CN103526035A - Method for recycling valuable metals from waste lithium ion batteries and/or other materials - Google Patents
Method for recycling valuable metals from waste lithium ion batteries and/or other materials Download PDFInfo
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- CN103526035A CN103526035A CN201310531016.0A CN201310531016A CN103526035A CN 103526035 A CN103526035 A CN 103526035A CN 201310531016 A CN201310531016 A CN 201310531016A CN 103526035 A CN103526035 A CN 103526035A
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- ion battery
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- 239000002699 waste material Substances 0.000 title claims abstract description 90
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000004064 recycling Methods 0.000 title abstract description 9
- 150000002739 metals Chemical class 0.000 title abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 80
- 229910052802 copper Inorganic materials 0.000 claims abstract description 54
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000571 coke Substances 0.000 claims abstract description 24
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 239000010949 copper Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 51
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 230000004907 flux Effects 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 229910020630 Co Ni Inorganic materials 0.000 description 11
- 229910002440 Co–Ni Inorganic materials 0.000 description 11
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 9
- 239000002956 ash Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 4
- 229910000601 superalloy Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002620 method output Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- -1 nickel metal oxide Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recycling valuable metals from waste lithium ion batteries and/or other materials. The method comprises the following steps that the waste lithium ion batteries and/or the other materials, metallurgical coke and fluxing agents and/or waste containing one or more of Cu, Co and Ni are mixed to obtain mixed materials; the metallurgical coke accounts for 0-20wt % of the mixed materials, and CaO/SiO2 is equal to or higher than 1, or (CaO +MgO)/SiO2 is equal to or higher than 1 in the mixed materials; the mixed materials are subjected to reduction smelting under the temperature of 1400-1600 DEG C, and alloy containing valuable metals and slags are obtained. According to the method, alkaline slags are adopted for smelting, efficient recycling of valuable metals can be achieved, and the amount of valuable metals in slags is reduced.
Description
Technical field
The present invention relates to resource and environment technical field, particularly a kind of method that reclaims valuable metal from waste and old lithium ion battery and/or its material.
Background technology
Lithium ion battery is since nineteen ninety commercialization, because it has that energy density is large, operating voltage is high, has extended cycle life and the advantage such as memory-less effect, be widely used in the communication electronic products such as mobile phone and notebook computer and various electronic instrument and power tool.As the production and consumption big country of lithium ion battery in the world, China only lithium ion battery ultimate production of 2012 just reaches 4,000,000,000.And along with the development of the fast universal and power truck industry of hyundai electronics communication equipment etc., the consumption of secondary cell increases severely, and can produce a large amount of waste and old lithium ion batteries thereupon.Waste and old lithium ion battery contains the valuable metals such as more cobalt, nickel and lithium on the one hand, and recovery value is high; On the other hand, its poisonous or hazardous compound containing is also more, as directly discarded or mishandling, not only wastes resource, and can cause more serious problem of environmental pollution, therefore, must waste and old lithium ion battery be recycled sophistication.
In recent years, the recycling technology of waste and old lithium ion battery has been carried out to much research both at home and abroad.Press adopted smelting technology different, the recovery processing technique of waste and old lithium ion battery can be divided into wet method and pyrogenic process two classes.At present, the recycling technology of the waste and old lithium ion battery of domestic-developed mainly concentrates on wet processing process, the Chinese patent literature that is CN102517448A as publication number discloses the reclaiming method of metal ion in a kind of waste and old lithium ion battery, the method by waste and old lithium ion battery electric discharge, disassemble and obtain positive electrode material, then use positive electrode material described in N-Methyl pyrrolidone (NMP) supersound process, then calcining makes LiCoO
2powder, after acid is molten, adds manganese salt and nickel salt and LiOH, directly makes tertiary cathode material.This wet processing process need to carry out the pretreatment process that machinery is disassembled to waste and old lithium ion battery; because this process exists the risk of environmental pollution of explosion safety risk or organism volatilization; generally adopt now and in protective atmosphere, disassemble or cryogenic freezing is disassembled; but; this just makes recycling ability be limited by very large, and facility investment and running cost are higher.
And aspect thermal process, as a kind of cobalt, nickel-based battery list stove retailoring treatment process of containing of the open Liao You Umicore of US716920B2 patent company exploitation, it is specifically put into furnace refractory and the flux of old and useless battery and disintegrate material, iron content in a high temperature shaft furnace, by controlling the redox condition in shaft furnace, output contains the alloy of Co, Ni and contains the slag of Fe >=20wt%, Co≤20wt%, Ni≤20wt%, then this alloy is further processed, reclaimed Co, Ni.Safe explosion and risk of environmental pollution that this technique has advantages of can process all kinds battery waste, avoid battery to disassemble exists in process, but, it adopts acid slag melting, in slag, Co, Cu content are still respectively up to 1.5wt%, 0.9wt%, slag cannot directly be abandoned, need further dilution to process, complex process.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of method that reclaims valuable metal from waste and old lithium ion battery and/or its material, method provided by the invention can realize the high efficiente callback of valuable metal, reduce the content of valuable metal in slag, the requirement of having avoided slag to need further dilution to process, technique is simple.
The invention provides a kind of method that reclaims valuable metal from waste and old lithium ion battery and/or its material, comprise the following steps:
Waste and old lithium ion battery and/or its material, metallurgical coke are mixed with flux and/or containing the waste material of one or more in Cu, Co and Ni, obtain mixture; Described metallurgical coke accounts for 0～20wt% of mixture; In described mixture, CaO/SiO2>=1 or (CaO+MgO)/SiO
2>=1;
Described mixture is carried out to retailoring at the temperature of 1400 ℃～1600 ℃, obtain alloy and slag containing valuable metal.
Preferably, in described mixture, CaO/SiO
2=1.01～3 or (CaO+MgO)/SiO
2=1.01～3.
Preferably, described flux is one or more in Wingdale, rhombspar, silica and aluminum oxide.
Preferably, described is one or more in copper smelting slag, cobalt metallurgical slag and nickel metallurgical slag containing the waste material of one or more in Cu, Co and Ni.
Preferably, described waste and old lithium ion battery is one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery;
Described waste and old lithium ion battery material is for containing one or more lithium ion battery processing waste in Cu, Co and Ni.
Compared with prior art, it is recycling object that waste and old lithium ion battery and/or its material are take in the present invention, with a certain amount of metallurgical coke, and flux and/or mix containing the waste material of one or more in Cu, Co and Ni, form mixture, then at the temperature of 1400 ℃～1600 ℃, carry out retailoring, obtain alloy and slag containing valuable metal; In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1.In the retailoring process of one or more battery wastes containing Co or Ni, temperature is 1400 ℃～1600 ℃, in described battery waste, graphite carbon and aluminium etc. can, by Cu, Co in mixture and Ni reduction, form the alloy containing valuable metal, as Cu-Co-Ni alloy; SiO
2, CaO, Al
2o
3can with impurity element effect, form slag.The present invention controls the CaO/SiO of mixture
2>=1 or (CaO+MgO)/SiO
2>=1, adopt basic slag melting, in the high efficiente callback that realizes valuable metal, reduce the content of valuable metal in slag.Experiment shows, in the alloy of method provided by the invention institute output the rate of recovery of Cu, Co and Ni all >=95wt%, in slag the content of Cu, Co and Ni all≤0.5wt%, slag can directly be discarded without further dilution, has simplified technique.
Accompanying drawing explanation
Fig. 1 reclaims the process flow sheet of valuable metal for what the embodiment of the present invention provided from waste and old lithium ion battery and/or its material.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The invention provides a kind of method that reclaims valuable metal from waste and old lithium ion battery and/or its material, comprising:
Steps A) by waste and old lithium ion battery and/or its material;
Metallurgical coke; With
Flux and/or mix containing the waste material of one or more in Cu, Co and Ni, obtains mixture;
Described metallurgical coke accounts for 0～20wt% of mixture;
In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1;
Step B) described mixture is carried out to retailoring at the temperature of 1400 ℃～1600 ℃, obtain alloy and slag containing valuable metal.
For the deficiency existing in current waste and old lithium ion battery recycling technology, the present invention proposes a kind of novelty by waste and old lithium ion battery and/or its material Direct Reductive Melting, with the method for high efficiente callback copper, cobalt, nickel valuable metal, this technique has significant economy, environment and social benefit.
Fig. 1 be the embodiment of the present invention provide from waste and old lithium ion battery and/or its material, reclaim the process flow sheet of valuable metal.
Referring to Fig. 1, first the embodiment of the present invention mixes waste and old lithium ion battery, metallurgical slag, Wingdale and silica and metallurgical coke, obtains mixture.
The present invention reclaims copper, cobalt, nickel valuable metal from waste and old lithium ion battery and/or its material, described waste and old lithium ion battery and material thereof comprise waste and old lithium ion battery and waste and old lithium ion battery material, wherein, described waste and old lithium ion battery material is preferably containing one or more lithium ion battery processing waste in Cu, Co and Ni, produces battery refuse material or the defective material containing Cu, Co, Ni of output in lithium ion battery process; Described waste and old lithium ion battery is preferably one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery, more preferably at least one in waste and old lithium-ion battery with steel shell and waste aluminum case lithium ion battery.Also can say, in the present invention, described waste and old lithium ion battery comprises box hat, aluminum hull and polymkeric substance three types.In the present invention, described waste and old lithium ion battery and material thereof can, directly into stove melting, avoid disassembling environmental pollution and risk of explosion in process without disassembling.
In an embodiment of the present invention, the typical composition of described waste and old lithium ion battery and material thereof is: Fe1wt%～40wt%; Cu5wt%～10wt%; Co5wt%～16wt%; Ni2wt%～2.5wt%; Al1wt%～35wt%; C5wt%～15wt%.To those skilled in the art, described waste and old lithium ion battery and material thereof also comprise inevitable impurity element, and the present invention is not particularly limited this.
The present invention adopts metallurgical coke and flux and/or is raw material containing the waste material of one or more in Cu, Co and Ni, with described waste and old lithium ion battery and/or its material mixing, obtains mixture.
Wherein, it is raw material that the present invention can contain the waste material of one or more in Cu, Co and Ni, and it is preferably one or more in copper smelting slag (copper ashes), cobalt metallurgical slag (cobalt slag) and nickel metallurgical slag (nickel slag).Described metallurgical slag is the waste material containing Cu, Co or Ni etc. well known to those skilled in the art, preferably comprises: the SiO of 15wt%～60wt%
2; The CaO of 1wt%～15wt%; The MgO of 0～15wt%.The present invention makes full use of the SiO wherein containing
2with CaO etc., part substitutes or substitutes flux completely, can significantly reduce the consumption of flux, contributes to reduce production costs.
In an embodiment of the present invention, the typical composition of copper ashes is: Cu0.5wt%～9.6wt%; TFe22wt%～55wt%; SiO
218wt%～40wt%; CaO1wt%～6wt%; Al
2o
30.9wt%～5wt%; MgO0.9wt%～5wt%.Wherein, Cu is preferably 1wt%～5wt%; TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt%～45wt%.To those skilled in the art, described copper ashes also comprises inevitable impurity element, and the present invention is not particularly limited this.
In an embodiment of the present invention, the typical composition of cobalt slag is: Co3wt%～3.5wt%; Cu3wt%～4wt%; TFe22wt%～55wt%; SiO
218wt%～40wt%; CaO1wt%～5wt%; Al
2o
32wt%～5wt%; MgO3wt%～5wt%.Wherein, TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt%～45wt%.To those skilled in the art, described cobalt slag also comprises inevitable impurity element, and the present invention is not particularly limited this.
In an embodiment of the present invention, the typical composition of nickel slag is: Ni0.2wt%～0.5wt%; Co0.05wt%～0.2wt%; Cu0.2wt%～0.5wt%; TFe20wt%～50wt%; SiO
222wt%～60wt%; CaO1wt%～5wt%; Al
2o
30～10wt%; MgO5wt%～10wt%.Wherein, Ni is preferably 0.2wt%～0.3wt%; Cu is preferably 0.2wt%～0.3wt%; TFe is total iron well known to those skilled in the art or full iron, is preferably 30wt%～45wt%.To those skilled in the art, described nickel slag also comprises inevitable impurity element, and the present invention is not particularly limited this.
The present invention can allocate flux as required into, and described flux is preferably one or more in Wingdale, rhombspar, silica and aluminum oxide, more preferably at least one in Wingdale and silica.Described flux is well known to those skilled in the art, and the present invention preferably adopts the flux that is crushed to 10mm～50mm.
The present invention can adopt metallurgical coke as reductive agent, described metallurgical coke be for smelting iron, the general name of the coke of molten iron, ferroalloy smelting and non-ferrous metal.Described metallurgical coke adopts this area to commonly use, and the present invention is not particularly limited it.
In embodiments of the present invention, by described metallurgical slag is this, containing the mixture that in Cu, Co and Ni, the raw materials such as waste material, Wingdale and silica of one or more are mixed to get, contain CaO and SiO
2deng, and, CaO/SiO
2>=1, be preferably 1.01～3, more preferably 1.1～2; Or (CaO+MgO)/SiO
2>=1, be preferably 1.01～3, more preferably 1.1～2.The present invention adopts basic slag melting, in the high efficiente callback that realizes valuable metal, reduces the content of valuable metal in slag.
The present invention gets the raw materials ready, is obtained by mixing mixture in proportion by above-mentioned material, and concrete batching can be: the described 0～50wt% that preferably accounts for mixture containing the waste material of one or more in Cu, Co and Ni, more preferably 1wt%～49.8wt%; Due to described, containing the waste material of one or more in Cu, Co and Ni, can partially or completely substitute flux, described flux preferably accounts for 0～50wt% of mixture, more preferably 1wt%～45wt%; Due to the carbon in waste and old lithium ion battery and material thereof and metallic aluminium, can make reductive agent, the present invention can not add melting under metallurgical coke, output Cu-Co-Ni alloy, and described metallurgical coke accounts for 0～20wt% of mixture, is preferably 1～15wt%; Surplus is waste and old lithium ion battery and/or its material.Wherein, described flux and be 0 should be different time containing one or more waste material in Cu, Co and Ni.
Obtain after mixture, the embodiment of the present invention is dropped in shaft furnace carries out retailoring, and temperature is 1400 ℃～1600 ℃, obtains Cu-Co-Ni alloy as Cu-Co-Ni-Fe alloy, and slag and flue dust.
It is equipment well known to those skilled in the art that the present invention carries out retailoring shaft furnace used, and it can be divided into preheating zone, pyrolysis zone and three, retailoring district part from top to bottom.Described shaft furnace has alloy mouth and slag notch, is respectively used to emit alloy and slag.
To described shaft furnace, drop into after mixture, in preheating zone, in stove, temperature is controlled at below 300 ℃, and old and useless battery material slowly heats up, and has avoided battery to blast; In pyrolysis zone, in stove, temperature is elevated to 700 ℃ of left and right, the organism generation pyrolysis such as the plastics in battery material, and the heat of generation can be preheating zone gas energy is provided; In retailoring district, in stove, temperature is 1400 ℃～1600 ℃, be preferably 1450 ℃～1550 ℃, more than 1300 ℃, in battery material, graphite carbon and aluminium and metallurgical coke can be by Cu, Co in mixture and Ni reduction, form Cu-Co-Ni alloy, described Cu-Co-Ni alloy is alloy well known to those skilled in the art; SiO
2, CaO, Al
2o
3can with impurity element effect, can form containing Cu, Co and Ni all≤slag of 0.5wt%, in described slag the grade of Cu, Co and Ni all≤0.5wt%.And the temperature of flue gas that rises to furnace roof is at 250 ℃～700 ℃, owing to containing the organism such as fluorine and chlorine in flue gas, need process by high-temperature flue gas quench system, to avoid the generation of Dioxins.
The present invention is not particularly limited charging capacity, adopts this area conventional process, if rate of feeding is 300kg/h; Smelting time can be 30min～90min.
Obtain after Cu-Co-Ni alloy and slag, the present invention carries out analysis of chemical elements to it.Experiment shows, in the alloy of method output provided by the invention the rate of recovery of Cu, Co and Ni all >=95wt%, organic efficiency is higher; In slag the content of Cu, Co and Ni all≤0.5wt%, the requirement of having avoided slag to need further dilution to process, technique is simple.
Described Cu-Co-Ni alloy can by powder by atomization and further powder leach, leach liquefaction and separating-purifying etc., obtain can market sale metal or compound products; And described slag can be used as material of construction use.
In sum, the present invention adopts CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1 mixture carries out melting, adopt basic slag melting, realize battery refuse material and containing one or more waste material in Cu, Co and Ni as discarded metallurgical slag in the high efficiente callback of valuable metal, effectively reduce the content of valuable metal in slag, there is significant economy, environmental and social benefits.
Further, the present invention is in reclaiming battery in valuables material, solved the recycling problem containing valuable metal Cu, Co, Ni in one or more waste material in Cu, Co and Ni, developed a kind of with " give up " novel process of comprehensively recovering valuable metal of " giving up " smelting.
In addition, the present invention preferably adopts aluminum hull waste and old lithium ion battery and/or its material, and it contains a large amount of metal A l, can add the oxygen of the interior reaction zone of metallurgical material supplementary furnace of metal oxide or containing metal oxide, and the Al in battery material is converted into Al
2o
3, and discharge a large amount of heat energy, thus can realize pyritic smelting.That is to say, the present invention utilizes plastics organic compound combustion and burning exothermic heat of reaction in battery material, can realize pyritic smelting; Utilize metal aluminum foil in battery material, graphite carbon to make reductive agent, cobalt, nickel metal oxide can be reduced into metal, take full advantage of the various compositions in battery material.
In order further to understand the present invention, below in conjunction with embodiment, the method that reclaims valuable metal from waste and old lithium ion battery and/or its material provided by the invention is specifically described.
The chief component composition of the waste and old lithium ion battery using in following examples is referring to table 1, and table 1 is the chief component composition of embodiment of the present invention waste and old lithium ion battery used.
The chief component composition of table 1 embodiment of the present invention waste and old lithium ion battery used
Embodiment 1
Waste and old lithium-ion battery with steel shell, Wingdale, silica and metallurgical coke are mixed, obtain mixture, wherein, by the mixing of getting the raw materials ready of the metallurgical coke of the silica of the Wingdale of 23.7wt%, 17.3wt%, 12wt%; In described mixture, CaO/SiO
2=1.3.
Described mixture is put in shaft furnace and carried out retailoring by the speed of 300kg/h, and smelting temperature is 1450 ℃, and smelting time is 60min, and furnace roof flue-gas temperature is 450 ℃.Treat that slag is completely separated with alloy melt, superalloy and slag are emitted from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 96.9%, 98.1% and 96.8%; In slag, containing Cu, Co and Ni, be respectively 0.35wt%, 0.31wt% and 0.05wt%.Result shows, the present invention, in the high efficiente callback that realizes valuable metal, has reduced the content of valuable metal in slag.
Embodiment 2
Waste and old lithium-ion battery with steel shell, copper ashes (Cu1wt%, TFe42wt%), nickel slag (Cu0.2wt%, Ni0.35wt%, TFe44wt%), cobalt slag (Cu3wt%, Co3.5wt%, TFe42wt%), Wingdale and metallurgical coke are mixed, obtain mixture, wherein, by the mixing of getting the raw materials ready of the nickel slag of the cobalt slag of the copper ashes of 10.4wt%, 6.9wt%, 17.3wt%, the Wingdale of 21.7wt%, the metallurgical coke of 9wt%; In described mixture, CaO/SiO
2=1.3.
Described mixture is put in shaft furnace and carried out retailoring by the speed of 300kg/h, and smelting temperature is 1450 ℃, and smelting time is 60min, and furnace roof flue-gas temperature is 450 ℃.Treat that slag is completely separated with alloy melt, superalloy and slag are emitted from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 97.1%, 96.9% and 96.0%; In slag, containing Cu, Co and Ni, be respectively 0.29wt%, 0.40wt% and 0.08wt%.Result shows, the present invention, in the high efficiente callback that realizes valuable metal, has reduced the content of valuable metal in slag.
Embodiment 3
Waste aluminum case lithium ion battery, copper ashes (Cu1wt%, TFe42wt%) and Wingdale are mixed, obtain mixture, wherein, by the mixing of getting the raw materials ready of the Wingdale of the copper ashes of 49.8wt%, 25.4wt%; In described mixture, CaO/SiO
2=1.3.
Described mixture is put in shaft furnace and carried out retailoring by the speed of 300kg/h, and smelting temperature is 1450 ℃, and smelting time is 60min, and furnace roof flue-gas temperature is 450 ℃.Treat that slag is completely separated with alloy melt, superalloy and slag are emitted from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 95.8%, 97.0% and 95.2%; In slag, containing Cu, Co and Ni, be respectively 0.45wt%, 0.41wt% and 0.10wt%.Result shows, the present invention, in the high efficiente callback that realizes valuable metal, has reduced the content of valuable metal in slag.
Embodiment 4
Waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery, copper ashes (Cu1wt%, TFe42wt%), Wingdale, silica and metallurgical coke are mixed, obtain mixture, wherein, the quality of waste and old lithium-ion battery with steel shell is 1.3 times of quality of waste aluminum case lithium ion battery, by the mixing of getting the raw materials ready of the metallurgical coke of the Wingdale of the copper ashes of 28.8wt%, 28.3wt%, 11.5wt%; In described mixture, CaO/SiO
2=1.5.
Described mixture is put in shaft furnace and carried out retailoring by the speed of 300kg/h, and smelting temperature is 1450 ℃, and smelting time is 60min, and furnace roof flue-gas temperature is 450 ℃.Treat that slag is completely separated with alloy melt, superalloy and slag are emitted from alloy mouth and slag notch respectively, obtain Cu-Co-Ni alloy and slag.
In the alloy of output, the rate of recovery of Cu, Co and Ni is respectively 96.5%, 97.7% and 96.3%; In slag, containing Cu, Co and Ni, be respectively 0.33wt%, 0.30wt% and 0.08wt%.Result shows, the present invention, in the high efficiente callback that realizes valuable metal, has reduced the content of valuable metal in slag.
As seen from the above embodiment, in the alloy of method output provided by the invention the rate of recovery of Cu, Co and Ni all >=95wt%, organic efficiency is higher; In slag the content of Cu, Co and Ni all≤0.5wt%, slag is processed without further dilution, can directly discard, technique is simple.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (5)
1. from waste and old lithium ion battery and/or its material, reclaim a method for valuable metal, comprise the following steps:
Waste and old lithium ion battery and/or its material, metallurgical coke are mixed with flux and/or containing the waste material of one or more in Cu, Co and Ni, obtain mixture; Described metallurgical coke accounts for 0～20wt% of mixture; In described mixture, CaO/SiO
2>=1 or (CaO+MgO)/SiO
2>=1;
Described mixture is carried out to retailoring at the temperature of 1400 ℃～1600 ℃, obtain alloy and slag containing valuable metal.
2. method according to claim 1, is characterized in that, in described mixture, and CaO/SiO
2=1.01～3 or (CaO+MgO)/SiO
2=1.01～3.
3. method according to claim 1, is characterized in that, described flux is one or more in Wingdale, rhombspar, silica and aluminum oxide.
4. method according to claim 1, is characterized in that, described is one or more in copper smelting slag, cobalt metallurgical slag and nickel metallurgical slag containing the waste material of one or more in Cu, Co and Ni.
5. method according to claim 1, is characterized in that, described waste and old lithium ion battery is one or more in waste and old lithium-ion battery with steel shell, waste aluminum case lithium ion battery and waste polymer lithium ion battery;
Described waste and old lithium ion battery material is for containing one or more lithium ion battery processing waste in Cu, Co and Ni.
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