 A CN201811200438 A CN 201811200438A CN 109402394 A CN109402394 A CN 109402394A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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Abstract
The invention discloses a kind of methods of comprehensively recovering valuable metal from lithium ion cell electrode waste material, comprising the following steps: (1) handles lithium ion cell electrode waste material through acidleach-removal of impurities, obtain the purified solution of nickel and cobalt containing manganese lithium；(2) purified solution, precipitating reagent and reducing agent of nickel and cobalt containing manganese lithium are mixed, selective precipitation separates nickel cobalt manganese, obtains nickel cobalt manganese precipitation slag and rich lithium solution；(3) richness lithium solution obtained in step (2) is handled using bipolar membrane electrodialysis method, obtains lithium hydroxide solution and dilute acid soln；(4) lithium hydroxide solution obtained in step (3) is concentrated by evaporation processing to get concentrated mother liquor and battery-stage monohydrate lithium hydroxide product is arrived.Method of the invention, process flow is simple, processing cost is low, three-waste free discharge, nickel in the mixed solution of nickel and cobalt containing manganese lithium, cobalt, manganese, lithium the rate of recovery be all larger than 99%.
Description
Technical field
The invention belongs to valuable metal recovery field more particularly to a kind of methods that valuable metal is recycled from lithium battery.
Background technique
Flourishing for new-energy automobile industry, is concerned energy metal.To solve the industry resource guarantee of lithium electricity
Bottleneck problem, major Li electricity enterprise actively expand the raw material sources of nickel cobalt manganese lithium.Cobalt and lithium are short due to domestic Resources
Scarce, external limit such as exploits and exports at the factors, has become keystone resources problem urgently to be resolved in industry at present.
Rich in metals such as nickel cobalt manganese lithiums in scrap lithium ion battery, it has also become the valuable source source of energy metal in short supply.
Over nearly 3 years, the extraction and separation technologies such as pyrogenic process, the wet process of recycling nickel cobalt manganese lithium are extracted from waste and old lithium ion battery and are occurred in succession, and
Industry conversion is realized successively, and such as by the end of in March, 2018, the enterprise of country's layout power battery recycling has reached more than 400 families.From
From the point of view of extractive technique, each corporate boss will use wet processing process, i.e. nickel and cobalt containing manganese lithium waste material first makes valuable gold through the molten processing of acid
Category is transferred to solution, and the later period separates and recovers nickel cobalt manganese lithium from solution again；Currently, for point of nickel cobalt manganese lithium in complicated solution system
From, mainly there is preferential precipitation to divide the methods of lithium, preferential extraction point nickel cobalt manganese, either first separating Li still first separates nickel cobalt manganese,
All have that process flow is long, recovery rate of valuable metals is not high, lithium salts quality is irregular, generate a large amount of high sodium waste-waters, technique is owed
The problems such as environmentally friendly, not yet makes a breakthrough.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided
Recovery rate of valuable metals is high, process flow is short, processing cost is low, environmentally protective integrates back from lithium ion cell electrode waste material
The method for receiving valuable metal.In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A method of the comprehensively recovering valuable metal from lithium ion cell electrode waste material, comprising the following steps:
(1) lithium ion cell electrode waste material is handled through acidleach-removal of impurities, obtains the purified solution (nickel cobalt of nickel and cobalt containing manganese lithium
Manganese is divalent)；
(2) purified solution, precipitating reagent and reducing agent of nickel and cobalt containing manganese lithium are mixed, selective precipitation separates nickel cobalt manganese, obtains
To nickel cobalt manganese precipitation slag and rich lithium solution；
(3) by richness lithium solution obtained in step (2) using bipolar membrane electrodialysis method handle, obtain lithium hydroxide solution and
Dilute acid soln；
(4) lithium hydroxide solution obtained in step (3) is concentrated by evaporation processing to get concentrated mother liquor and LITHIUM BATTERY is arrived
Monohydrate lithium hydroxide product.
In the above method, it is preferred that in the step (2), nickel cobalt manganese precipitation slag can be used for making using the molten processing of acid, acquisition
The nickel cobalt manganese mixed solution of standby lithium ion battery ternary precursor.
In the above method, it is preferred that in the step (2), the process that selective precipitation separates nickel cobalt manganese includes following step
It is rapid:
S1: purified solution, precipitating reagent and the reducing agent that nickel and cobalt containing manganese lithium is added into the reaction kettle equipped with underflow are sunk
It forms sediment and reacts, keep heating and stirring, control the purified solution of nickel and cobalt containing manganese lithium and the adding speed of precipitating reagent to control solution
PH value is 8-14；
S2: after the purified solution addition to nickel and cobalt containing manganese lithium, continue the pH stable for adding precipitating reagent control slurry
In 10-12, stop addition precipitating reagent, insulated and stirred ageing reaction；
S3: the slurry after being aged in S2 is separated by solid-liquid separation to obtain precipitation slag and mother liquor of precipitation of ammonium, gained precipitation slag is nickel
Cobalt manganese precipitation slag, gained mother liquor of precipitation of ammonium are rich lithium solution.
In the above method, it is preferred that the underflow is mother liquor of precipitation of ammonium obtained in week-base water or S3, and controls the pH of underflow
Value is 10-12.
In the above method, it is preferred that in the S1, when precipitation reaction, keeping reaction temperature is 30-95 DEG C；In the S2,
When insulated and stirred ageing reaction, control reaction temperature is 30-95 DEG C, reaction time 0.1-6h.
In the step of above method (2), when selective precipitation separates nickel cobalt manganese, the crystal form of nickel cobalt manganese precipitating is not wanted
It asks, as long as can generate large granular spherical is easy to filtering, therefore, in step (2) not to the control of reaction temperature, pH value
Too high requirement can reduce production cost.
In the above method, it is preferred that the reducing agent be ascorbic acid, glucose, sulphite and hydrazine hydrate in extremely
Few one kind.The addition of reducing agent is active oxygen present in control solution, and avoiding manganese from being oxidized, (manganese is unfavorable for crystalline substance after being oxidized
The growth of type is difficult to filter removal in subsequent process), cause in rich lithium solution that impurity content is excessively high, it is difficult to realize nickel cobalt manganese with
Lithium efficiently separates.
In the above method, it is preferred that the additive amount of the reducing agent is manganese content in the purified solution of nickel and cobalt containing manganese lithium
0.5-2.0 times.The additional amount of reducing agent needs accurate control, is added excessively, and high process cost also brings along impurity, is added
It is very few, the purpose of consumption active oxygen is not achieved.
In the above method, it is preferred that the precipitating reagent is to obtain in sodium hydroxide, potassium hydroxide, lithium hydroxide or step (4)
At least one of concentrated mother liquor arrived.When precipitating reagent is sodium hydroxide, potassium hydroxide, lithium hydroxide, controlling its concentration is
10-1000g/L。
In the above method, it is preferred that be used for acidleach in the dilute acid soln return step (1) generated in the step (3)
Journey；The concentrated mother liquor return step (1) generated in the step (4) or (2) are for adjusting pH value of solution.
In the above method, it is preferred that in the purified solution of the nickel and cobalt containing manganese lithium, other gold of control in addition to nickel cobalt manganese lithium
Belong to ion concentration and is no more than 10ppm.Studies have shown that the impurity ion content contained in solution need to control within the above range,
So the qualified lithium hydroxide that can prepare LITHIUM BATTERY lithium hydroxide product could be directly obtained in subsequent bipolar membrane electrodialysis
Solution；If exceeding above range, the richness lithium solution is miscellaneous in lithium hydroxide solution obtained after bipolar membrane electrodialysis treatment
Matter content is higher, and lithium hydroxide product quality is low.
Compared with the prior art, the advantages of the present invention are as follows:
1, using method of the invention, nickel in the mixed solution of nickel and cobalt containing manganese lithium, cobalt, manganese, lithium the rate of recovery be all larger than
99%.
2, method of the invention introduces the technology of preferential precipitation separation nickel cobalt manganese, avoids traditional preferential sinker and limited
The problems such as a large amount of foreign ions of introducing present in extraction and separation nickel cobalt manganese and the low lithium rate of recovery.
3, method of the invention, by the chemical property difference of nickel cobalt manganese lithium, realized by chemical precipitation nickel cobalt manganese with
The Selective Separation of lithium is sunk by control (avoiding manganese from being oxidized as reducing agent is added) Lai Gaishan nickel cobalt manganese slag of reaction condition
Drop and strainability, have the advantages that good separating effect, metal high income.
4, method of the invention, process flow is simple, processing cost is low, three-waste free discharge.
5, the method for the present invention can handle the nickel and cobalt containing manganese lithium mixed solution of various various concentration contents, and technological adaptability is wide.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
Hunan Battery Plant provide waste and old ternary cell anode waste (through safe-discharge, physics dismantling, separation aluminium foil,
The positive-active waste material obtained after separation conductive agent and binder), it handles to obtain nickel and cobalt containing manganese lithium through sulfuric acid leaching-removal of impurities
Purified solution (nickel cobalt manganese is divalent), ingredient is as shown in table 1.
The method of comprehensively recovering valuable metal from the purified solution of above-mentioned nickel and cobalt containing manganese lithium, comprising the following steps:
(1) in the purified solution of nickel and cobalt containing manganese lithium, sodium sulfite is added as reducing agent, reducing agent additive amount is nickel and cobalt containing
0.75 times of manganese content in the purified solution of manganese lithium, using 40%NaOH solution as precipitating reagent, into nickel and cobalt containing manganese lithium purified solution
It is slowly added lye, control reaction temperature is 70 DEG C, terminal pH=10.5, so that nickel cobalt manganese is converted into precipitating, lye is protected after adding
Temperature ageing reaction 2h, obtains nickel cobalt manganese precipitating and rich lithium solution through solid-liquid separation treatment, rich lithium solution composition is as shown in table 1；
(2) nickel cobalt manganese precipitating is dissolved using dilute sulfuric acid, obtains nickel cobalt manganese mixed solution, specific ingredient is as shown in table 1, can send
Toward ternary precursor processing unit；
(3) rich lithium solution is directly entered bipolar membrane electrodialysis system, and the hydroxide that concentration is 3mol/L is obtained in alkaline chamber
Lithium and sodium hydroxide mixed solution obtain the sulfuric acid solution that concentration is 1.5mol/L in acid compartment, and sulfuric acid solution, which returns, is used as electrode
The leachate of waste material；
(4) lithium hydroxide is handled with sodium hydroxide mixed solution through evaporation and concentration, obtains battery by controlling cycles of concentration
Stage monohydrate lithium hydroxide powder and concentrated mother liquor；Concentrated mother liquor can return to step (1) as precipitating reagent.
The main chemical compositions and content of involved each solution are as shown in table 1 in the present embodiment, in the present embodiment,
Nickel, cobalt, manganese, lithium the rate of recovery be respectively 99.9%, 99.8%, 99.95% and 99.2%.
Table 1: the main chemical compositions and content (unit: g/L) of each solution involved in embodiment 1
| Element | Li | Ni | Co | Mn | Al | Fe | Cu | Na |
| The purified solution of nickel and cobalt containing manganese lithium | 10.80 | 34.5 | 12.1 | 22.6 | 0.010 | 0.008 | 0.005 | 0.010 |
| Nickel cobalt manganese mixed solution | 0.001 | 67.30 | 23.63 | 43.95 | 0.003 | 0.002 | 0.001 | 26.54 |
| Rich lithium solution | 10.34 | 0.004 | 0.003 | 0.001 | 0.006 | 0.002 | 0.002 | 54.52 |
Embodiment 2:
Changsha Battery Plant provide waste and old ternary cell anode waste (through safe-discharge, physics dismantling, separation aluminium foil,
The positive-active waste material obtained after separation conductive agent and binder), it handles to obtain nickel and cobalt containing manganese lithium through salt Ore Leaching-removal of impurities
Purified solution (nickel cobalt manganese is divalent), ingredient is as shown in table 2 below；
The method of comprehensively recovering valuable metal from the purified solution of above-mentioned nickel and cobalt containing manganese lithium, comprising the following steps:
(1) 80% hydrazine hydrate is added as reducing agent in the purified solution of nickel and cobalt containing manganese lithium, and reducing agent additive amount is nickel and cobalt containing
1.0 times of manganese content in the purified solution of manganese lithium, using 20%LiOH solution as precipitating reagent, into the purified solution of nickel and cobalt containing manganese lithium
It is slowly added precipitating reagent, control reaction temperature is 50 DEG C, terminal pH=11, so that nickel cobalt manganese is converted into precipitating, after precipitating reagent adds
Heat preservation ageing reaction 3h, obtains nickel cobalt manganese precipitating and rich lithium solution, rich lithium solution composition such as the following table 2 institute through solid-liquid separation treatment
Show；
(2) nickel cobalt manganese precipitating is dissolved using dilute sulfuric acid, obtains nickel cobalt manganese mixed solution, ingredient is as shown in table 2 below, this is molten
Liquid can be sent to ternary precursor processing unit；
(3) rich lithium solution is directly entered bipolar membrane electrodialysis system, and the hydroxide that concentration is 4mol/L is obtained in alkaline chamber
Lithium solution, the hydrochloric acid solution that concentration is 2mol/L is obtained in acid compartment, and hydrochloric acid solution returns to the leachate for being used as electrode waste material；
(4) lithium hydroxide mixed solution is handled through evaporation and concentration, obtains LITHIUM BATTERY list water hydrogen-oxygen by controlling cycles of concentration
Change lithium powder and concentrated mother liquor；Concentrated mother liquor can return to step (1) as precipitating reagent.
The main chemical compositions and content of involved each solution are as shown in table 2 below in the present embodiment, in the present embodiment,
Nickel, cobalt, manganese, lithium the rate of recovery be respectively 99.89%, 99.85%, 99.92% and 99.5%.
Table 2: the main chemical compositions and content (unit: g/L) of each material involved in embodiment 2
Embodiment 3:
Jiangxi Battery Plant provide waste and old cobalt acid lithium and lithium manganate cell positive electrode waste material (through safe-discharge, physics dismantling,
The positive-active waste material obtained after separation aluminium foil, separation conductive agent and binder), nickel and cobalt containing is handled through sulfuric acid leaching-removal of impurities
The purified solution (nickel cobalt manganese is divalent) of manganese lithium, ingredient is as shown in table 3 below；
The method of comprehensively recovering valuable metal from the purified solution of above-mentioned nickel and cobalt containing manganese lithium, comprising the following steps:
(1) the dilute LiOH solution of 100mL is added in a kettle, opens and adds gentle agitation；
(2) after underflow is warming up to 80 DEG C in reaction kettle, nickel and cobalt containing manganese lithium is added into reaction kettle by peristaltic pump simultaneously
Purified solution and embodiment 2 in step (4) output concentrated mother liquor, wherein added in the purified solution of nickel and cobalt containing manganese lithium also
Former agent ascorbic acid, additional amount are 1.5 times of manganese content in solution, control the purified solution and concentrated mother liquor of nickel and cobalt containing manganese lithium
Rate of addition, keep reaction kettle in mixed slurry pH be 10-11, keep plus gentle agitation, react slurry sufficiently；Wait contain
After the mixed solution of nickel cobalt manganese lithium is added dropwise, continue that concentrated mother liquor is slowly added dropwise, until the pH of mixed slurry stablizes 11.5,
Stop that aqueous slkali is added dropwise again, keep the temperature (80 DEG C) and continue to stir, is aged 1h；Separation of solid and liquid obtains nickel cobalt manganese slag and rich lithium solution,
Rich lithium solution composition is as shown in table 3 below；
(3) the nickel cobalt manganese slag that step (2) obtains is dissolved through dilute sulfuric acid, obtains nickel cobalt manganese mixed solution, and specific ingredient is as follows
Shown in table 3, ternary precursor preparation unit can be sent to；
(4) rich lithium solution is directly entered bipolar membrane electrodialysis system, and the hydrogen-oxygen that concentration is 3.5mol/L is obtained in alkaline chamber
Change lithium solution, the sulfuric acid solution that concentration is 1.75mol/L is obtained in acid compartment, sulfuric acid solution can return to be leached as electrode waste material
Liquid；
(5) lithium hydroxide solution is handled through evaporation and concentration, obtains battery-stage monohydrate lithium hydroxide powder and concentrated mother liquor, dense
Contracting mother liquor can return to step (2) as precipitating reagent.
The main chemical compositions and content of involved each solution are as shown in table 3 below in the present embodiment, in the present embodiment,
Nickel, cobalt, manganese, lithium the rate of recovery be respectively 99.8%, 99.6%, 99.9% and 99.2%.
Table 3: the main chemical compositions and content (unit: g/L) of each material involved in embodiment 3
| Element | Li | Ni | Co | Mn | Al | Fe | Cu | Na |
| The purified solution of nickel and cobalt containing manganese lithium | 6.25 | 8.42 | 22.6 | 36.8 | 0.006 | 0.004 | 0.002 | 0.001 |
| Nickel cobalt manganese mixed liquor | 0.01 | 20.74 | 55.92 | 90.87 | 0.01 | 0.02 | 0.01 | 0.01 |
| Rich lithium solution | 6.05 | 0.03 | 0.02 | 0.04 | 0.04 | 0.02 | 0.01 | 0.01 |
Composition detection, detection knot are carried out to monohydrate lithium hydroxide product obtained in embodiment 1, embodiment 2 and embodiment 3
Fruit is as shown in table 4 below.
Table 4: the main component (unit: %) of monohydrate lithium hydroxide product in embodiment 1-3
By upper table 4 it is found that the purity and impurity content of the monohydrate lithium hydroxide product being prepared in embodiment 1-3 are full
The requirement of sufficient LITHIUM BATTERY national standard.
Claims (10)
1. a kind of method of the comprehensively recovering valuable metal from lithium ion cell electrode waste material, which is characterized in that including following step
It is rapid:
(1) lithium ion cell electrode waste material is handled through acidleach-removal of impurities, obtains the purified solution of nickel and cobalt containing manganese lithium；
(2) purified solution, precipitating reagent and reducing agent of nickel and cobalt containing manganese lithium are mixed, selective precipitation separates nickel cobalt manganese, obtains nickel
Cobalt manganese precipitation slag and rich lithium solution；
(3) richness lithium solution obtained in step (2) is handled using bipolar membrane electrodialysis method, obtains lithium hydroxide solution and diluted acid
Solution；
(4) lithium hydroxide solution obtained in step (3) is concentrated by evaporation processing to get concentrated mother liquor and LITHIUM BATTERY list water is arrived
Lithium hydroxide product.
2. the method according to claim 1, wherein nickel cobalt manganese precipitation slag is using the molten place of acid in the step (2)
Reason obtains the nickel cobalt manganese mixed solution that can be used for preparing lithium ion battery ternary precursor.
3. the method according to claim 1, wherein selective precipitation separates nickel cobalt manganese in the step (2)
Process the following steps are included:
S1: purified solution, precipitating reagent and the reducing agent that nickel and cobalt containing manganese lithium is added into the reaction kettle equipped with underflow precipitate anti-
It answers, keeps heating and stirring, control the purified solution of nickel and cobalt containing manganese lithium and the adding speed of precipitating reagent to control the pH value of solution
For 8-14；
S2: after the purified solution addition to nickel and cobalt containing manganese lithium, the pH stable for continuing to add precipitating reagent control slurry is in 10-
12, stop addition precipitating reagent, insulated and stirred ageing reaction；
S3: the slurry after being aged in S2 is separated by solid-liquid separation to obtain precipitation slag and mother liquor of precipitation of ammonium, gained precipitation slag is nickel cobalt manganese
Precipitation slag, gained mother liquor of precipitation of ammonium are rich lithium solution.
4. according to the method described in claim 3, it is characterized in that, the underflow is to precipitate mother obtained in week-base water or S3
Liquid, and the pH value for controlling underflow is 10-12.
5. according to the method described in claim 3, it is characterized in that, in the S1, when precipitation reaction, the reaction temperature is kept to be
30-95℃；In the S2, when insulated and stirred ageing is reacted, control reaction temperature is 30-95 DEG C, reaction time 0.1-6h.
6. method according to any one of claims 1-5, which is characterized in that the reducing agent is ascorbic acid, grape
At least one of sugar, sulphite and hydrazine hydrate.
7. according to the method described in claim 6, it is characterized in that, the additive amount of the reducing agent is the purification of nickel and cobalt containing manganese lithium
0.5-2.0 times of manganese content in solution.
8. method according to any one of claims 1-5, which is characterized in that the precipitating reagent is sodium hydroxide, hydrogen-oxygen
At least one of concentrated mother liquor obtained in change potassium, lithium hydroxide or step (4).
9. method according to any one of claims 1-5, which is characterized in that the diluted acid generated in the step (3) is molten
Acidleach process is used in liquid return step (1)；The concentrated mother liquor return step (1) generated in the step (4) or (2) are for adjusting
Save pH value of solution.
10. method according to any one of claims 1-5, which is characterized in that the purified solution of the nickel and cobalt containing manganese lithium
In, other metal ion contents controlled in addition to nickel cobalt manganese lithium are no more than 10ppm.
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