CN108832219A - A kind of waste lithium cell electrolyte disposition collection method and disposition collection device - Google Patents
A kind of waste lithium cell electrolyte disposition collection method and disposition collection device Download PDFInfo
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- CN108832219A CN108832219A CN201810890047.8A CN201810890047A CN108832219A CN 108832219 A CN108832219 A CN 108832219A CN 201810890047 A CN201810890047 A CN 201810890047A CN 108832219 A CN108832219 A CN 108832219A
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- reacting furnace
- lithium cell
- waste lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 4
- 230000007096 poisonous effect Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 20
- 239000007789 gas Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000004064 recycling Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000004519 grease Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- -1 tetrafluoroborate Chemical compound 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000007158 vacuum pyrolysis Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to the methods that a kind of disposition of waste lithium cell electrolyte is collected comprising following steps：1）Waste lithium cell to be disposed is placed in reacting furnace；2）Overheated steam is passed through in reacting furnace, the air in reacting furnace is discharged；3）Continue to be passed through superheated vapour into reacting furnace, make full of superheated vapour inside reacting furnace, and keep temperature constant, waste lithium cell is opened under high-temperature vapor and pressure effect, and overheated steam enters inside battery, reacts with electrolyte；4）It reacts the product generated and flows out reacting furnace with superheated vapour, after condensing, liquid carries out water-oil separating and obtains organic matter and waste water respectively, and gaseous material is collected separately.The electroless liquid leakage of this method, avoids electrolyte and contacts generation side reaction with oxygen or air under the high temperature conditions, generate poisonous and harmful substance.The method of the present invention has the characteristics that recovery efficiency height, green low-carbon, environmental protection and energy saving, is convenient for industrialization.
Description
Technical field
The invention belongs to power accumulators to be recycled technical field, and in particular to a kind of waste lithium cell electrolyte disposition
Collection method and disposition collection device.
Background technique
Lithium ion battery has obtained quick hair in energy storage, electric car, computer, communication and consumer electronics product field
Exhibition and extensive use, scale and quantity constantly expand increase, especially with the fast development of electric car and universal, power electric
The production in pond and usage amount are multiplied year by year.According to power battery service life（It is 3 ~ 5 years average）, correlative study data are aobvious
Show, the estimated China automobile power cell yield of the year two thousand twenty is up to 25.7 ten thousand tons, this data is up within 2022
42.2 ten thousand tons.
With the rapid decrease of lithium battery cost, the coming years, waste lithium cell will be presented explosion type cumulative bad and increase
Gesture, health, environment, security risk cumulative effect amplify at double, can not be ignored, if cannot effectively be recycled, not only can
It results in waste of resources（Especially electrolyte, because it contains poisonous and harmful substance）, and easily occur in the natural environment secondary anti-
It answers, causes secondary pollution.Therefore, just seem particularly critical to the recycling disposal of waste lithium cell.
However, the research in terms of lithium battery electrolytes recycling disposal both at home and abroad and few at present, correlation technique technology is not
Architectonical, market application are also immature.
Such as：Document（Tong Dongge, Lai Qiongyu, Ji Xiaoyang, the recycling [J] of waste lithium ion cell anode material lithium cobaltate,
Journal of Chemical Industry and Engineering 56（2005）1967-1970.）PC is recycled into electrolyte as solvent, then carries out LiPF6Purification with PC is returned
It receives, realizes electrolyte recycling.
Document（Lv little San, Lei Lixu, remaining small text etc., a kind of method [J] of waste and old lithium ion battery ingredient separation, battery
37（2007）79-80.）Battery fragment is put into reactor, it is rinsed with polar organic solvent at room temperature, electrolyte is same
When be dissolved in organic solvent, primary recovery product motor liquid is obtained after extraction and separation, by further purifying, adjusting concentration, is made
Product has certain conductivity, theoretically can be with reuse.
The processing of a kind of recovery processing waste lithium cell electrolyte of ZL 201310562566.9 invention and electrolyte waste water
Method is first handled waste and old electrolyte, and electrolyte reaction generation exhaust gas is then passed through waste water and is absorbed, thus
It is removed in wastewater treatment process, water outlet is finally ensured into effluent quality by RO reverse osmosis units, generated concentrated water for RO, use
Powder electroless plating-ultrafiltration combination technique removes organic pollutant therein.
ZL 201110427431.2 is using organic solvent contained by the isolated electrolyte of high vacuum rectification under vacuum, rectifying
It recycles after purification.Lithium hexafluoro phosphate crude product is put into dissolution kettle, the lithium hexafluoro phosphate of hydrogen fluoride solution dissolution recycling is added, so
It will be put into crystallization kettle after solution filtering afterwards and purified, sieved, dried, packed, recycling obtains product lithium hexafluoro phosphate.
ZL 200480040543.0 is added to and is contained using a kind of reagent that basic composition is fluorine-containing alkali metal or ammonium fluoride
In the organic solvent for having lithium hexafluoro phosphate or LiBF4, the mixed solution then obtained, which is distilled or evaporated removing, to be had
Solvent.The both thermally and chemically unstable lithium hexafluoro phosphate of property（Or LiBF4）Both thermally and chemically property is converted into stablize
Hexafluorophosphate（Or tetrafluoroborate）And lithium fluoride.
Document（L. Sun, K. Qiu, Vacuum pyrolysis and hydrometallurgical process
For the recovery of valuable metals from spent lithium-ion batteries [J], J
Hazard Mater. 194（2011）378-384.）Using organic viscous in vacuum pyrolysis technology separating waste, worn bell ion battery
Tie agent and electrolyte.Holding system pressure is lower than 1.0 kPa, and the condensed gas of thermal decomposition product is collected in -10 DEG C of cold-trap.Point
Analysis discovery, the thermal decomposition product of collection is mainly carbon fluorine organic compound, avoid environmental pollution caused by the discharge of fluoride and
The wasting of resources.
Document（M. J. Lain, Recycling of lithium ion cells and batteries[J], J
Power Sources 97-98（2001）736 -738.）Research is thought, solvent appropriate may be selected（Acetonitrile, N- methylpyrrole
Alkanone）The electrolyte in battery system is leached at 50 DEG C, after solid content is separated with solvent, passes through vacuum distillation recycling circulation
It is remaining using solvent, it is pure electrolyte.
Waste and old lithium ion battery is placed in supercritical reaction kettle by US 200300186110A1, is added into reaction kettle
CO2, the temperature and pressure of reaction kettle is adjusted, CO is made2Reach supercriticality, lithium-ion battery electrolytes exposure is simultaneously dissolved in super
Critical CO2In, finally by supercritical CO from reaction kettle2It is separated with lithium ion battery, the supercritical CO in collecting kettle2Restore normal
Electrolyte is precipitated in pressure.This method utilizes liquid and above-critical state CO2The dissolution properties excellent to apolar substance, by electrolyte
It is separated from waste and old lithium ion battery.
US 5888463A is cooling at -195.6 DEG C by lithium battery using liquid nitrogen, and at this temperature crushing battery, then
LiOH solution is injected into dusty material, so that electrolyte is reacted, is generated stable lithium salt solution.Lithium salt solution is further dense
Contracting and purification, can get the LiOH or Li of commercialization2CO3.But this method does not solve the problems, such as the processing of fluoride.
It in summary it can be seen, both at home and abroad in terms of waste lithium cell electrolyte processing and technology that not formed environmental protection is practical,
The prior art easily causes secondary pollution.
Summary of the invention
Present invention aims to overcome that prior art defect, provides a kind of waste lithium cell electrolyte disposition collection method,
It mainly uses high-temperature vapor to heat waste lithium cell, and so that the organic solvent in electrolyte is carbonized is gas, and fluorine-containing lithium salts is molten
The high-temperature vapor of Xie Yu condensation is hankered, and realizes that the disposition of lithium battery electrolytes is collected under oxygen-free environment.Entire disposition is collected
The electroless liquid leakage of process, also avoids contacting with oxygen or air under the high temperature conditions because of electrolyte generating poisonous and harmful
Substance, this method have many advantages, such as recovery efficiency height, green low-carbon, environmental protection and energy saving, are convenient for industrialization.
The present invention also provides a kind of waste lithium cell electrolyte suitable for the above method to dispose collection device.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method that the disposition of waste lithium cell electrolyte is collected comprising following steps：
1）Waste lithium cell to be disposed is placed in reacting furnace；
2）Overheated steam is passed through in reacting furnace, the air in reacting furnace is discharged；
3）Continue to be passed through superheated vapour into reacting furnace, make full of superheated vapour inside reacting furnace, and keep temperature constant,
Waste lithium cell is opened under high-temperature vapor and pressure effect, and overheated steam enters inside battery, occurs with electrolyte
Reaction；
4）It reacts the product generated and flows out reacting furnace with superheated vapour, after condensing, liquid carries out water-oil separating difference
It obtains organic matter and waste water, gaseous material is collected separately.
In the present invention, the waste lithium cell includes waste and old energy-storage lithium battery, waste power lithium battery and waste and old meter
Calculation machine, communication and consumer electronics product lithium battery etc..The lithium battery type includes ferric phosphate lithium cell, ternary lithium electricity
Pond, lithium manganate battery and cobalt acid lithium battery etc..The lithium battery specification include rectangular soft package lithium battery, rectangular steel shell lithium battery,
Square aluminum plastic housing lithium battery, cylinder type lithium battery etc..
Specifically, step 1）In, waste lithium cell to be processed can be placed on pallet or bracket, then be placed in reacting furnace
In, close the door of reacting furnace.
Preferably, step 2）In, overheated steam temperature controls between 200 DEG C to 800 DEG C；The overheated steam is
After hardness is heated no more than 8 degree of softened water, i.e., by tap water, first softened hydrotreater carries out sofening treatment, obtains
After softened water of the hardness no more than 8 degree, it is heated to be overheated steam using hot steam generator.It is 2m with volume3Reaction
For furnace, superheated vapour is continuously ventilated 10~50min with the flow velocity of 5~30L/min, can be whole by the air in reacting furnace
Discharge.
Specifically, step 3）In, the control of reacting furnace pressure is controlled in 0.5-7.5MPa, reacting furnace temperature in 200-800
DEG C, the reaction time controlled in 2-5 hour.Reacting furnace is heated using the method for electromagnetic heating, to keep superheated water to steam
Stripping temperature is within the set range.Under anaerobic high temperature action, electrolyte detaches waste lithium cell.Reaction generates liquid grease
Mixture and gaseous material（Organic solvent carbonization is gas and grease in electrolyte, and fluorine-containing lithium salts is dissolved in the high temperature of condensation
Vapor is hankered）.
Specifically, step 4）In, after gaseous material can be collected by exhaust fan, then burning processing is carried out, flammable gas
Body generates water and carbon dioxide.Gaseous material is mostly volatile organic compounds（volatile organic compounds,
VOCs）, usable burner carries out burning processing, and imflammable gas generates water and carbon dioxide through burning.Burner is to make to fire
The device that material and air spray mixed firinor fuel burning in a certain way is referred to as, and belongs to this field common apparatus, details are not described herein.
A kind of waste lithium cell electrolyte disposition collection device suitable for the above method comprising sequentially connected by pipeline
Superheated steam generator, reacting furnace, condenser and the oil water separator connect.
Specifically, the superheated steam generator is connected with softening hydrotreater, to soften to tap water.
Further, exhaust fan is covered with above the oil water separator, exhaust fan connects burner；Oil water separator
Oil outlet connects fuel reserve tank（To collect the organic matter isolated through oil water separator）, the water outlet connection of oil water separator
Sewage collecting box（To collect the waste water isolated through oil water separator）.
In the present invention, superheated steam generator is to be heated to be superheated vapour of the temperature at 200-800 DEG C for water；Oil
Separator obtains organic matter and waste water to separate oil water mixture respectively；Soften hydrotreater to will be common
Tap water is softened.Reacting furnace uses this field conventional structure, and e.g., reacting furnace can be the cylindric of upper and lower opening,
The fire door for placing waste lithium cell is offered at the top of reacting furnace；Reaction furnace outer wall is successively coated with heating layer（I.e. outside furnace body
Wall is wound with the electromagnetic induction coil to heat, and function is that furnace body can be heated to 200 DEG C to 800 DEG C）And heat preservation
Layer（Such as asbestos layer）.The upper opening of reacting furnace connects superheated steam generator by pipeline, and the under shed of reacting furnace passes through pipeline
Connect the entrance of condenser.
It reacts the product generated and flows out reacting furnace with superheated steam, after condenser condenses（Organic grease floats on water
On face, inorganic salts soluble easily in water are soluble in water in electrolyte）, further separated into oil water separator.
In addition, corrosion-inhibiting coating can be applied inside reacting furnace to extend the service life of reacting furnace.Innovation of the invention
Point essentially consists in the connection relationship of each component, the superheated steam generator being related in device, reacting furnace, condenser, grease point
From the conventional equipment that device, softening hydrotreater, burner etc. were all made of or bought this field, these are the normal of this field
See equipment, the present invention repeats no more about its structure.
Compared to the prior art, beneficial effects of the present invention：
The present invention realizes that the disposition of electrolyte in waste lithium cell is collected using the lower pyrolysis of superheated steam protection, mainly uses high temperature
Vapor heats waste lithium cell, and organic solvent carbonization is gas in electrolyte, and the high-temperature water that fluorine-containing lithium salts is dissolved in condensation steams
Gas is hankered, and realizes that the disposition of lithium battery electrolytes is collected under oxygen-free environment.The entire electroless liquid leakage of disposition collection process,
It avoids electrolyte to contact with oxygen or air under the high temperature conditions, generates poisonous and harmful substance, have recovery efficiency high, green
Low-carbon, is convenient for the features such as industrialization at environmental protection and energy saving.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that waste lithium cell electrolyte of the present invention disposes collection device；
Fig. 2 is the flow diagram that waste lithium cell electrolyte of the present invention disposes collection method.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
As shown in Figure 1, a kind of waste lithium cell electrolyte disposes collection device comprising steamed by the sequentially connected overheat of pipeline
Vapour generator 3, reacting furnace 4, condenser 5 and oil water separator 6；The superheated steam generator 3, reacting furnace 4 and condenser 5 are equal
It is connected using stainless steel pipes；
The superheated steam generator 3 is connected with softening hydrotreater 2, and to soften to tap water, tap water is contained in
In water tank 1, softening hydrotreater 2 is connected with water tank 1；
Exhaust fan 9 is covered with above the oil water separator 6, exhaust fan 9 connects burner 10；The oil outlet of oil water separator 6
Connect fuel reserve tank 7（To collect the organic matter isolated through oil water separator）, the water outlet connection waste water of oil water separator 6
Collecting box 8（To collect the waste water isolated through oil water separator）.
As illustrated in fig. 1 and 2, the method that the disposition of waste lithium cell electrolyte is collected is carried out using above-mentioned apparatus comprising such as
Lower step：Reacting furnace volume is about 2m3,
1）50kg waste power lithium battery is taken, battery types are lithium iron phosphate lithium battery, and specification is the rectangular soft-package battery of 60Ah, outside
Shape is having a size of 220 mm × 123 mm × 5mm.Waste lithium cell to be disposed is placed on pallet, then is placed in reacting furnace 4,
Close the door of reacting furnace；It is recycled according to following steps：
2）It with hardness is obtained after softening 2 sofening treatment of hydrotreater, 30 min is 5 degree of softening by the pure tap water in water tank 1
Water；Then softened water is sent to heating in superheated steam generator 3, overheated steam is obtained after about 50min, steam temperature is
625 DEG C, pressure 0.99MPa；
3）Overheated steam is entered in reacting furnace 4 with the flow velocity of 15 L/min, and the air in reacting furnace 4 is discharged after about 20 min；
4）Reacting furnace is heated to 630 DEG C and keeps 2h, waste lithium cell is under anaerobic high temperature action, safety valve（Or lose heart
Mouthful）It is opened, overheated steam enters inside battery, reacts with electrolyte；
5）It reacts the product generated and flows out reacting furnace 4 with superheated vapour, condensed after the condensation of condenser 5（Organic solvent condensation
It is swum on condensed water at grease, inorganic salts soluble easily in water are soluble in water in electrolyte）, obtain the oil water mixture of liquid
It is further separated into oil water separator, gaseous material is collected separately；
6）Oil water mixture enters oil water separator 6, and the organic matter for collecting upper layer amounts to 100 g, and organic matter enters through oil outlet
Fuel reserve tank 7；
7）Waste water after oil water separator 6 separates enters sewage collecting box 8 through water outlet, and ion component is mainly iron, lithium, phosphorus
Acid group and fluorine；
8）Exhaust gas（Predominantly H2、CH4、CO、CO2）, burning processing is carried out into burner 10 by exhaust fan 9, is discharged after burning
Gas componant out is mainly vapor and CO2。
Embodiment 2
A kind of waste lithium cell electrolyte disposition collection method comprising following steps：
Other contents and operation with embodiment 1, except that：
In step 1）In, the waste and old energy-storage lithium battery of 80kg is taken, battery types are ferric phosphate lithium cell, and specification is that 180Ah is rectangular
Steel shell battery, outer dimension are 178 mm × 278 mm × 70mm；
In step 2）In, softened water hardness is 6 degree, and steam temperature is 645 DEG C, pressure 1.07MPa；
In step 3）In, overheated steam is entered in reacting furnace with the flow velocity of 10 L/min, is discharged in reacting furnace after 30 min
Air；
In step 4）In, it is heated to 660 DEG C inside reacting furnace and keeps 150 min；
In step 6）The middle organic matter for collecting upper layer amounts to 130 g；
In step 7）In, waste water intermediate ion ingredient is mainly nickel, cobalt, manganese, lithium and fluorine.
Embodiment 3
A kind of waste lithium cell electrolyte disposition collection method comprising following steps：
Other contents and operation with embodiment 1, except that：
In step 1）In, the waste and old laptop lithium battery of 60kg is taken, battery types are cobalt acid lithium battery, specification 3000mAh
Rectangular cylindrical battery, outer dimension are diameter 18mm, height 65mm；
In step 2）In, softened water hardness is 4 degree, and steam temperature is 685 DEG C, pressure 2.0MPa；
In step 3）In, overheated steam is entered in reacting furnace with the flow velocity of 19L/min, is discharged in reacting furnace after 18 min
Air；
In step 4）In, it is heated to 690 DEG C inside reacting furnace and keeps 130 min；
In step 6）The middle organic matter for collecting upper layer amounts to 105 g；
In step 7）In, waste water intermediate ion ingredient is mainly cobalt, lithium and fluorine.
Claims (8)
1. a kind of method that the disposition of waste lithium cell electrolyte is collected, which is characterized in that include the following steps：
1）Waste lithium cell to be disposed is placed in reacting furnace；
2）Overheated steam is passed through in reacting furnace, the air in reacting furnace is discharged；
3）Continue to be passed through superheated vapour into reacting furnace, make full of superheated vapour inside reacting furnace, and keep temperature constant,
Waste lithium cell is opened under high-temperature vapor and pressure effect, and overheated steam enters inside battery, occurs with electrolyte
Reaction；
4）It reacts the product generated and flows out reacting furnace with superheated vapour, after condensing, liquid carries out water-oil separating difference
It obtains organic matter and waste water, gaseous material is collected separately.
2. waste lithium cell electrolyte collection method according to claim 1, which is characterized in that step 1）In, it will be wait locate
Reason waste lithium cell is placed on pallet or bracket, then is placed in reacting furnace.
3. waste lithium cell electrolyte collection method according to claim 1, which is characterized in that step 2）In, superheated water
Steam temperature controls between 200 DEG C to 800 DEG C；The overheated steam is after hardness is heated no more than 8 degree of softened water
And it obtains.
4. waste lithium cell electrolyte collection method according to claim 1, which is characterized in that step 3）In, reacting furnace
Pressure control is in 0.5-7.5MPa, and at 200-800 DEG C, the reaction time was controlled in 2-5 hour for reacting furnace temperature control.
5. waste lithium cell electrolyte collection method according to claim 1, which is characterized in that step 4）In, gaseous state object
Matter carries out burning processing after collecting by exhaust fan, imflammable gas generates water and carbon dioxide.
6. a kind of waste lithium cell electrolyte suitable for any the method for claim 1 to 5 disposes collection device, feature
It is, including passes through the sequentially connected superheated steam generator of pipeline, reacting furnace, condenser and oil water separator.
7. waste lithium cell electrolyte according to claim 6 disposes collection device, which is characterized in that the superheated steam
Generator is connected with softening hydrotreater.
8. waste lithium cell electrolyte according to claim 6 disposes collection device, which is characterized in that the water-oil separating
Exhaust fan is covered with above device, exhaust fan connects burner；The oil outlet of oil water separator connects fuel reserve tank, oil water separator
Water outlet connects sewage collecting box.
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