CN108110357A - A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate - Google Patents
A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate Download PDFInfo
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- CN108110357A CN108110357A CN201711338938.4A CN201711338938A CN108110357A CN 108110357 A CN108110357 A CN 108110357A CN 201711338938 A CN201711338938 A CN 201711338938A CN 108110357 A CN108110357 A CN 108110357A
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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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- 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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- 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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- 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
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Abstract
The invention discloses a kind of methods that valuable metal is recycled from positive material of waste lithium iron phosphate, specifically comprise the following steps：(1) it will disassemble, the lithium iron phosphate battery positive material progress thorough roasting oxidation after broken mill, Fe, Li metallic element in the cell positive material is made to generate Fe by roasting oxidation2O3、FePO4And Li3PO4；(2) it will be placed in dilute acid soln and impregnate, the Li3PO4 salt in roasting material is made fully to dissolve through the roasting material after the oxidation of step (1) thorough roasting, and filter, realize Li in roasting material3PO4With Fe2O3、FePO4Separation；(3) step of learning from else's experience (3) treated filtrate, and adjust the filtrate made alkaline makes the Li3PO4 in filtrate directly be precipitated for precipitation, so as to fulfill to solid-state Li3PO4Recycling.According to the method for the invention, technological process is short, easy to operate, at a low price environmental protection, and the high-grade prioritizing selection of lithium metal in lithium iron phosphate battery positive material material can be recycled, and has extensive prospects for commercial application.
Description
Technical field
It is more particularly to a kind of from waste and old ferric phosphate the present invention relates to a kind of to old and useless battery resource secondary recycling field
Phosphorus, iron, the method for three kinds of valuable metals of lithium are recycled in anode material of lithium battery.
Background technology
Under the dual-pressure of energy saving and emission reduction, new-energy automobile oneself become the direction of future automobile industrial development.With
Government widelys popularize, and new-energy automobile industry will enter Rapid development stage by the starting stage.Power battery is as new energy
The two of the parts of source automobile most critical, demand rapidly increases.Wherein, ferric phosphate carp battery is because with higher theoretical appearance
Amount, good discharge platform, outstanding cyclical stability and it is cheap the advantages that, be widely used in new-energy automobile.It is waste and old
Reasonable recycle of ferric phosphate carp material will promote the development of new-energy automobile industry, realize the comprehensive utilization of resource.
At present, the technique that high value element is recycled in a series of existing waste lithium iron phosphate batteries mainly includes wet method and soaks
Go out technique and solid phase method high-temperature calcination regeneration LiFePO4 technique.Its main flow of wet-leaching technique is through accompanying by old and useless battery
Burn, it is broken obtain batch mixing, iron, lithium mixing slag are then obtained except aluminium using alkaline process, then leach iron, elemental lithium simultaneously, selected afterwards
Property precipitates to obtain lithium product.As CN103280610A dissolves by alkaline process to obtain iron content lithium-containing solution, and iron is sunk with ferric phosphate
Shallow lake form removal, gained lithium-containing solution are further used for the recycling of elemental lithium.CN101847763A is then dissolved using organic solvent
And acidolysis, it then aids in adding in sodium sulfide acquisition elemental lithium.CN102956936A discloses a kind of based on acidleach and alkali leaching recycling
Using the method for valuable metal, refer to the positive electrode after burning after 0.5~2.0 time acidleach of pH value, acidleach filtrate readjustment pH value is sunk
Shallow lake aluminium, iron, copper, alkali lixivium are used to recycle lithium into two steps readjustment pH value.The research of high-temperature calcination is concentrated mainly on phosphoric acid
The regeneration of iron lithium anode material, as CN102280673A, CN102583297A, CN102751548A, CN104362408A are announced
High-temperature calcination prepares the technological parameter of LiFePO4 product under oxidative conditions.Based on current hydrometallurgy or high temperature
Metallurgical recovery process, although ferric phosphate lithium cell can be recycled, and obtains lithium iron phosphate positive material or lithium carbonate
Multiple products are waited, but there is following deficiency：
1st, in above-mentioned wet-leaching technique, generally require to use the object of the Strong oxdiatives highly acid such as hydrogen peroxide, sulfuric acid
Matter, process dangerous is high, be easy to cause the volatilization of hydrogen peroxide and sulfuric acid, causes environmental pollution, and to the corrosion-resistant of consersion unit
Property requirement it is high, equipment cost is high.And it does not leach elemental lithium preferentially, causes to leach acid or alkali immersion liquid consumption is very big, recycle work
Skill flow is complicated, recycles the lithium carbonate product of acquisition often because grade is low, it is impossible to directly be used as battery material recycling.
2nd, high-temperature calcination directly prepare lithium iron phosphate positive material often technological process it is long, it is necessary to stringenter detection and
Dosage regulating step, recovery process are difficult to, and be easy to cause the unqualified and wastage of material of product, therefore practical application
It is extremely limited.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency in the presence of the prior art, it is short to provide a kind of technological process, behaviour
Make simple, environmental protection at a low price, and high-grade prioritizing selection recycling can be carried out to the lithium metal in lithium iron phosphate battery anode waste material
Method.
In order to realize foregoing invention purpose, the present invention provides following technical schemes：
A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate, includes the following steps：
(1) roast：It will disassemble, the lithium iron phosphate battery positive material progress thorough roasting oxidation after broken mill, and make the electricity
Fe, Li metallic element in the positive electrode of pond generates Fe by roasting oxidation2O3、FePO4And Li3PO4；
(2) acidleach：It will be placed in dilute acid soln and impregnate, make the roasting through the roasting material after the oxidation of step (1) thorough roasting
Li3PO4 salt in imitation frosted glass fully dissolves, and filters, and realizes Li in roasting material3PO4With Fe2O3、FePO4Separation；
(3) alkali is precipitated：Step of learning from else's experience (3) treated filtrate, and the filtrate made alkaline is adjusted, make in filtrate
Li3PO4 is directly precipitated with coprecipitation mode, so as to fulfill to solid-state Li3PO4Recycling.
Lithium iron phosphate positive material is through disassembling, after the preliminary removal of impurities processing of broken mill in the step (1), the battery of gained
Positive electrode purity is preferable, then the cell positive material is carried out thorough roasting, makes middle Fe, Li of the cell anode waste
Metallic element is oxidized to Fe2O3、FePO4And Li3PO4, obtain the higher Fe of purity2O3、FePO4And Li3PO4Baking mixed material.And
And inventor has found to roast the Fe in obtained mixture through many experiments2O3And FePO4Show to be insoluble in the physics of diluted acid
Characteristic, so as to, by controlling acid dip solution pH value, can effectively realize that the roasting is mixed during step (2) dilute acid pretreatment
Close Fe in material2O3、FePO4And Li3PO4Separation of solid and liquid, the filter cake for filtering gained is containing Fe2O3、FePO4Pure mixture,
It can be directly used for synthesizing iron lithium phosphate after drying or the raw material as nontoxic antirust paint use.The filtrate is the phosphorus of higher degree
Sour lithium salt solution can be handled directly by carrying out alkaline adjusting in the step (3) to the filtrate pH value, obtained from filtrate
The lithium phosphate precipitation recovery product of middle precipitation.This dissolubility feature using lithium phosphate makes it fully molten in dilute acid soln
Xie Hou, then the mode of alkaline sedimentation precipitation is adjusted to, it can effectively ensure the high-grade for the lithium phosphate precipitated product being finally precipitated, from
And realize the purpose recycled to the high-grade of lithium phosphate.
Further, the calcination temperature in the step (1) is 200-1000 DEG C, is preferably 300-800 DEG C, further preferably
For 400-600 DEG C.
Further, the roasting time in the step (1) is 1-5h, is preferably 1.5-4h, further preferably 2-3h.
It is found through inventor's many experiments, only by the calcination temperature in the step (1) and roasting time control upper
In the range of stating, the fully oxidized generation Fe of LiFePO4 in cell positive material2O3、FePO4And Li3PO4Product, and after roasting
Obtained Fe2O3 can just show the characteristic insoluble in diluted acid, and then realize Fe2O3、FePO4And Li3PO4In step (2)
Processing is efficiently separated, and material is effectively avoided to burn or roasting oxidation not foot phenomenon.
Further, in the step (2) diluted acid can select one kind in dilute hydrochloric acid, dust technology, dilute sulfuric acid, phosphoric acid,diluted or
It is several, phosphoric acid,diluted is preferentially selected, can further prevent the introducing of other chemical compositions.And the roasting material after acid adding is adjusted mixes
The pH value for closing liquid is preferably controlled between 2.0-6.5, and further preferably control is in the range of PH=3.0-5.0.
By to by the preferred control of the acid solution pH value, it is ensured that carry out more sufficiently selection to lithium phosphate in roasting material
Property dissolving, to realize Li3PO4And Fe2O3、FePO4Efficiently separate, so as to fulfill to high-grade Li3PO4Carry out fully,
Effective recycling.Also, it is found through inventor's many experiments, the pH value of roasting material mixed liquor after acid adding is adjusted is less than
When 2.0, part FePO is had4It is dissolved in acid solution, causes the Li being finally precipitated3PO4In be mingled with part Fe (OH)3Precipitation reduces
The Li of recycling3PO4Grade；The pH value of roasting material mixed liquor after acid adding is adjusted can cause Li higher than 6.53PO4Dissolving is not filled
Point, the rate of recovery of last Li elements is caused to substantially reduce.
Further, pH value adjustment is carried out to the filtrate by soluble alkali materials in the step (3), it is described solvable
Property alkaline matter preferred sodium hydroxide, potassium hydroxide, one or more of ammonium hydroxide, and adjust the filtrate pH value control and exist
7.0-9.0 in the range of, it is preferably controlled in the range of PH=7.5-8.5.
The selection of the alkaline matter need to meet it is solvable not with the PO in filtrate4 3+The condition of reaction production precipitation, it is excellent
First select sodium hydroxide, potassium hydroxide, barium hydroxide, one or more of ammonium hydroxide, and pair plus alkali after filtrate pH value carry out
It is preferred that regulate and control, it is ensured that the Li in filtrate3PO4Making choice property is precipitated, so that it is guaranteed that the Li finally recycled3PO4The rate of recovery and
Recycle grade.
Further, the lithium iron phosphate battery positive material is being disassembled, during broken mill, after being screened using magnetic separation mode
Lithium iron phosphate battery positive material.
The lithium iron phosphate battery positive material is disassembled, during broken mill, further by environmentally friendly magnetic
Mode is selected to carry out removal of impurities selection to the LiFePO4 substance in the cell positive material, is made in pending cell positive material
The purity higher of LiFePO4.
Preferably as a kind of recycling valuable metal from positive material of waste lithium iron phosphate of the present invention
The specific embodiment of method, specifically comprises the following steps：
(1) roast：100 parts of the lithium iron phosphate battery anode waste material for disassembling, breaking mill is weighed, is put into 300-800 DEG C of roasting
Blowing air or oxygen roasting in stove, keep the temperature 1.5-4h, and waste gas is passed through lime slurry, and roasting material is taken out in cooling；
(2) acidleach：Add 200-600 parts of pure water, be pumped into stirred autoclave, be warming up to 30-90 DEG C, diluted acid is added dropwise and keeps PH=
Filtration washing after 2.0-6.5, dissolving reaction 1-4h；
(3) the filtrate tune PH=7.0-9.0 that will be obtained by filtration described in warp, lithium phosphate Precipitation in filtrate are realized pair
The recycling of lithium phosphate product.
It is highly preferred that the preferred embodiment as the present invention, one kind is returned from positive material of waste lithium iron phosphate
The method for receiving valuable metal, specifically comprises the following steps：
(1) waste lithium iron phosphate battery is taken to disassemble, 100 parts of anode waste after broken mill, is directly placed into and does not add any substance
Boat box in, in 400-600 DEG C of roaster blowing air or oxygen roasting, keep the temperature 2-3h, cooling take out roasting material；
(2) add 300-400 parts of pure water into the roasting material, be pumped into stirred autoclave, be warming up to 60-80 DEG C, be added dropwise dilute
Acid keeps PH=3.0-4.0, dissolving reaction 2-3h filterings, washing；
(3) the filtrate portion tune PH=7.5-8.5 obtained after filtering, precipitation obtain lithium phosphate, and filtering, clear water washing are dried
It is dry, draw lithium phosphate product；
(4) filter cake obtained after filtering is iron content and the pure mixture of phosphorus, and iron, P elements are recycled in drying.
Compared with prior art, beneficial effects of the present invention：
1. according to it is of the present invention it is a kind of from positive material of waste lithium iron phosphate recycle valuable metal method,
Only need to by disassembling, broken mill, the processing mode of magnetic separation high in environmental protection, realize removing to the LiFePO 4 material of cell positive material
After miscellaneous selection, fired oxidation, acidleach dissolving, alkali tune precipitation mode realization the high-grade of lithium phosphate is preferably recycled, without
Alkaline process is carried out after roasting except aluminium, entire process flow steps is greatlied simplify, has saved acid, lye usage amount, played Efficient Ring
Guarantor acts on.
2. according to it is of the present invention it is a kind of from positive material of waste lithium iron phosphate recycle valuable metal method,
It is precipitated carrying out acidleach dissolving and alkali tune to roasting material in processing step, need to only control filtrate in weak acid or alkalescent, into
One step avoids using the pollution problem of strong acid or highly basic to environment.
3. in a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate of the present invention, lead to
It crosses and utilizes the Fe obtained after roasting2O3、FePO4And Li3PO4Dissolubility feature, makes Fe2O3、FePO4And Li3PO4It is real in acid solution
It now efficiently separates, and makes Li3PO4After fully being dissolved in dilute acid soln, then the mode of alkaline sedimentation precipitation is adjusted to, it can be effective
The high-grade of lithium phosphate precipitated product being finally precipitated is ensured, so as to fulfill the mesh recycled to the high-grade of lithium phosphate
's.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
Positive material of waste lithium iron phosphate is disassembled, after the processing of broken mill, weighing 100 parts treated battery just
Pole material is put into not plus in the boat box of any substance, then is placed in blowing air or oxygen roasting, roasting in 200-1000 DEG C of roaster
It burns exhaust gas and is passed through lime slurry, after keeping the temperature 1-5h, stop heating cooling and take out roasting material；To 300-400 parts of roasting material plus pure water,
Mixed roasting material will be diluted to be pumped into stirred autoclave, be warming up to 30-90 DEG C, then dilute salt is added in into stirred autoclave
Acid stirs evenly, and adjusting ph value of mixture is 3.0-5.0, is filtered after dissolving 1-5h, is washed.Washing of Filter Cake drying is Fe2O3、
FePO4Mixture, synthesizing iron lithium phosphate is can be used as after drying or nontoxic antirust paint raw materials recovery recycles.Again to filtrate
Middle addition potassium hydroxide, it is 7.0-8.5 to adjust filtrate pH value, stands half an hour, you can obtain the lithium phosphate being precipitated from filtrate
Precipitation.
The Fe recycled after testing2O3、FePO4Mixture purity reaches 96.5%, and lithium phosphate purity reaches 97%, iron
The rate of recovery reach 95%, the rate of recovery of lithium is up to 97%.
Embodiment 2
Positive material of waste lithium iron phosphate is disassembled, breaks and grinds, after magnetic separation processing, weighing 100 parts, treated
Cell positive material is put into not plus in the boat box of any substance, is placed in blowing air or oxygen roasting in 300-800 DEG C of roaster,
Torrefaction waste gas is passed through lime slurry, after keeping the temperature 1.5-4h, stops heating cooling and takes out roasting material；To roasting material plus pure water 300-
400 parts, mixed roasting material will be diluted and be pumped into stirred autoclave, 30-90 DEG C is warming up to, then is added in into stirred autoclave
Phosphoric acid,diluted stirs evenly, and adjusting ph value of mixture is 2.5-4.5, is filtered after dissolving 1-4h, is washed.Washing of Filter Cake is dried
The pure mixture of Fe2O3, FePO4 can be used as synthesizing iron lithium phosphate or nontoxic antirust paint raw materials recovery Xun Huan profit after drying
With.Sodium hydroxide is added in into filtrate again, it is 7.0-9.0 to adjust filtrate pH value, stands half an hour, you can obtain analysing from filtrate
The lithium phosphate precipitation gone out.
The Fe recycled after testing2O3、FePO4Mixture purity reaches 97%, and lithium phosphate purity reaches more than 98%,
The rate of recovery of iron reaches 97.8%, and the rate of recovery of lithium is up to 98.4%.
Embodiment 3
Positive material of waste lithium iron phosphate is disassembled, breaks and grinds, after magnetic separation processing, weighing 100 parts, treated
Cell positive material is put into not plus in the boat box of any substance, is placed in blowing air or oxygen roasting in 400-600 DEG C of roaster,
Torrefaction waste gas is passed through lime slurry, after keeping the temperature 2-3h, stops heating cooling and takes out roasting material；To roasting material plus pure water 300-400
Part, mixed roasting material will be diluted and be pumped into stirred autoclave, be warming up to 60-80 DEG C, then added in into stirred autoclave dilute
Phosphoric acid stirs evenly, and adjusting ph value of mixture is 3.0-4.0, is filtered after dissolving 2-3h, is washed.Washing of Filter Cake is dried
Fe2O3、FePO4Pure mixture, can be used as after drying synthesizing iron lithium phosphate or nontoxic antirust paint raw materials recovery cycle profit
With；Sodium hydroxide is added in into filtrate again, it is 7.5-8.5 to adjust filtrate pH value, stands half an hour, you can obtain analysing from filtrate
The lithium phosphate precipitation gone out.
The Fe recycled after testing2O3、FePO4Mixture purity reaches 98%, and lithium phosphate purity reaches 99.3%, iron
The rate of recovery reach 98%, the rate of recovery of lithium is up to 99%.
Embodiment 4
Positive material of waste lithium iron phosphate is disassembled, breaks and grinds, after magnetic separation processing, weighing 100 parts, treated
Cell positive material is put into not plus in the boat box of any substance, is placed in blowing air or oxygen roasting in 350-700 DEG C of roaster,
Torrefaction waste gas is passed through lime slurry, after keeping the temperature 2-3h, stops heating cooling and takes out roasting material；To roasting material plus pure water 300-400
Part, mixed roasting material will be diluted and be pumped into stirred autoclave, be warming up to 30-90 DEG C, then added in into stirred autoclave dilute
Nitric acid stirs evenly, and adjusting ph value of mixture is 4.5-6.0, is filtered after dissolving 1-4h, is washed.Washing of Filter Cake is dried
Fe2O3、FePO4Pure mixture, can be used as after drying synthesizing iron lithium phosphate or nontoxic antirust paint raw materials recovery cycle profit
With.Sodium hydroxide is added in into filtrate again, it is 7.5-8.5 to adjust filtrate pH value, stands half an hour, you can obtain analysing from filtrate
The lithium phosphate precipitation gone out.
The Fe recycled after testing2O3、FePO4Mixture purity reaches 98%, and lithium phosphate purity reaches 98.7%, iron
The rate of recovery reach 96.5%, the rate of recovery of lithium is up to 98%.
Embodiment 5
Positive material of waste lithium iron phosphate is disassembled, breaks and grinds, after magnetic separation processing, weighing 100 parts, treated
Cell positive material is put into not plus in the boat box of any substance, is placed in blowing air or oxygen roasting in 400-800 DEG C of roaster,
Torrefaction waste gas is passed through lime slurry, after keeping the temperature 2-3h, stops heating cooling and takes out roasting material；To roasting material plus pure water 300-400
Part, mixed roasting material will be diluted and be pumped into stirred autoclave, be warming up to 30-90 DEG C, then added in into stirred autoclave dilute
Sulfuric acid stirs evenly, and adjusting ph value of mixture is 5.5-6.5, is filtered after dissolving 1-4h, is washed.Washing of Filter Cake is dried
Fe2O3、FePO4Pure mixture, can be used as after drying synthesizing iron lithium phosphate or nontoxic antirust paint raw materials recovery cycle profit
With.30% ammonium hydroxide is added in into filtrate again, it is 7.0-9.0 to adjust filtrate pH value, stands half an hour, you can obtain from filtrate
The lithium phosphate precipitation of precipitation.
The Fe recycled after testing2O3、FePO4Mixture purity reaches 97.8%, and lithium phosphate purity reaches 99%, iron
The rate of recovery reach 97.3%, the rate of recovery of lithium is up to 97.9%.
Comparative example 1
Using the processing step and condition described in same embodiment 3, difference lies in acidleach processing procedure, increase to stirring
The phosphoric acid,diluted dosage added in reaction kettle, stirs evenly, and adjusting ph value of mixture is 1-2.The Fe recycled after testing2O3、
FePO4Mixture purity is not substantially change as 97.8%, but the lithium phosphate purity recycled is decreased obviously as 95%, is being recycled
Lithium phosphate precipitation in contain iron hydroxide impurity.
Comparative example 2
Using the processing step and condition described in same embodiment 3, difference lies in acidleach processing procedure, reduce to filtrate
The phosphoric acid,diluted dosage of middle addition, it is 6.6-7 to make filtrate pH value.The Fe recycled after testing2O3、FePO4Mixture purity is not sent out
Raw substantially change reaches 97.5%, but the rate of recovery of lithium phosphate substantially reduces, and only 70%, the lithium phosphate purity being recovered to is not sent out
Raw significant changes are 99%.
Comparative example 3
Using the processing step and condition described in same embodiment 3, difference lies in being precipitated in alkali in processing procedure, increase to filter
The sodium hydroxide concentration added in liquid, it is 6-7 to make filtrate pH value.The Fe recycled after testing2O3、FePO4Mixture purity is not
It substantially change and reaches 97.8%, but the rate of recovery of lithium phosphate substantially reduces, only 60%, under the lithium phosphate purity being recovered to
It is reduced to 99%.
Comparative example 4
Using the processing step and condition described in same embodiment 3, difference lies in being precipitated in alkali in processing procedure, reduce to filter
The sodium hydroxide concentration added in liquid, it is 9-10 to make filtrate pH value.The Fe recycled after testing2O3、FePO4Mixture purity
It does not substantially change and reaches 97.8%, but the rate of recovery of lithium phosphate substantially reduces, only 65%, the lithium phosphate purity being recovered to
98.6% is not fallen to.
Comparative example 5
Using the processing step and condition described in same embodiment 3, difference lies in by the calcination temperature of roaster from 400-600
DEG C, rise to 1000-1200 DEG C.The Fe that recycling obtains is found after testing2O3、FePO4Mixture purity do not substantially change for
97.8%, but Fe2O3、FePO4The rate of recovery of mixture falls to 80%；The lithium phosphate purity of recycling is decreased obviously as 86%,
Contain more iron hydroxide impurity in the lithium phosphate precipitation of recycling.As it can be seen that the raising of temperature causes the Fe after roasting2O3To acid
Dissolubility generates variation, and the part Fe2O3 in recovery process acidleach is handled is caused to be dissolved in diluted acid, and then influences Fe2O3、FePO4
The rate of recovery and recycling lithium phosphate purity.
Comparative example 6
Using the processing step and condition described in same embodiment 3, difference lies in by the calcination temperature of roaster from 400-600
DEG C, it is reduced to 100-200 DEG C.Recycling obtains containing a large amount of unreacted LiFePO4s and minimal amount of in filter cake after testing
Ferric phosphate.The precipitation capacity that alkali is precipitated from filtrate is few, most of to be precipitated for ferrous hydroxide, and only minimal amount of lithium phosphate sinks
It forms sediment.
By the experimental result of comparative example 1-6, only by acid adding in recovery process flow or add alkali adjust after it is molten
Liquid pH value and the calcination temperature of cell positive material is controlled in numberical range of the present invention, could realized to phosphorus
The high-grade priority reclamation of sour lithium utilizes.
Claims (10)
- A kind of 1. method that valuable metal is recycled from positive material of waste lithium iron phosphate, which is characterized in that including as follows Step：(1) roast：It will disassemble, the lithium iron phosphate battery positive material progress thorough roasting oxidation after broken mill, and make the battery just Fe, Li metallic element in the material of pole generates Fe by roasting oxidation2O3、FePO4And Li3PO4；(2) acidleach：It will be placed in dilute acid soln and impregnate, make in roasting material through the roasting material after the oxidation of step (1) thorough roasting Li3PO4Salt dissolves, and filters, and realizes Li in roasting material3PO4With Fe2O3、FePO4Separation；(3) alkali is precipitated：Step of learning from else's experience (3) treated filtrate, and the filtrate made alkaline is adjusted, make the Li in filtrate3PO4Directly Precipitation is connect as precipitation, so as to fulfill to solid-state Li3PO4Recycling.
- 2. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1, It is characterized in that, the calcination temperature in the step (1) is 200-1000 DEG C, it is preferably 300-800 DEG C, further preferably 400-600℃。
- 3. a kind of side that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1 or 2 Method, which is characterized in that the roasting time in the step (1) is 1-5h, is preferably 1.5-4h, further preferably 2-3h.
- 4. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1, It is characterized in that, diluted acid can select one kind or several in dilute hydrochloric acid, dust technology, dilute sulfuric acid, phosphoric acid,diluted in the step (2) Kind.
- 5. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 4, It is characterized in that, the pH value of the diluted acid is controlled between 2.0-6.5, it is preferably controlled between PH=3.0-5.0.
- 6. according to a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate of claim 1, feature It is, pH value adjustment, the soluble alkali is carried out to the filtrate by adding in soluble alkali materials in the step (3) One or more of the preferred sodium hydroxide of substance, potassium hydroxide, ammonium hydroxide.
- 7. a kind of side that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1 or 7 Method, which is characterized in that PH is preferably controlled in the range of 7.0-9.0 to filtrate pH value adjustment control in the step (3) In the range of=7.5-8.5.
- 8. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1, It is characterized in that, the lithium iron phosphate battery positive material is being disassembled, during broken mill, the phosphorus after being screened using magnetic separation mode Sour lithium iron battery positive electrode.
- 9. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1, It is characterized in that, specifically comprise the following steps：(1) roast：100 parts of the lithium iron phosphate battery positive material for disassembling, breaking mill is weighed, is put into 300-800 DEG C of roaster Blowing air or oxygen roasting keep the temperature 1.5-4h, and waste gas is passed through lime slurry, and roasting material is taken out in cooling；(2) acidleach：Add 200-600 parts of pure water, be pumped into stirred autoclave, be warming up to 30-90 DEG C, diluted acid is added dropwise and keeps PH=3- It filters, washs after 6.5, dissolving reaction 1-4h；(3) the filtrate tune PH=7.0-9.0 that will be obtained by filtration described in warp, lithium phosphate Precipitation in filtrate, that is, realize to phosphoric acid The recycling of lithium product.
- 10. a kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate according to claim 1, It is characterized in that, specifically comprise the following steps：(1) waste lithium iron phosphate battery is taken to disassemble, 100 parts of anode waste after broken mill, is put into not plus in the boat box of any substance, Blowing air or oxygen roasting, keep the temperature 2-3h in 400-600 DEG C of roaster, and roasting material is taken out in cooling；(2) add 300-400 parts of pure water into the roasting material, be pumped into stirred autoclave, be warming up to 60-80 DEG C, diluted acid is added dropwise, protect Hold PH=3.0-4.0, dissolving reaction 2-3h filterings, washing；(3) the filtrate portion tune PH=7.5-8.5 obtained after filtering, precipitation obtain lithium phosphate, and filtering, clear water washing, drying obtain Go out lithium phosphate product；(4) filter cake obtained after filtering is iron content and the pure mixture of phosphorus, and iron, P elements are recycled in drying.
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