CN109750163A - A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery - Google Patents
A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery Download PDFInfo
- Publication number
- CN109750163A CN109750163A CN201811519880.8A CN201811519880A CN109750163A CN 109750163 A CN109750163 A CN 109750163A CN 201811519880 A CN201811519880 A CN 201811519880A CN 109750163 A CN109750163 A CN 109750163A
- Authority
- CN
- China
- Prior art keywords
- iron lithium
- ternary
- lithium
- tertiary cathode
- anode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000011084 recovery Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000010406 cathode material Substances 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002386 leaching Methods 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000010828 elution Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000002893 slag Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 33
- 238000007789 sealing Methods 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 27
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000009991 scouring Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 3
- 239000011572 manganese Substances 0.000 abstract description 17
- 229910052748 manganese Inorganic materials 0.000 abstract description 16
- 238000003825 pressing Methods 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 abstract description 2
- 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 abstract 1
- 230000008569 process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910019573 CozO2 Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses the processing methods of a kind of tertiary cathode material and iron lithium anode material synthetical recovery, using lithium old and useless battery as metals such as raw materials recovery lithium, nickel, cobalt, manganese.The invention mainly includes steps: (1) size mixing, (2) reducing leaching, (3) Oxidation Leaching, (4) filters pressing, (5) online elution etc..Slave lithium old and useless battery of the invention is the method for the metals such as raw material synthetical recovery lithium, nickel, cobalt, manganese, in terms of existing technologies, its advantage is that raw material is simple, it is only necessary to tertiary cathode material, iron lithium anode material, concentrated hydrochloric acid, it can two kinds of anode material for lithium-ion batteries of integrated treatment；Lithium, nickel, cobalt, manganese recovery ratio are high, and environmental-friendly, production cost is low, effectively improves some shortcomings existing in the prior art.
Description
Technical field
The present invention relates to battery recycling technical fields, comprehensive more particularly to a kind of tertiary cathode material and iron lithium anode material
The method for closing recycling.
Background technique
Serondary lithium battery is widely used in 3C number, electric tool, electric bicycle and electronic because of its excellent performance
The fields such as automobile.In recent years, consumer increasingly increases the demand of such product, leads to the yield of lithium ion battery and waste and old
The quantity of lithium ion battery constantly increases, it is contemplated that 2020, the quantity of whole world waste and old lithium ion battery will be more than 25,000,000,000
Only.In waste and old lithium ion battery, the content of various metals is very considerable, many even to have been over its containing in ore
Amount, therefore there is very high recovery value.
At this stage, the recovery processing technology of lithium battery has become the hot spot of society, currently to the recycling master of old and useless battery
Concentrate on how recycling the valuable metal element in battery.The recovery method of existing waste lithium cell is broadly divided into pyrogenic process and wet
Method two ways, and industrially, wet process is relatively inexpensive, safe and environment-friendly, and therefore, application is relatively broad.It is being directed to ternary material
Hydrometallurgic recovery in, recycling separation metal obtains step after electric discharge, dismantling, sorting, crushing, the molten reducing leaching of acid, then gradually
To pure leachate, such as patent 201510967179.2, such method recycling step is relatively complicated, and energy consumption is high, and Product recycling
Process is in great demand to other materials；Or the ratio of the metal in leachate is adjusted by the way that Ni, Mn, Co ion is additionally added
Example, adds complexing agent and retrieves ternary precursor, later with Li2CO3Commercial ternary material is obtained after ball milling sintering, such as specially
Benefit 201610095291.6, such method still needs to increase other metal-containing compounds, and own material cannot be made full use of excellent
Gesture.And in the hydrometallurgic recovery of LiFePO 4 material, step is electric discharge, dismantling, alkali soluble, filtering, the oxidizing leaching of acid, removes
Miscellaneous plus sodium carbonate obtains Li2CO3Product, such as patent CN103280610, the method is also very big to the demand of other materials.
Summary of the invention
For this purpose, the purpose of the present invention is to provide the method for tertiary cathode material and iron lithium anode material synthetical recovery, energy
Enough while two kinds of anode material for lithium-ion batteries of recovery processing, and without adding in the prior art individually recovery processing tertiary cathode
Reducing agent (such as H in material acid dissolution2O2), oxidant (such as NaClO in LiFePO 4 material acid dissolution3), it reduces
Production cost, simple process and the rate of recovery are high, effectively improve some shortcomings existing in the prior art, include the following steps:
(1) size mixing: iron lithium powder is placed in the first sealing reaction kettle, and water is added to size mixing, and it is 4:1~6:1 that liquid, which consolidates mass ratio, is stirred
Mix slurry.
(2) reducing leaching: dense salt is added in the second sealing reaction kettle in the nickel cobalt manganese total mole number of measurement ternary powder
The H of concentrated hydrochloric acid is added in acid+Total moles ratio with the nickel cobalt manganese of ternary powder is 6:1~8:1, then in sealed states slowly
Ternary powder, stirring is added, reaction generates chlorine；
(3) Oxidation Leaching: the chlorine that step (2) also generates is passed through in the first sealing reaction kettle and carries out first order absorption, instead
After answering 2h~4h, then reaction kettle is sealed through first and is passed through two-level absorption tower, have aqueous slkali in the two-level absorption tower, by described
Aqueous slkali absorbs extra chlorine.
(4) filter: after fully reacting, by second seal reaction kettle in solution be filtered, obtain ternary leachate and
Ternary leached mud；The solution in reaction kettle is sealed by first to be filtered, and obtains iron lithium leachate and iron lithium leached mud.
(5) online elution: ternary leached mud elutes online obtains ternary leacheate and ternary elution slag, and iron lithium leached mud exists
Line elutes to obtain iron lithium leacheate and iron lithium elutes slag, by elute slag from ternary and iron lithium elute recycled in slag lithium, nickel, cobalt,
Manganese element.
The processing method of a kind of tertiary cathode material and iron lithium anode material synthetical recovery of the invention, using above-mentioned step
Suddenly, in terms of existing technologies, its advantage is that raw material is simple, it is only necessary to tertiary cathode material, iron lithium anode material, concentrated hydrochloric acid
And aqueous slkali, it can integrate while handle two kinds of anode material for lithium-ion batteries；Lithium, nickel, cobalt, manganese recovery ratio are high, and the rate of recovery is big
In 96%, and it is environmental-friendly, production cost is low, effectively improves some shortcomings existing in the prior art.
Further, in step (1), agitating mode is mechanical stirring, and mixing time is 0.5h~1.5h.
Further, in step (2), mixing time is 2h~4h.
Further, in step (2), the mass percentage concentration that concentrated hydrochloric acid is added is 30%~38%.
Further, in step (2), the speed that ternary powder is added is 2g/min~4g/min, by being slowly added into
Ternary powder can make reaction more abundant.
Further, in step (3), the chlorine is slowly introducing in the first sealing reaction kettle by flow control valve and is carried out
First order absorption, while the iron lithium slurry in the first sealing reaction kettle is quickly stirred, and at normal temperature, it is small to be stirred to react 2~4
When.
Further, in step (3), aqueous slkali is inorganic alkali solution.
Further, the mass percentage concentration of the inorganic alkali solution is 3%~6%.
Further, the inorganic alkali solution can be sodium hydroxide solution.
Further, in step (5), leaching scouring water and ternary elution slag mass ratio are 3:1~4:1, drench scouring water and iron
It is 3:1~4:1 that lithium, which elutes slag mass ratio,.
Detailed description of the invention
The above-mentioned and/or additional aspect and advantage of the embodiment of the present invention are from the description of the embodiment in conjunction with the following figures
It will be apparent and be readily appreciated that, in which:
Fig. 1 is the process flow chart of the embodiment of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Referring to Fig. 1, the method for a kind of tertiary cathode material and iron lithium anode material synthetical recovery of the invention, please refers to
Fig. 1, including following process flow:
(1) it sizes mixing: anode material for lithium-ion batteries iron lithium powder being placed in the first sealing reaction kettle, adds water to size mixing, liquid
Gu mass ratio is 4:1~6:1, stirring is slurried.
(2) reducing leaching: measuring the nickel cobalt manganese total mole number of another anode material for lithium-ion batteries ternary powder, toward the
Concentrated hydrochloric acid is added in two sealing reaction kettles, the H of concentrated hydrochloric acid is added+Total moles ratio with the nickel cobalt manganese of ternary powder is 6:1~8:
1, it is then slowly added to ternary powder in sealed states, stirs, reaction generates chlorine；
(3) Oxidation Leaching: the chlorine that step (2) also generates is passed through in the first sealing reaction kettle and carries out first order absorption, instead
After answering 2h~4h, then reaction kettle is sealed through first and is passed through two-level absorption tower, have aqueous slkali in the two-level absorption tower, by described
Aqueous slkali absorbs extra chlorine.
(4) filter: after fully reacting, by second seal reaction kettle in solution be filtered, obtain ternary leachate and
Ternary leached mud；The solution in reaction kettle is sealed by first to be filtered, and obtains iron lithium leachate and iron lithium leached mud.
(5) online elution: ternary leached mud elutes online obtains ternary leacheate and ternary elution slag, and iron lithium leached mud exists
Line elutes to obtain iron lithium leacheate and iron lithium elutes slag, elutes slag by ternary and iron lithium elutes and recycles lithium, nickel, cobalt, manganese in slag
Element.
The method of a kind of tertiary cathode material and iron lithium anode material synthetical recovery of the invention, specifically can also be described
The first necessary favorable sealing property of sealing reaction kettle in step (1), and the export mouth of flow control valve need to be had, its advantage is that
It prevents chlorine from leaking, pollutes environment, and can control the rate of chlorine input the first sealing reaction kettle, make fully reacting；Step (2)
With concentrated hydrochloric acid, its advantage is that can produce chlorine with ternary powder acidleach, chlorine can be further used as in iron lithium powder leaching process
Oxidant, reduce production cost, simple process effectively improves some shortcomings existing in the prior art；Step (3) institute
Stating chlorine input the first sealing reaction kettle is to be slowly introducing by safety valve, its advantage is that reaction rate can be effectively controlled, is guaranteed
The safety of production.
The step (2), (3) reactive ion equation be as follows:
2LiNixMnyCozO2+8H++2Cl-=2 (xNi2++yMn2++zCo2+)+Cl2(g)+2Li++4H2O
X+y+z=1
2LiFePO4+Cl2=2Li++2Cl-+2FePO4
Embodiment 1:
(1) it sizes mixing: 80g iron lithium powder (Li:3.84%, percentage are mass percent) being taken to be placed in the first sealing reaction kettle
It is interior, add water to size mixing, it is 4:1 that liquid, which consolidates mass ratio, and stirring is slurried.
(2) reducing leaching: dense salt is added in the second sealing reaction kettle in the nickel cobalt manganese total mole number of measurement ternary powder
The H of concentrated hydrochloric acid is added in acid+Total moles ratio with the nickel cobalt manganese of ternary powder is 6:1, is then slowly added to three in sealed states
First powder 117g is stirred to react 3h, generates chlorine；
(3) Oxidation Leaching: the chlorine that step (2) also generates is passed through in the first sealing reaction kettle and carries out first order absorption, instead
After answering 2h~4h, then reaction kettle is sealed through first and is passed through two-level absorption tower, have sodium hydroxide solution in the two-level absorption tower, lead to
It crosses the sodium hydroxide solution and absorbs extra chlorine.
(4) filter: after fully reacting, by second seal reaction kettle in solution be filtered, obtain ternary leachate and
Ternary leached mud；The solution in reaction kettle is sealed by first to be filtered, and obtains iron lithium leachate and iron lithium leached mud.
(5) online elution: ternary leached mud elutes online obtains ternary leacheate and ternary elution slag, and iron lithium leached mud exists
Line elutes to obtain iron lithium leacheate and iron lithium elutes slag, elutes slag by ternary and iron lithium elutes and recycles lithium, nickel, cobalt, manganese in slag
Element.
Through test and calculating, in ternary leachate, lithium, nickel, cobalt, the rate of recovery of manganese are high, respectively 98.1%, 98.2%,
97.9%, 98.3%；In iron lithium leachate, the rate of recovery of lithium is high, is 96.1%.
Embodiment 2:
(1) it sizes mixing: 80 grams of iron lithium powders (Li:3.84%, percentage are mass percent) being taken to be placed in the first sealing reaction
In kettle, water is added to size mixing, it is 4:1 that liquid, which consolidates mass ratio, is slurried within mechanical stirring 1 hour.
(2) reducing leaching: 500ml concentrated hydrochloric acid is added in the second sealing reaction kettle, the mass percentage concentration of concentrated hydrochloric acid is
30%, be slowly added in sealed states 117 grams of ternary powders (Li:5.46%, Ni:20.84%, Co:8.33%, Mn:
19.42%, percentage is mass percent), the H of concentrated hydrochloric acid is added+Total moles ratio with the nickel cobalt manganese of ternary powder is 7:1,
It is stirred to react 3 hours；
(3) Oxidation Leaching: the chlorine that step (2) reduction acidleach is generated is adjusted by flow control valve and is flowed through discharge pipe
First order absorption is carried out in the iron lithium slurry that speed input is quickly stirred, at normal temperature, is stirred to react 3 hours.Remaining chlorine input two
Grade absorption tower is the sodium hydroxide solution that mass percentage concentration is 5% in two-level absorption tower.
(4) filters pressing: after fully reacting, the solution second sealed in reaction kettle carries out filters pressing, obtains the leaching of 531ml ternary
Liquid and ternary leached mud；The solution first sealed in reaction kettle carries out filters pressing, obtains 276ml iron lithium leachate and iron lithium leaches
Slag.
(5) online elution: ternary leached mud is eluted with water online respectively again with iron lithium leached mud, obtains the leaching of 106ml ternary
Washing lotion and 15.80g ternary elute slag, and 216ml iron lithium leacheate and 34.05g iron lithium elute slag, elute slag and iron lithium by ternary
It elutes and recycles lithium, nickel, cobalt, manganese element in slag.Drenching scouring water and ternary elution slag mass ratio is 4:1, and leaching scouring water and iron lithium drench
Washery slag mass ratio is 4:1.
Through test and calculating, in ternary leachate, lithium, nickel, cobalt, the rate of recovery of manganese are high, respectively 98.5%, 98.4%,
98.6%, 98.3%；In iron lithium leachate, the rate of recovery of lithium is high, is 96.3%.
Embodiment 3:
(1) it sizes mixing: 80 grams of iron lithium powders (Li:3.84%, percentage are mass percent) being taken to be placed in the first sealing reaction
In kettle, water is added to size mixing, it is 5:1 that liquid, which consolidates mass ratio, is slurried within mechanical stirring 1 hour.
(2) reducing leaching: concentrated hydrochloric acid often is added in the second sealing reaction kettle, 600ml concentrated hydrochloric acid is added, in sealing state
Under be slowly added to 100 grams of ternary powders (Li:5.46%, Ni:20.84%, Co:8.33%, Mn:19.42%, percentage be matter
Measure percentage), the H of concentrated hydrochloric acid is added+Total moles ratio with the nickel cobalt manganese of ternary powder is 7.5:1, is stirred to react 4 hours；
(3) Oxidation Leaching: the chlorine that step (2) reduction acidleach is generated is adjusted by flow control valve and is flowed through discharge pipe
First order absorption is carried out in the iron lithium slurry that speed input is quickly stirred, at normal temperature, is stirred to react 4 hours.Remaining chlorine input two
Grade absorption tower is the sodium hydroxide solution that mass percentage concentration is 3% in two-level absorption tower.
(4) filters pressing: after fully reacting, the solution second sealed in reaction kettle carries out filters pressing, obtains the leaching of 637ml ternary
Liquid and ternary leached mud；The solution first sealed in reaction kettle carries out filters pressing, obtains 355ml iron lithium leachate and iron lithium leaches
Slag.
(5) online elution: ternary leached mud is eluted with water online respectively again with iron lithium leached mud, obtains the leaching of 187ml ternary
Washing lotion and 14.52g ternary elute slag, and 165ml iron lithium leacheate and 26.95g iron lithium elute slag, to recycle lithium, nickel, cobalt, manganese
Element.It drenches scouring water and ternary elution slag mass ratio is 3:1, leaching scouring water and iron lithium elution slag mass ratio are 3:1.
Through test and calculating, in ternary leachate, lithium, nickel, cobalt, the rate of recovery of manganese are high, respectively 98.8%, 98.3%,
99.1%, 98.8%；In iron lithium leachate, the rate of recovery of lithium is high, is 97.5%.
Embodiment 4:
(1) it sizes mixing: taking 80 grams of iron lithium powders (Li:3.84%) to be placed in self-control sealing reaction kettle 1, add water to size mixing, liquid is solid
Mass ratio is 6:1, is slurried within mechanical stirring 1 hour.
(2) reducing leaching: concentrated hydrochloric acid often is added in self-control sealing reaction kettle 2,600ml concentrated hydrochloric acid, the matter of concentrated hydrochloric acid is added
Measure percentage concentration be 30%, be slowly added in sealed states 120 grams of ternary powders (Li:5.46%, Ni:20.84%, Co:
8.33%, Mn:19.42%), the H of concentrated hydrochloric acid is added+Total moles ratio with the nickel cobalt manganese of ternary powder is 6:1, is stirred to react 3
Hour；
(3) Oxidation Leaching: the chlorine that step (2) reduction acidleach is generated is adjusted by flow control valve and is flowed through discharge pipe
First order absorption is carried out in the iron lithium slurry that speed input is quickly stirred, at normal temperature, is stirred to react 4 hours.Remaining chlorine input two
Grade absorption tower is the sodium hydroxide solution that mass percentage concentration is 6% in two-level absorption tower.
(4) filters pressing: after fully reacting, ternary reaction kettle solution is subjected to filters pressing, obtains 657ml ternary leachate and ternary
Filter residue；Iron lithium reaction kettle solution is subjected to filters pressing, obtains 584ml iron lithium leachate and iron lithium filter residue.
(5) online elution: ternary leached mud is eluted with water online respectively again with iron lithium leached mud, obtains the elution of 207 ternarys
Liquid and 16.13g ternary elute slag, and 231ml iron lithium leacheate and 27.64g iron lithium elute slag, to recycle lithium, nickel, cobalt, manganese member
Element.It drenches scouring water and wet slag mass ratio is 4:1.
(6) it is tested and is calculated, in ternary leachate, lithium, nickel, cobalt, the rate of recovery of manganese are high, respectively 98.9%,
99.2%, 98.7%, 99.0%；In iron lithium leachate, the rate of recovery of lithium is high, is 97.2%.
Embodiment 5:
(1) it sizes mixing: taking 100 grams of iron lithium powders (Li:3.84%) to be placed in self-control sealing reaction kettle 1, add water to size mixing, liquid is solid
Mass ratio is 5:1, is slurried within mechanical stirring 2 hours.
(2) reducing leaching: 500ml concentrated hydrochloric acid is added in self-control sealing reaction kettle 2, the mass percentage concentration of concentrated hydrochloric acid is
38%, be slowly added in sealed states 117 grams of ternary powders (Li:5.46%, Ni:20.84%, Co:8.33%, Mn:
19.42%) H of concentrated hydrochloric acid, is added+Total moles ratio with the nickel cobalt manganese of ternary powder is 7:1, is stirred to react 3.5 hours；
(3) Oxidation Leaching: the chlorine that step (2) reduction acidleach is generated is adjusted by flow control valve and is flowed through discharge pipe
First order absorption is carried out in the iron lithium slurry that speed input is quickly stirred, at normal temperature, is stirred to react 4 hours.Remaining chlorine input two
Grade absorption tower is the sodium hydroxide solution that mass percentage concentration is 5% in two-level absorption tower.
(4) filters pressing: after fully reacting, ternary reaction kettle solution is subjected to filters pressing, obtains 548ml ternary leachate and ternary
Leached mud；Iron lithium reaction kettle solution is subjected to filters pressing, obtains 493ml iron lithium leachate and iron lithium leached mud.
(5) online elution: ternary leached mud is eluted with water online respectively again with iron lithium leached mud, obtains the leaching of 112ml ternary
Washing lotion and 14.96g ternary elute slag, and 389ml iron lithium leacheate and 49.25g iron lithium elute slag, to recycle lithium, nickel, cobalt, manganese
Element.It drenches scouring water and wet slag mass ratio is 4:1.
(6) it is tested and is calculated, in ternary leachate, lithium, nickel, cobalt, the rate of recovery of manganese are high, respectively 98.3%,
98.4%, 98.2%, 98.0%；In iron lithium leachate, the rate of recovery of lithium is high, is 96.1%.
The chemical composition analysis of each leachate is shown in Table 1 in above-described embodiment.
The chemical composition analysis of each leachate in 1 embodiment of table
The chemical composition analysis of each leacheate is shown in Table 2 in above-described embodiment.
The chemical composition analysis of each leacheate in 2 embodiment of table
The chemical composition analysis that slag is respectively eluted in above-described embodiment is shown in Table 3.
The chemical composition analysis of slag is respectively eluted in 3 embodiment of table
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
One or more embodiment or examples in can be combined in any suitable manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
A variety of change, modification, replacement and modification can be carried out to these embodiments in the case where being detached from the principle of the present invention and objective, this
The range of invention is defined by the claims and their equivalents.
Claims (10)
1. a kind of method of tertiary cathode material and iron lithium anode material synthetical recovery, characterized by the following steps:
(1) size mixing: iron lithium powder is placed in the first sealing reaction kettle, and water is added to size mixing, and it is 4:1~6:1 that liquid, which consolidates mass ratio, is stirred into
Slurry.
(2) reducing leaching: the nickel cobalt manganese total mole number of measurement ternary powder is added concentrated hydrochloric acid in the second sealing reaction kettle, adds
Enter the H of concentrated hydrochloric acid+Total moles ratio with the nickel cobalt manganese of ternary powder is 6:1~8:1, and ternary powder is then added in sealed states
Material, stirring, reaction generate chlorine；
(3) Oxidation Leaching: the chlorine that step (2) generate being passed through in the first sealing reaction kettle and carries out first order absorption, and reaction 2h~
After 4h, then reaction kettle is sealed through first and is passed through two-level absorption tower, have aqueous slkali in the two-level absorption tower, pass through the aqueous slkali
Absorb extra chlorine.
(4) it filters: after fully reacting, sealing the solution in reaction kettle for second and be filtered, obtain ternary leachate and ternary
Leached mud；The solution in reaction kettle is sealed by first to be filtered, and obtains iron lithium leachate and iron lithium leached mud.
(5) online elution: ternary leached mud elutes online obtains ternary leacheate and ternary elution slag, and iron lithium leached mud drenches online
It washes to obtain iron lithium leacheate and iron lithium elutes slag, eluted in slag and iron lithium elution slag from ternary and recycle lithium, nickel, cobalt, manganese element.
2. the method for a kind of tertiary cathode material according to claim 1 and iron lithium anode material synthetical recovery, feature
Be: in step (1), agitating mode is mechanical stirring, and mixing time is 0.5h~1.5h.
3. the method for a kind of tertiary cathode material according to claim 1 and iron lithium anode material synthetical recovery, feature
Be: in step (2), mixing time is 2h~4h.
4. the method for a kind of tertiary cathode material according to claim 1 and iron lithium anode material synthetical recovery, feature
Be: in step (2), the mass percentage concentration that concentrated hydrochloric acid is added is 30%~38%.
5. the method for a kind of tertiary cathode material according to claim 4 and iron lithium anode material synthetical recovery, feature
Be: in step (2), the speed that ternary powder is added is 2g/min~4g/min.
6. the method for a kind of tertiary cathode material according to claim 1 and iron lithium anode material synthetical recovery, feature
Be: in step (3), the chlorine is passed through in the first reaction kettle by flow control valve and carries out first order absorption, while first is close
Iron lithium slurry in envelope reaction kettle is stirred, and at normal temperature, is stirred to react 2~4 hours.
7. the method for a kind of tertiary cathode material according to claim 6 and iron lithium anode material synthetical recovery, feature
Be: in step (3), aqueous slkali is inorganic alkali solution.
8. the method for a kind of tertiary cathode material according to claim 7 and iron lithium anode material synthetical recovery, feature
Be: the mass percentage concentration of the inorganic alkali solution is 3%~6%.
9. the method for a kind of tertiary cathode material according to claim 8 and iron lithium anode material synthetical recovery, feature
Be: the inorganic alkali solution is sodium hydroxide solution.
10. the method for a kind of tertiary cathode material according to claim 1 and iron lithium anode material synthetical recovery, feature
Be: in step (5), leaching scouring water and ternary elution slag mass ratio are 3:1~4:1, and leaching scouring water and iron lithium elute slag amount
Than for 3:1~4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811519880.8A CN109750163A (en) | 2018-12-12 | 2018-12-12 | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811519880.8A CN109750163A (en) | 2018-12-12 | 2018-12-12 | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109750163A true CN109750163A (en) | 2019-05-14 |
Family
ID=66403829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811519880.8A Pending CN109750163A (en) | 2018-12-12 | 2018-12-12 | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109750163A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484043A (en) * | 2020-03-05 | 2020-08-04 | 赣州龙凯科技有限公司 | Comprehensive recovery method of waste lithium manganate and lithium iron phosphate cathode material |
| CN111799524A (en) * | 2020-07-13 | 2020-10-20 | 中钢集团南京新材料研究院有限公司 | A method for preparing a five-element high-entropy lithium battery material precursor from a decommissioned lithium battery cathode sheet |
| CN116902999A (en) * | 2023-05-31 | 2023-10-20 | 广东盛祥新材料科技有限公司 | Ternary powder/lithium iron powder/lithium carbonate processing method and waste battery recycling method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
| CN108504865A (en) * | 2018-03-30 | 2018-09-07 | 中国科学院过程工程研究所 | A method of strengthening waste lithium ion cell anode active material and leaches |
-
2018
- 2018-12-12 CN CN201811519880.8A patent/CN109750163A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
| CN108504865A (en) * | 2018-03-30 | 2018-09-07 | 中国科学院过程工程研究所 | A method of strengthening waste lithium ion cell anode active material and leaches |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484043A (en) * | 2020-03-05 | 2020-08-04 | 赣州龙凯科技有限公司 | Comprehensive recovery method of waste lithium manganate and lithium iron phosphate cathode material |
| CN111799524A (en) * | 2020-07-13 | 2020-10-20 | 中钢集团南京新材料研究院有限公司 | A method for preparing a five-element high-entropy lithium battery material precursor from a decommissioned lithium battery cathode sheet |
| CN111799524B (en) * | 2020-07-13 | 2023-12-26 | 中钢集团南京新材料研究院有限公司 | Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate |
| CN116902999A (en) * | 2023-05-31 | 2023-10-20 | 广东盛祥新材料科技有限公司 | Ternary powder/lithium iron powder/lithium carbonate processing method and waste battery recycling method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101619394B (en) | Method for leaching anode and cathode mixed material of waste lithium nickel manganese cobalt battery | |
| CN101643243B (en) | Method for recycling copper, nickel, chromium, zinc and iron from plating sludge | |
| CN103274471B (en) | Method for preparing electronic-grade manganese sulfate by utilizing ferro-manganese alloy furnace slag | |
| CN101928831B (en) | Leaching method of anode material of lithium cobalt oxide waste battery | |
| CN101624653A (en) | Method for leaching mixed cathode and anode materials from waste nickel-cadmium batteries | |
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN106048251B (en) | A kind of process of clean and effective processing setting form | |
| CN109439907A (en) | A method of iron aluminium is removed from the pickle liquor during recycling used Li ion cell | |
| CN101503761A (en) | Method for separating and recycling valuable metal from pressure leached high sulphur slag | |
| WO2017127950A1 (en) | Molten salt chemical method for recovering waste hard alloy | |
| CN107630146A (en) | nickel recovery method | |
| CN101648702A (en) | Method for preparing tellurium dioxide by using crude tellurium as raw material | |
| CN100417475C (en) | A method for producing metal zinc powder with zinc dust and zinc dross | |
| CN109750163A (en) | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery | |
| CN103274470A (en) | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag | |
| CN101481144B (en) | Clean production method for preparing potassium chromate from chromic iron | |
| CN103789542B (en) | A kind of wet reducing leaching method of manganese oxide mineral | |
| CN105779777A (en) | Method for separating and recycling nickel and cobalt from nickel and cobalt slag | |
| CN107739829A (en) | The recovery method of nickel element, cobalt element, copper and Zn-ef ficiency in smelting laterite-nickel ores and in slag | |
| CN106756069A (en) | A kind of method that valuable metal is reclaimed in the waste residue from zinc abstraction | |
| CN102534247A (en) | Method for leaching valuable metal | |
| CN109599602A (en) | The method that the waste and old positive electrode of a kind of pair of lithium battery carries out resource utilization | |
| CN105110300B (en) | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur | |
| CN106927486A (en) | A kind of method for sintering extraction potassium chloride in ash | |
| CN108706844A (en) | Iron, chromium, the separation and recovery method of aluminium and its application in more metal hazardous wastes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190514 |