CN108330286A - A method of synthetical recovery cobalt and lithium from cobalt acid lithium waste material - Google Patents
A method of synthetical recovery cobalt and lithium from cobalt acid lithium waste material Download PDFInfo
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- CN108330286A CN108330286A CN201810096632.0A CN201810096632A CN108330286A CN 108330286 A CN108330286 A CN 108330286A CN 201810096632 A CN201810096632 A CN 201810096632A CN 108330286 A CN108330286 A CN 108330286A
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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
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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
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a kind of methods of synthetical recovery cobalt and lithium in cobalt acid lithium waste material, and in particular to valuable metal recovery utilizes field, and this method includes：After cobalt acid lithium waste material is first leached filtering with acid solution, gained filtrate adsorbs resins selective adsorption of cobalt with polyvalent metal, after recycling cobalt；Remaining filtrate is isolated into lithium hydroxide and acid solution with Bipolar Membrane again, completes elemental lithium recycling, the acid solution isolated can be recycled directly.The method according to the present invention, easy to operate easily-controllable, chemical raw material used is single, while effectively realization to the abundant synthetical recovery of cobalt, lithium metal high-purity in cobalt acid lithium waste material, it can also realize and acid solution raw material used is recycled, environment-friendly high-efficiency, industrial utility value height.
Description
Technical field
The present invention relates to precious metals recovery methods in a kind of waste lithium cell positive electrode, more particularly to a kind of from cobalt
The method of synthetical recovery cobalt and lithium in acid lithium battery waste material.
Background technology
Cobalt acid lithium battery is widely used in the electronic products such as mobile phone, notes body, as a kind of common lithium battery due to electricity
The reasons such as sub- model change is fast, user's usage amount is big, there is a large amount of cobalt acid lithium battery stopping using with electronic product
And it discards.But discarded cobalt acid lithium battery has very high recovery value by disassembling the positive pole material of lithium cobalt acid separated,
Wherein cobalt content is up to 60% or more, while also containing 7% or more lithium, and China's cobalt and lithium are more rare, therefore comprehensive
The cobalt and lithium recycled in cobalt acid lithium has very high application value.
In existing cobalt acid lithium waste material purification technique, since cobalt is transition metal element, lithium is alkali family metallic element,
With very big otherness, typically by the cobalt acid lithium waste material of preliminary treatment, after the removal of impurities of acidleach dissolution filter, by cobalt and lithium
After being dissolved in acid solution, then through alkaline chemical precipitation cobalt, and with carbonate deposition crystallize mode the lithium in acid dip solution is extracted
Come.But the impurity largely substituted by alkaloid substance can be introduced during alkaline chemical precipitation cobalt so that after being settled out cobalt, to the later stage
The purification difficulty of the purification of lithium increases, and can only be purified, is purified to by way of the multiple precipitated crystal using sodium carbonate
This is very high.
Invention content
It is an object of the invention to overcome the above-mentioned deficiency in the presence of the prior art, one kind is provided from cobalt acid lithium waste material
The new method of synthetical recovery cobalt and lithium, this method is simple and easy to control, and cost for purification is low, and can realize and not introduce other impurities premise
Under, it to the cobalt and lithium progress comprehensive reutilization in cobalt acid lithium battery, while realizing and purification is recycled with sulfuric acid, efficiently
Environmental protection.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical schemes：
A method of synthetical recovery cobalt and lithium from cobalt acid lithium waste material, which is characterized in that first by cobalt acid lithium waste material acid
After liquid leaches filtering, gained filtrate adsorbs resins selective adsorption of cobalt with polyvalent metal, to recycle cobalt；Then, it then will remain
Remaining filtrate isolates lithium hydroxide and acid solution with Bipolar Membrane, completes elemental lithium recycling.
Wherein, " polyvalent metal absorption resin " of the present invention be a kind of selective absorbing chemical valence of finger to finger be divalent and
The absorption resin of the above metal ion of divalent.
According to above-mentioned technical proposal, the present invention provides the new method of synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium,
By the way that cobalt acid lithium waste material after acidleach is filtered to remove other solid impurities, to be obtained to the acidleach filtering containing cobalt, lithium metal element
Liquid；The filtrate is adsorbed into resin by the cobalt ions selective absorption in filtrate with polyvalent metal again, cobalt is returned to realize
After receipts；Bipolar membrane electrodialysis technology is selected again, and the water in residual filtrate is ionized into H+And OH-Ion, gained H+Ion and solution
In acid ion combine generate acid, gained OH-Ion is then with lithium metal ions binding at lithium hydroxide, thus by residual filtrate
In lithium acid salt solution be separated into the acid solution and lithium hydroxide solution of high-purity, gained lithium hydroxide solution can be through further concentrating
Crystallization obtains that crystalline lithium can be aoxidized directly as the high-purity hydrogen that lithium battery raw materials for production use；The acid solution isolated then may be used
It recycles and utilizes as leachate direct circulation.Add the processing side of carbonate repeated precipitation again relative to existing acidleach-alkaline chemical precipitation
For formula, the method for the invention, easy to operate easily-controllable, chemical raw material used in technique is single, not only effectively avoids alkaline matter
Difficulty problem is purified using later stage lithium metal is increased, moreover it is possible to realization fully recycling to acid solution raw material used, environment-friendly high-efficiency,
Industrial utility value is high.
Based on the above-mentioned technical proposal, in a kind of waste material from cobalt acid lithium of the present invention synthetical recovery cobalt and lithium method,
Specifically comprise the following steps：
S1：Acidleach is filtered：Cobalt acid lithium waste material is diluted with water into cobalt acid lithium slurry, then acid is added into cobalt acid lithium slurry
Liquid, it is 1-2 to adjust the cobalt acid lithium slurry pH value, is warming up to 70-90 DEG C, under stirring condition, maintains the cobalt acid lithium slurry pH
Value is that 1-2 filters reaction paste after reacting 2-3 hours；
S2：Polyvalent metal adsorbs resins selective adsorption of cobalt：By filtering gained filtrate with the flow velocity of 2-10BV/h, by more
Valence metal adsorption resin, and controlled at 5-70 DEG C, the polyvalent metal absorption resins selective is made to inhale the cobalt in filtrate
It is attached；
S3：Bipolar Membrane separating Li：By the filtrate after adsorption of cobalt, continue to be separated into lithium hydroxide and acid solution with Bipolar Membrane, institute
Lithium hydroxide solution, be lithium hydroxide crystal to get to the recovery product of elemental lithium through further condensing crystallizing；Gained acid solution
It can be recycled directly as the leachate in step 1.
According to above-mentioned preferred embodiment, by corresponding to technological parameter in the method for the invention processing step and each step
It is specific to limit, further ensure that and improve the recovering effect to cobalt and lithium.Specifically：
First, in acidleach filtration step, the cobalt acid lithium material liquid pH value 1-2 is controlled, is on the one hand intended to the cobalt
Cobalt, lithium metal in sour lithium slurry carry out selective solution, are ensuring the cobalt in cobalt acid lithium slurry, lithium metal carrying out maximum limit
Degree dissolving simultaneously, prevents the dissolving of other impurities metal from entering in acid dip solution, to play the role of filtering and impurity removing；Another party
Face maintains the acid dip solution pH to be maintained within the scope of 1-2, it is also contemplated that utilizes multivalence to adsorb resin in conjunction in the step 2
When selective absorption cobalt metal element, prevent acidity is excessively high from causing, to adsorption of cobalt resin, to play the role of de-parsing, and then influence pair
The adsorption effect of cobalt metal.
In addition, in the step 2, to reach the selective absorption effect to cobalt metal element, the present invention passes through selection
Polyvalent metal adsorbs resin, and cooperation controls the filtrate flow velocity 2-10BV/h, makes the polyvalent metal absorption resin by filtrate
The middle above metal of divalent carries out fully selective absorption, and purpose is detached to reach cobalt metal.Wherein, to 5-70 DEG C of temperature
Control is then to play appropriate adjusting to filtrate viscosity under the premise of guarantee has not received heat damage to absorption resin and adsorbent
Effect, and then preferred resin is to the adsorption effect of cobalt metal in filtrate.
Further, the extraordinary chelate resin that the polyvalent metal absorption resin is model CH-A.
The CH-A special types chelate resin is a kind of with very durable huge poroid polyvalent metal selective absorption huge legendary turtle
Resin, the resin are to the selective absorption sequence of polyvalent metal：Ni>Co>Mg>Ca>Na>Li.The resin is to cobalt, nickel metal
It is that the preferred polyvalent metal in the method for the invention for selective absorption Call Provision metal adsorbs with higher compatibility
Resin.
Further, the acid solution in the step 1 selects one or more of hydrochloric acid, sulfuric acid.
Further, after the polyvalent metal in the step 2 adsorbs resin by the cobalt adsorption saturation in filtrate, use is a concentration of
The sulfuric acid or hydrochloric acid of 4-10% adsorbs polyvalent metal in the cobalt backwash to solution in resin, as desorbed solution to obtain height
The cobalt salt solution of concentration is cobalt salt crystal through further condensing crystallizing, to obtain the recovery product of cobalt element.
Further, the flow velocity for controlling the desorbed solution is 1-5BV/h.
Further, when using Bipolar Membrane separating filtrate in the step 3, controlling the current density being passed through to the Bipolar Membrane is
20-80mA/cm2。
Further, in a kind of waste material from cobalt acid lithium of the present invention synthetical recovery cobalt and lithium method, further include：Incited somebody to action
Filter gained filter residue reducing agent carries out reducing leaching with the acid solution, is filtered after leaching, after gained filtrate pH is adjusted to 1-2,
The Bipolar Membrane separating Li processing in polyvalent metal absorption resin adsorption Cobalt and the step 3 in the step 2 is carried out again.
Technique is utilized for valuable metal recovery in existing cobalt acid lithium waste material, especially in hydrometallurgy recovery process,
To the cobalt in waste material, the low problem of the lithium metal rate of recovery, applicants have found that due in cobalt acid lithium waste material part cobalt with high price
Form exists, and during acidleach, the cobalt of this part high price form and is wrapped up by the cobalt metallic crystal of these high price forms
Lithium metal element, can not all be dissolved in acid dip solution, so as to cause there are about the cobalt of 30%-40%, lithium metals to enter filter
Slag can not recycle.
For this purpose, the preferred embodiment as the method for the invention, increase mixes down acidleach filtered filtration residue with reducing agent,
Acidleach again is carried out, the high-valence state cobalt in filter residue is restored at a low price, to which the cobalt of the part and its lithium metal of package leach
To after filtrate, then it is filtered deslagging, and the filtrate after reducing leaching is carried out to multivalence Choice of Resin of the present invention successively
Property adsorption of cobalt, the processing step of Bipolar Membrane separating Li, to realize abundant recycling to cobalt, lithium metal in cobalt acid lithium waste material.According to
According to above-mentioned preferred embodiment, filters the content of cobalt and lithium in deslagging and be below 0.3%, the recycling of cobalt and lithium in the cobalt acid lithium waste material
Rate is up to 99.7% or more.
Further, one or more of sodium sulfite, sulfur dioxide, thiosulfuric acid can be selected in the reducing agent.
Further, a kind of preferred reality as synthetical recovery cobalt and lithium method in a kind of waste material from cobalt acid lithium of the present invention
Scheme is applied, is specifically comprised the following steps：
S1：Cobalt acid lithium waste material is diluted with water into 20% cobalt acid lithium slurry, then sulfuric acid is added into cobalt acid lithium slurry, is adjusted
It is 1-2 to save the cobalt acid lithium slurry pH value, is warming up to 80 DEG C, under stirring condition, and it is 1-2 to maintain the cobalt acid lithium slurry pH value,
After reaction 2-3 hours, reaction paste is filtered；
S2：Filtering gained filtrate is passed through into the extraordinary chelate resin that height is 800mm or more with the flow velocity of 2-10BV/h
CH-A, and controlled at 5-70 DEG C, the extraordinary chelate resin CH-A selectivity is made to adsorb the cobalt in filtrate；It is to be adsorbed full
With it is rear, use a concentration of 4-10% sulfuric acid or hydrochloric acid as desorbed solution, by the cobalt backwash in extraordinary chelate resin CH-A to solution
In, the cobalt salt solution of high concentration is obtained, and concentrated crystallization is cobalt salt crystal, realizes the recycling to cobalt element；Wherein, it controls
The flow velocity for making the desorbed solution is 1-5BV/h；
S3：By the filtrate after adsorption of cobalt, continue with bipolar film process, controlling the current density being passed through in the Bipolar Membrane is
20-80mA/cm2, to which filtrate electrodialysis is separated into lithium hydroxide and sulfuric acid, the concentrated crystallization of gained lithium hydroxide solution,
Obtain high-purity hydrogen oxidation crystalline lithium；The leachate that gained sulfuric acid can be used as step 1 recycles；
S4:Filtering gained filter residue in step 1 is taken, reducing agent and sulfuric acid solution is added, adjusts pH under the conditions of 1-2, to carry out
Reducing leaching carries out secondary filter, then the gained filtrate progress step 2 and step 3 after secondary filter is handled after leaching, from
And it will realize and high price cobalt in gained filter residue, the recycling of the lithium of high price cobalt cladding filtered to step 1.
According to above-mentioned preferred embodiment, by technological parameters such as integrated artistic sequence of steps, reactive materials into one
Step is specific to be limited, by the processing of the step 1 acidleach filter liquor, in step 4 to the processing phase region of filtrate after reducing leaching
Point, so that it is guaranteed that in step 1 to step 3 processing procedure, under the premise of other substances are added outside without acid solution, realize to cobalt acid
The high-purity recycling of cobalt, lithium metal in lithium waste material.Meanwhile it being soaked in conjunction with the reduction for filtering gained filter residue in step 4 to acidleach
Go out recycling, realizes the high-recovery recycling to cobalt, lithium metal in cobalt acid lithium waste material.
Compared with prior art, beneficial effects of the present invention：
1, for existing cobalt acid lithium waste recovery technique, one kind of the present invention is comprehensive from cobalt acid lithium waste material
The method of Call Provision and lithium, easy to operate easily-controllable, chemical raw material used is single, after not only effectively avoiding alkaline matter from using increase
Phase lithium metal purifies difficulty problem, moreover it is possible to realize fully recycling to acid solution raw material used, environment-friendly high-efficiency, industry practicality valence
Value is high.
2, further, according to the present invention in the slave cobalt acid lithium waste material in the method for synthetical recovery cobalt and lithium, each step
It is mutually linked collaboration, is realized to cobalt, the abundant synthetical recovery of lithium metal high-purity in cobalt acid lithium waste material, while realizing to acid solution used
Recycle, improve raw material availability, reduce process costs.
3, according to the present invention in a kind of waste material from cobalt acid lithium synthetical recovery cobalt and lithium method, in conjunction with to step 1
After middle acidleach filtering after the reducing leaching of gained filter residue, to the recycling treatment process of cobalt in leachate, lithium metal, effectively overcome
In existing wet recycling process, cobalt, lithium metal recycle incomplete problem, make the rate of recovery of final cobalt and lithium be up to 99.7% with
On.
4, according to the present invention in a kind of waste material from cobalt acid lithium synthetical recovery cobalt and lithium method, the hydrogen-oxygen recycled
It is high to change lithium purity, can be used directly as lithium battery raw materials for production, industrial utility value is high.
Specific implementation mode
With reference to test example and specific implementation mode, the present invention is described in further detail.But this should not be understood
It is only limitted to embodiment below for the range of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that the content of present invention is realized
The range of invention.
Embodiment 1
S1：100g cobalt acid lithium waste materials are added in 1L water and is stirred continuously and heats, after being heated to 80 DEG C, are slowly added to
Sulfuric acid makes reaction pH maintain 1.After slurry reaction 2 hours, reaction paste is filtered.After testing, wherein cobalt content is filtrate
58g/L, lithium content 5.7g/L.
S2：It is the extraordinary chelate resin CH-A of 800mm by height again by filtering gained filtrate with the flow velocity of 2-4BV/h,
And it is 5-30 DEG C to control filtrate temperature, and the extraordinary chelate resin CH-A selectivity is made to adsorb the cobalt in filtrate；It is to be adsorbed full
With it is rear, use a concentration of 4-5% sulfuric acid or hydrochloric acid as desorbed solution, will be inhaled in extraordinary chelate resin CH-A with 1-5BV/h flow velocitys
In attached cobalt backwash to solution, the cobalt salt solution of high concentration is obtained, and concentrated crystallization obtains the cobalt that purity is 97.5% or more
Salt crystal.
After testing, wherein cobalt content is 0.0009g/L to filtrate after adsorption of cobalt, and lithium content is still 5.7g/L.
S3：The filtrate after adsorption of cobalt is continued again with bipolar film process, to control the current density being passed through in the Bipolar Membrane
For 20-30mA/cm2, to which filtrate electrodialysis is separated into lithium hydroxide and sulfuric acid, the concentrated knot of gained lithium hydroxide solution
Crystalline substance obtains the lithium hydroxide crystal that purity is 98.8%；The leachate that gained sulfuric acid can be used as step 1 recycles.
In summary after the processing step, cobalt lithium metal overall content is about 36% in gained filter residue after testing, described
The cobalt rate of recovery is about 70%, and the lithium rate of recovery is about 79%.
Embodiment 2
S1：150g cobalt acid lithium waste materials are added in 1L water and is stirred continuously and heats, after heating degree is heated to 85 DEG C, are delayed
It is slow that hydrochloric acid is added, so that reaction pH is maintained 1.5.After slurry reaction 2 hours, reaction paste is filtered.Filtrate after testing, wherein cobalt
Content is 70g/L, lithium content 7.3g/L.
S2：Filtering gained filtrate is passed through into the extraordinary chelate resin CH- that height is 900mm with the flow velocity of 5-7BV/h again
A, and it is 30-50 DEG C to control filtrate temperature, so that the extraordinary chelate resin CH-A selectivity is adsorbed the cobalt in filtrate complete；
After testing, it is still 7.3g/L that wherein cobalt content is 0.0006g/L lithium contents to filtrate after adsorption of cobalt.
S3：Filtrate after the adsorption of cobalt is continued with bipolar film process, to control the current density being passed through in the Bipolar Membrane
For 40-60mA/cm2, to which filtrate electrodialysis is separated into lithium hydroxide and sulfuric acid, the concentrated knot of gained lithium hydroxide solution
Crystalline substance, it is 99.2% lithium hydroxide crystal to obtain purity；The leachate that gained sulfuric acid can be used as step 1 recycles.
S4：By the extraordinary chelate resin CH-A after cobalt adsorption saturation in the step 2, with the sulfuric acid of a concentration of 6-8% or
Hydrochloric acid obtains the cobalt salt of high concentration as desorbed solution with 1-5BV/h flow velocitys by the cobalt backwash to solution adsorbed in the resin
Solution, and concentrated crystallization obtains the cobalt salt crystal that purity is 98.9%.
In summary after the processing step, cobalt lithium metal overall content is about 30% in gained filter residue after testing, described
The cobalt rate of recovery is about 78%, and the lithium rate of recovery is about 82%.
Embodiment 3
S1：200g cobalt acid lithium waste materials are added in 1L water and is stirred continuously and heats, after heating degree is heated to 90 DEG C, are delayed
It is slow that sulfuric acid is added, so that reaction pH is maintained 2.After slurry reaction 2 hours, reaction paste is filtered.After testing, wherein cobalt is filtrate
92g/L, lithium 9.8g/L.
S2：Filtering gained filtrate is passed through into the extraordinary chelating tree that height is 800mm -1200MM with the flow velocity of 7BV/h again
Fat CH-A, and it is 50-70 DEG C to control filtrate temperature, and the extraordinary chelate resin CH-A selectivity is made to adsorb the cobalt in filtrate；
After saturation to be adsorbed, use a concentration of 9-10% sulfuric acid or hydrochloric acid as desorbed solution, with 1-5BV/h flow velocitys by extraordinary chelate resin
In the cobalt backwash to solution adsorbed in CH-A, the cobalt salt solution of high concentration is obtained, and it is 98.2% that concentrated crystallization, which obtains purity,
Cobalt salt crystal.
After testing, wherein cobalt content is 0.0008g/L to filtrate after adsorption of cobalt, and lithium content is still 9.8g/L.
S3：Filtrate after the adsorption of cobalt is continued with bipolar film process, to control the current density being passed through in the Bipolar Membrane
For 60-80mA/cm2, to which filtrate electrodialysis is separated into lithium hydroxide and sulfuric acid, the concentrated knot of gained lithium hydroxide solution
Crystalline substance obtains the lithium hydroxide crystal that purity is 98.3%；The leachate that gained sulfuric acid can be used as step 1 recycles.
S4：Filtering gained filter residue in step 1 is taken, reducing agent and sulfuric acid solution is added, adjusts PH under the conditions of 1-2, to carry out
Reducing leaching carries out secondary filter, then the gained filtrate progress step 2 and step 3 after secondary filter is handled after leaching, from
And it will realize and high price cobalt in gained filter residue, the recycling of the lithium of high price cobalt cladding filtered to step 1.Wherein, the reducing agent is optional
With one or more of sodium sulfite, sulfur dioxide, thiosulfuric acid.
In summary after the processing step, cobalt lithium metal overall content is about 0.01% in gained filter residue after testing, institute
It is about 99.8% to state the cobalt rate of recovery, and the lithium rate of recovery is about 99.76%.
Comparative example 1
To verify in acidleach filtration step, the cobalt acid lithium slurry pH=1-2 controls are to cobalt, lithium gold in cobalt acid lithium waste material
Belonging to recovering effect influences, and following contrast experiment's example is arranged relative to embodiment 1 in inventor：
Comparative example 1-1
The comparative example is arranged relative to embodiment 1, and compared with Example 1, difference lies in by step 1 acidleach
In filter processing, the cobalt acid lithium slurry pH is adjusted to 0.1-0.5, remaining step of preparation process and parameter all same.
After testing, cobalt content is significantly increased to 0.012g/L in the filtrate in the step 3 after adsorption of cobalt, final to be made
Cobalt salt crystal purity fall to 90.23%, it is 87.6% that gained lithium hydroxide crystal, which is remarkably decreased,.
Comparative example 1-2
The comparative example is arranged relative to embodiment 1, and compared with Example 1, difference lies in take step 1 acidleach
In filtration treatment, the cobalt acid lithium slurry pH is adjusted to 4-5, remaining step of preparation process and parameter all same.
After testing, cobalt content is significantly increased to 0.018g/L in the filtrate in the step 3 after adsorption of cobalt, final to be made
Cobalt salt crystal purity fall to 89.23%, it is 70.6% that gained lithium hydroxide crystal, which is remarkably decreased,.
Comparative example 2
Cobalt, lithium metal recovering effect in cobalt acid lithium waste material are influenced to verify the desorbed solution acid concentration (4-10%), Shen
It asks someone that following contrast experiment's example is arranged relative to embodiment 1：
Comparative example 2-1
The comparative example is arranged relative to embodiment 1, and compared with Example 1, difference lies in by the parsing in embodiment 1
Liquid is transformed to a concentration of 12% sulfuric acid, remaining step of preparation process and parameter all same.
After testing, obtained cobalt salt crystal weight is finally parsed to reduce, it is 50.9% that the cobalt rate of recovery, which is remarkably decreased, remaining
Parameter does not occur significant change.
Comparative example 2-2
The comparative example is arranged relative to embodiment 1, and compared with Example 1, difference lies in by the parsing in embodiment 1
Liquid is transformed to a concentration of 2-3% sulfuric acid, remaining step of preparation process and parameter all same.
After testing, it finally parses obtained cobalt salt crystal weight to reduce, the cobalt rate of recovery is remarkably decreased as 55.6% remaining ginseng
Number does not occur significant change.
Claims (10)
1. a kind of method of synthetical recovery cobalt and lithium in waste material from cobalt acid lithium, which is characterized in that first by cobalt acid lithium waste material acid solution
After leaching filtering, gained filtrate adsorbs resins selective adsorption of cobalt with polyvalent metal, to recycle cobalt；It then, then will be remaining
Filtrate isolate lithium hydroxide and acid solution with Bipolar Membrane, complete elemental lithium recycling.
2. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 1, which is characterized in that tool
Body includes the following steps：
S1：Acidleach is filtered：Cobalt acid lithium waste material is diluted with water into cobalt acid lithium slurry, then acid solution is added into cobalt acid lithium slurry, is adjusted
It is 1-2 to save the cobalt acid lithium slurry pH value, is warming up to 70-90 DEG C, and under stirring condition, it is 1- to maintain the cobalt acid lithium slurry pH value
2, after reacting 2-3 hours, reaction paste is filtered；
S2：Polyvalent metal adsorbs resins selective adsorption of cobalt：By filtering gained filtrate with the flow velocity of 2-10BV/h, pass through multivalence gold
Belong to absorption resin, and controlled at 5-70 DEG C, makes the adsorbing the cobalt in filtrate of polyvalent metal absorption resins selective；
S3：Bipolar Membrane separating Li：By the filtrate after adsorption of cobalt, continue to be separated into lithium hydroxide and acid solution, gained hydrogen with Bipolar Membrane
Lithia solution is lithium hydroxide crystal to get to the recovery product of elemental lithium through further condensing crystallizing；Gained acid solution can be straight
It connects and is recycled as the leachate in step 1.
3. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 2, which is characterized in that institute
State the extraordinary chelate resin that polyvalent metal absorption resin is model CH-A.
4. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 2, which is characterized in that institute
It states acid solution and selects one or more of sulfuric acid, hydrochloric acid.
5. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 2, which is characterized in that wait for
Polyvalent metal absorption resin in the step 2 is by after the cobalt adsorption saturation in filtrate, with the sulfuric acid or salt of a concentration of 4-10%
Acid is used as desorbed solution, polyvalent metal is adsorbed in the cobalt backwash to solution in resin, cobalt salt solution is obtained, through further concentrating knot
Crystalline substance is cobalt salt crystal, to obtain the recovery product of cobalt element.
6. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 5, which is characterized in that control
The flow velocity for making the desorbed solution is 1-5BV/h.
7. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 2, which is characterized in that institute
When stating in step 3 with Bipolar Membrane separating filtrate, it is 20-80mA/cm to control the current density being passed through to the Bipolar Membrane2。
8. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 2, which is characterized in that also
Including：
S1 is filtered into gained filter residue reducing agent and carries out reducing leaching with the acid solution, is filtered after leaching, by gained filtrate pH tune
After section is 1-2, then carry out the bipolar UF membrane in polyvalent metal absorption resin adsorption cobalt and the step 3 in the step 2
Lithium processing.
9. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 8, which is characterized in that institute
State reducing agent select sodium sulfite, sulfur dioxide, one or more of thiosulfuric acid.
10. the method for synthetical recovery cobalt and lithium in a kind of waste material from cobalt acid lithium according to claim 1, which is characterized in that
Specifically comprise the following steps：
S1：Cobalt acid lithium waste material is diluted with water into 20% cobalt acid lithium slurry, then sulfuric acid is added into cobalt acid lithium slurry, adjusts institute
It is 1-2 to state cobalt acid lithium slurry pH value, is warming up to 80 DEG C, under stirring condition, and it is 1-2, reaction to maintain the cobalt acid lithium slurry pH value
After 2-3 hours, reaction paste is filtered；
S2：Gained filtrate will be filtered, is the extraordinary chelate resin CH-A of 800mm or more by height with the flow velocity of 2-10BV/h,
And controlled at 5-70 DEG C, the extraordinary chelate resin CH-A selectivity is made to adsorb the cobalt in filtrate；After saturation to be adsorbed,
The sulfuric acid or hydrochloric acid for using a concentration of 4-10% are obtained as desorbed solution by the cobalt backwash to solution in extraordinary chelate resin CH-A
To cobalt salt solution, and concentrated crystallization is cobalt salt crystal, realizes the recycling to cobalt element；Wherein, the stream of the desorbed solution is controlled
Speed is 1-5BV/h；
S3：By the filtrate after adsorption of cobalt, continue to control the current density being passed through in the Bipolar Membrane with bipolar film process to be 20-
80mA/cm2, to which filtrate electrodialysis is separated into lithium hydroxide and sulfuric acid, the concentrated crystallization of gained lithium hydroxide solution obtains
Lithium hydroxide crystal；The leachate that gained sulfuric acid can be used as step 1 recycles；
S4:Filtering gained filter residue in step 1 is taken, reducing agent and sulfuric acid solution is added, adjusts pH under the conditions of 1-2, to be restored
It leaches, secondary filter is carried out after leaching, then the gained filtrate progress step 2 and step 3 after secondary filter are handled, thus will
Realize the recycling that high price cobalt and the lithium of high price cobalt cladding in gained filter residue are filtered to step 1.
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| CN110468280A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | A kind of method that ion-exchange recycles valuable metal in waste and old cobalt acid lithium battery |
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Application publication date: 20180727 |