CN111589278B - System and method for recycling water of recovered waste lithium ion battery - Google Patents
System and method for recycling water of recovered waste lithium ion battery Download PDFInfo
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- CN111589278B CN111589278B CN202010343278.4A CN202010343278A CN111589278B CN 111589278 B CN111589278 B CN 111589278B CN 202010343278 A CN202010343278 A CN 202010343278A CN 111589278 B CN111589278 B CN 111589278B
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- 238000000034 method Methods 0.000 title claims abstract description 137
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004064 recycling Methods 0.000 title claims abstract description 54
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 262
- 238000002386 leaching Methods 0.000 claims abstract description 218
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 177
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 177
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 79
- 239000012452 mother liquor Substances 0.000 claims abstract description 66
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003546 flue gas Substances 0.000 claims abstract description 48
- 238000003825 pressing Methods 0.000 claims abstract description 43
- 238000001556 precipitation Methods 0.000 claims abstract description 39
- 238000000746 purification Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 33
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 33
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 32
- 238000000605 extraction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 32
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 28
- 238000003763 carbonization Methods 0.000 claims description 24
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 20
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000006703 hydration reaction Methods 0.000 claims description 14
- 239000012736 aqueous medium Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000013067 intermediate product Substances 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 239000002609 medium Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/265—Drying gases or vapours by refrigeration (condensation)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
Abstract
The application provides a retrieve old and useless lithium ion battery water cyclic utilization system includes: the lithium extraction unit comprises a lithium extraction leaching unit and a flue gas purification unit communicated with the lithium extraction leaching unit; the lithium extraction unit is used for purifying and separating lithium ions and comprises a lithium bicarbonate leaching process section, a lithium hydroxide leaching process section, a neutralization lithium precipitation process section and a filter pressing purification process section, wherein the lithium bicarbonate leaching process section and the lithium hydroxide leaching process section are respectively communicated with the neutralization lithium precipitation process section, neutralization lithium precipitation reaction is carried out in the neutralization lithium precipitation process section to obtain lithium carbonate crystal precipitation liquid, then filter pressing is carried out through the filter pressing purification process section to separate low-concentration lithium-containing mother liquid, and the low-concentration lithium-containing mother liquid is respectively conveyed to the lithium bicarbonate leaching process section, the lithium hydroxide leaching process section and the flue gas purification unit; the flue gas purification unit is used for purifying the flue gas, recycling the water vapor in the flue gas and leaching the fluorine-containing compounds in the flue gas by lithium-containing mother liquor. The system can realize water saving and zero discharge of waste water.
Description
Technical Field
The application belongs to the technical field of resource recovery, and particularly relates to a system and a method for recycling waste lithium ion battery water.
Background
Since the lithium ion battery enters the market, the lithium ion battery is widely applied to electronic information products, electric tools, electric automobile industries and the like due to the advantages of high energy density, high voltage, good cycle performance, small self-discharge, safe operation and the like. The lithium ion battery anode material mainly comprises lithium cobaltate, lithium manganate, a ternary material of nickel cobalt lithium manganate, lithium iron phosphate and the like, and the cathode material mainly comprises natural graphite, artificial graphite and the like. Because the service life of the lithium ion battery is limited, the lithium ion battery enters a large-scale elimination period after being used for five or six years, and the battery belongs to serious pollution solid waste, along with the retirement of a large amount of lithium ion batteries, the comprehensive recycling of the waste lithium ion batteries becomes an important production chain for recycling new energy lithium batteries, and the construction of a perfect environment-friendly waste lithium battery 'solid waste recycling' system becomes the development trend of the lithium battery industry.
At present, the water purification and recycling cost in the comprehensive recycling system of the waste lithium batteries is high, a large amount of new water is needed for supplement, distilled water is generally obtained by an MVR evaporation crystallization mode for recycling, and the energy consumption is very high.
Therefore, an environment-friendly and efficient water circulation system is urgently needed to be developed so as to realize water conservation and zero discharge of waste water of the whole recovery production line.
Disclosure of Invention
In view of this, an object of the present application is to provide a system and a method for recycling water from waste lithium ion batteries, so as to solve the problems of high cost of water purification and recycling in a comprehensive waste lithium battery recycling system and the need of supplementing a large amount of new water.
In order to achieve the above object, one aspect of the present application provides a system for recycling water from waste lithium ion batteries, including: the lithium extraction unit comprises a lithium extraction leaching unit and a flue gas purification unit communicated with the lithium extraction leaching unit;
the lithium extraction unit is used for purifying and separating lithium ions and comprises a lithium bicarbonate leaching process section, a lithium hydroxide leaching process section, a neutralization lithium precipitation process section and a filter pressing purification process section, wherein the lithium bicarbonate leaching process section and the lithium hydroxide leaching process section are respectively communicated with the neutralization lithium precipitation process section, neutralization lithium precipitation reaction is carried out in the neutralization lithium precipitation process section to obtain lithium carbonate crystal precipitation liquid, then filter pressing is carried out through the filter pressing purification process section to separate lithium-containing mother liquid, and the lithium-containing mother liquid is respectively conveyed to the lithium bicarbonate leaching process section, the lithium hydroxide leaching process section and the flue gas purification unit;
the flue gas purification unit is used for purifying the flue gas, recycling the water vapor in the flue gas and leaching the fluorine-containing compounds in the flue gas by lithium-containing mother liquor.
Optionally, the system for recycling the recovered waste lithium ion battery water further comprises an aqueous medium cooling unit for cooling the leaching lithium extraction unit and the flue gas purification unit.
Optionally, the leaching lithium extraction unit further comprises a lithium-rich process section in communication with the lithium hydroxide leaching process section for increasing the lithium content.
The application also provides a recycling method for recycling the water of the waste lithium ion battery, and the recycling system for recycling the water of the waste lithium ion battery comprises the following steps:
conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage to carry out hydration reaction and leaching treatment on the material containing lithium oxide, and leaching and separating out a lithium hydroxide leaching solution;
conveying the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process section to carry out carbonization reaction and leaching treatment on the material containing lithium carbonate, and leaching and separating to obtain a leaching solution containing lithium bicarbonate;
mixing the lithium hydroxide leachate and the leachate containing lithium bicarbonate to perform neutralization and lithium precipitation reaction, performing pressure filtration on a lithium carbonate crystal precipitation liquid obtained by the reaction to separate lithium-containing mother liquor and lithium carbonate, and recycling the lithium-containing mother liquor to a lithium hydroxide leaching process section and a lithium bicarbonate leaching process section;
and conveying the third part of the lithium-containing mother liquor to a flue gas purification unit to react with fluoride to generate a lithium fluoride aqueous solution, and performing filter pressing on the lithium fluoride aqueous solution to separate lithium fluoride and the filter pressing aqueous solution.
Optionally, the first part of the lithium-containing mother liquor is conveyed to a lithium hydroxide leaching process section to perform hydration reaction and leaching treatment on the material containing lithium oxide, and in the step of leaching and separating out the lithium hydroxide leachate, the leaching treatment step includes: and leaching the material containing lithium oxide by adopting multi-stage semi-closed cycle, wherein the lithium content of the lithium-containing mother liquor is 2-4 g/L, and the lithium content in the leached lithium hydroxide leachate is 8-12 g/L.
Optionally, the step of conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage to perform hydration reaction and leaching treatment on the material containing lithium oxide, and leaching and separating out a lithium hydroxide leachate includes:
conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process section to perform ball milling on a material containing lithium oxide, generating lithium hydroxide through hydration reaction, leaching the lithium hydroxide, performing filter pressing after the leaching, and performing filter pressing to separate a lithium hydroxide leaching solution and a first leaching filter cake.
Optionally, the step of conveying the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process stage to perform carbonization reaction and leaching treatment on the material containing lithium carbonate, and leaching and separating out a lithium bicarbonate leaching solution includes:
introducing carbon dioxide into the lithium bicarbonate leaching process section to perform carbonization reaction to generate lithium bicarbonate, controlling the carbonization temperature to be 15-45 ℃ and the carbonization time to be 1-5 h;
respectively conveying the second part of the lithium-containing mother liquor and the first leached filter cake to a lithium bicarbonate leaching process section for leaching treatment, and controlling the solid-liquid mass ratio of the first leached filter cake to the second part of the lithium-containing mother liquor to be 1: and 2-20, performing filter pressing treatment after leaching treatment, and separating a leachate containing lithium bicarbonate through filter pressing.
Optionally, the step of sending the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process stage to perform carbonization reaction and leaching treatment on the material containing lithium carbonate, and leaching and separating out a leaching solution containing lithium bicarbonate, wherein the leaching treatment step includes:
and leaching the material containing lithium carbonate by adopting multi-stage semi-closed cycle leaching, wherein the lithium content of the lithium-containing mother liquor is 2-4 g/L, and the lithium content of the leached leaching solution containing lithium bicarbonate is 6-9 g/L.
Optionally, in the step of mixing the lithium hydroxide leachate with the leachate containing lithium bicarbonate to perform a neutralization lithium precipitation reaction, and performing pressure filtration on the mixture obtained by the reaction to separate a lithium-containing mother liquor and lithium carbonate, the volume ratio of the lithium hydroxide leachate to the leachate containing lithium bicarbonate is 2.0-1.0: 1, carrying out neutralization and lithium precipitation reaction.
Optionally, the step of conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage to perform hydration reaction and leaching treatment on the material containing lithium oxide, and after leaching and separating out a lithium hydroxide leachate, further includes:
and (3) carrying out lithium enrichment treatment on a part of the lithium hydroxide leaching solution.
Optionally, the flue gas purification unit comprises an intermediate product dosing process section, and the filter-pressing aqueous solution is reused in the intermediate product dosing process section.
Compared with the prior art, the method has the following beneficial effects:
according to the embodiment of the application, by adopting the leaching lithium extraction unit of the acid-free wet process, the flue gas purification unit and the water medium cooling unit which can recycle steam in flue gas, the annual new water supplement amount of the waste lithium ion battery water recycling system is controlled within 5%, the water cost is reduced, zero discharge of waste water can be realized, and the waste lithium ion battery water recycling system is more environment-friendly and efficient.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a system for recycling water from waste lithium ion batteries according to a first embodiment of the present application;
fig. 2 is a schematic flow chart of a method for recycling water from waste lithium ion batteries according to a second embodiment of the present application;
wherein, each reference mark in the figure is:
100-leaching lithium extraction unit; 200-a flue gas purification unit; 300-aqueous medium cooling unit.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application.
Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" - "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
On the one hand, the embodiment of the application provides a system for recycling water of waste lithium ion batteries. The anode material of the waste lithium ion battery is mainly cobalt nickel lithium manganate, lithium cobaltate, lithium manganate and the like, and the cathode material is mainly carbon or graphene material; the process of recycling the waste lithium ion battery generally comprises pretreatment, dissolution and leaching of electrode materials, and separation and recovery of valuable metal elements in leachate.
Specifically, the pretreatment step comprises:
in the discharge pretreatment, because most of the residual electric quantity in the waste lithium ion batteries needs to be completely discharged before treatment, otherwise, in the subsequent treatment, the residual energy can release a large amount of heat in a centralized manner, and adverse effects such as potential safety hazards can be caused.
Crushing and separating, namely, combining the electrode material with other substances such as organic matters such as binders and the like by separation technologies such as multistage crushing, screening and the like, removing iron sheets, copper foils and aluminum foils, realizing separation and enrichment of the electrode material, obtaining an intermediate product taking the anode and cathode mixed material as a main component, and adding an ecological activator for compounding according to main material elements contained in the intermediate product.
And (2) performing heat treatment, namely removing insoluble organic matters, carbon powder and the like in the waste lithium ion battery by adopting high-temperature roasting and the like, and separating an electrode material from a current collector, wherein the positive electrode material is subjected to a carbothermic reaction in the process, lithium carbonate and lithium oxide can be reduced to obtain a large amount of metal oxide, fluorine in the electrolyte can be removed, and the flue gas generated in the heat treatment process contains fluoride and a large amount of water vapor.
Specifically, the dissolution leaching step of the electrode material includes:
the dissolution leaching of the electrode material may be achieved by a leaching process such as water leaching to obtain a solution containing ions such as lithium ions, cobalt ions, etc.
Referring to fig. 1, the system for recycling water from waste lithium ion batteries according to the embodiment of the present application includes: a lithium leaching and extracting unit 100 and a flue gas purification unit 200 communicated with the lithium leaching and extracting unit 100; the leaching lithium extraction unit 100 is used for purifying and separating lithium ions, and comprises a lithium bicarbonate leaching process section, a lithium hydroxide leaching process section, a neutralization lithium precipitation process section and a filter pressing purification process section, wherein the lithium bicarbonate leaching process section and the lithium hydroxide leaching process section are respectively communicated with the neutralization lithium precipitation process section, neutralization lithium precipitation reaction is carried out in the neutralization lithium precipitation process section to obtain lithium carbonate crystal precipitation liquid, then filter pressing is carried out through the filter pressing purification process section to separate lithium-containing mother liquid, and the lithium-containing mother liquid is respectively conveyed to the lithium bicarbonate leaching process section, the lithium hydroxide leaching process section and the flue gas purification unit; wherein the lithium-containing mother liquor is an aqueous solution containing lithium hydroxide.
The flue gas purification unit 200 is used for purifying flue gas, recycling water vapor in the flue gas and leaching fluorine-containing compounds in the flue gas through lithium-containing mother liquor.
A spray tower can be arranged in the flue gas purification unit 200, flue gas generated by high-temperature roasting contains fluoride and a large amount of water vapor, the flue gas and lithium-containing mother liquor are respectively introduced into the spray tower, the flue gas is purified and condensed, the water vapor is condensed into wastewater, more than 98% of wastewater can be recycled, the fluoride reacts with LiOH in the lithium-containing mother liquor to generate lithium fluoride, the lithium-containing mother liquor leaches a mixture obtained after reaction in the spray tower to extract a lithium fluoride aqueous solution, and the lithium fluoride aqueous solution in the spray tower enters a lithium fluoride filter-pressing purification process section for filter-pressing treatment to obtain a lithium fluoride byproduct and a filter-pressing aqueous solution; the filter pressing water solution is further reused in an intermediate product batching process section in the flue gas purification unit for compounding of intermediate products, the water content of the compounded product is about 30%, the compounded product is conveyed to a heat treatment process section for high-temperature roasting, water and residual lipid substances contained in the compounded product are volatilized or reacted to form water vapor, Volatile Organic Compounds (VOCs) and the like, and the water vapor enters a spray tower again to realize condensation and recycling of a large amount of water vapor in the flue gas.
According to the embodiment of the application, the lithium extraction unit adopting the acid-free wet process and the flue gas purification unit capable of recycling the water vapor in the flue gas are adopted, so that the water vapor in the lithium-containing mother liquor or the flue gas is fully recycled, the new water supplement amount is reduced, the process route of the system is simple, water is saved, the environment is protected, the efficiency is high, and zero discharge of wastewater can be realized.
The system for recycling water of the waste lithium ion battery in the embodiment of the application further comprises: the aqueous medium cooling unit 300. The aqueous medium unit 300 is used as an external water circulation unit of the system, and can perform cooling treatment on the lithium leaching unit 100 and the flue gas purification unit 200, and can perform cooling treatment on other equipment in the system.
Specifically, the aqueous medium cooling unit 300 may cool the aqueous medium of the devices such as the circulation pump in the lithium extraction unit 100 and the flue gas purification unit 200, and may also cool the high-temperature roasting device used in the heat treatment process, and the high-efficiency heat exchanger is used for heat transfer, and the waste heat enters the waste heat utilization system, such as the floor heating system used in offices, the lithium bicarbonate leaching process section, and the lithium hydroxide leaching process section. After the waste heat exchange is finished, the water temperature is reduced, the water enters a cooling water tempering pool to reduce the water temperature to room temperature, the hardness (concentration of calcium and magnesium ions in water) of the cooling water can be ensured to be less than or equal to 500mg/L, and the total turbidity (SS) of the cooling water is ensured to be less than or equal to 170ppm, and finally the cooling water is conveyed to water medium cooling equipment such as high-temperature roasting equipment and a circulating pump by a suction pump to form a water medium cooling unit, so that the recycling of the cooling water is realized. The waste lithium battery recycling device can effectively avoid the generation of a large amount of waste water in the waste lithium battery recycling production process, and can fully utilize the waste heat of the waste lithium battery.
As a specific example, according to the production and use conditions, 3 months are taken as a continuous production cycle, 1500 tons of waste lithium batteries are treated, water can be saved by more than 5 ten thousand tons, and statistics of the new water replenishment rate are shown in table 1:
TABLE 1
As can be seen from the table 1, the amount of fresh water supply of the recycled waste lithium ion battery water recycling system in the embodiment of the application can be controlled within 5% every year, and the water cost is reduced.
Further, in order to prevent the amount of water required for neutralizing lithium bicarbonate and lithium hydroxide in the lithium precipitation neutralization process section from exceeding the neutralization matching range and break the water balance, the leaching lithium extraction unit 100 may further include a lithium-rich process section communicated with the lithium hydroxide leaching process section.
On the other hand, the embodiment of the application provides a method for recycling water of waste lithium ion batteries.
Referring to fig. 2, the method for recycling water of recycled waste lithium ion batteries according to the embodiment of the present application adopts the system for recycling water of recycled waste lithium ion batteries according to the embodiment, and includes the following steps:
s100, conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process section to carry out hydration reaction and leaching treatment on a material containing lithium oxide, and leaching and separating a lithium hydroxide leaching solution;
wherein the lithium-containing mother liquor is an aqueous solution containing lithium hydroxide, the lithium content is 2-4 g/L, and lithium oxide Li obtained by high-temperature roasting is mainly contained in the lithium oxide-containing material before the lithium-containing mother liquor is not input2O and other impurities; carrying out hydration reaction and leaching treatment on lithium oxide by adopting lithium-containing mother liquor, and obtaining lithium hydroxide after leaching, wherein the following reactions occur in the hydration process:
Li2O+H2O→2LiOH。
s200, conveying the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process section to carry out carbonization reaction and leaching treatment on a material containing lithium carbonate, and leaching and separating a leaching solution containing lithium bicarbonate;
wherein, before lithium-containing mother liquor is not input, lithium carbonate Li obtained by high-temperature roasting is mainly contained in the material containing lithium carbonate2CO3And itOther impurities, lithium carbonate in this state is of low quality and cannot be directly exported as a product, so further recrystallization treatment is required. Inputting carbon dioxide to a lithium bicarbonate leaching process section to perform carbonization reaction of carbon dioxide and lithium carbonate to generate lithium bicarbonate, performing leaching treatment by adopting lithium-containing mother liquor, performing carbonization treatment on lithium carbonate to obtain lithium bicarbonate with higher solubility, and obtaining a leaching solution containing the lithium bicarbonate in the lithium bicarbonate leaching process section, wherein the leaching solution containing the lithium bicarbonate comprises the lithium bicarbonate and residual lithium hydroxide; after carbonization, lithium bicarbonate can be generated, the reaction is an irreversible reaction, and the carbonization reaction is as follows:
Li2CO3+CO2+H2O→2LiHCO3；
LiOH+CO2→LiHCO3。
s300, mixing the lithium hydroxide leaching solution and the leaching solution containing lithium bicarbonate to perform neutralization lithium precipitation reaction, performing pressure filtration on a lithium carbonate crystal precipitation solution obtained by the reaction to separate lithium-containing mother solution and lithium carbonate, and recycling the lithium-containing mother solution to a lithium hydroxide leaching process section and a lithium bicarbonate leaching process section. Wherein lithium carbonate can be sold as a product.
Conveying the lithium hydroxide leachate and the leachate containing lithium bicarbonate to a neutralization lithium precipitation process section for neutralization lithium precipitation reaction to generate lithium-containing mother liquor and lithium carbonate, wherein the neutralization lithium precipitation reaction process is as follows:
LiOH+LiHCO3→Li2CO3+H2O。
s400, conveying a third part of the lithium-containing mother liquor to a flue gas purification unit to react with fluoride to generate a lithium fluoride aqueous solution, and performing filter pressing on the lithium fluoride aqueous solution to separate lithium fluoride and the filter pressing aqueous solution.
Wherein, step S100 includes:
s110, conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process section to perform ball milling on a material containing lithium oxide, generating lithium hydroxide through hydration reaction, leaching the lithium hydroxide, performing filter pressing after the leaching, and performing filter pressing to separate a lithium hydroxide leaching solution and a first leaching filter cake.
As a specific embodiment, step S110 may include:
s111, conveying the lithium-containing mother liquor to a lithium hydroxide leaching process section to obtain a first mixture, and controlling the mass percentage of the lithium-containing mother liquor to be 20% -40% relative to the mass percentage of a material containing lithium oxide: ball-milling 100% until the granularity of the material reaches more than 85% with 200-400 meshes, and discharging part of the first mixture to a buffer barrel 1# at the front end of the neutralization and lithium precipitation process section for later use;
s112, delivering the lithium-containing mother liquor into the first mixture in the lithium hydroxide leaching process section again, and controlling the solid-liquid mass ratio of the first mixture to the lithium-containing mother liquor to be 1: and 2-20, carrying out leaching treatment to obtain a second mixture.
The feeding concentration condition in the ball milling process can be ensured by adding the lithium-containing mother liquor in the ball milling process, the first mixture can reach the particle size condition of 200-400 meshes by ball milling, and the optimal water leaching process condition can be achieved by subsequently adding the lithium-containing mother liquor in the first mixture. The total weight of the lithium-containing mother liquor added in step S111 and step S112, respectively, is the total weight of the first portion of the lithium-containing mother liquor.
S113, performing filter pressing treatment on the second mixture, and performing filter pressing separation on the lithium hydroxide leaching solution and the first leaching filter cake.
And the second mixture can be subjected to filter pressing by adopting an ultrafiltration membrane, macromolecular substances and solid substances in the second mixture are intercepted, and LiOH in the second mixture does not reach the solubility and cannot be intercepted. Filtering to obtain filtrate, namely lithium hydroxide leachate, wherein the main component of the filtrate is LiOH, and transferring the lithium hydroxide leachate out to enter a No. 1 buffer barrel at the front end of a neutralization lithium precipitation process section for later use; and the filter cake obtained after filter pressing is the first leached filter cake.
Specifically, the step of the leaching process in step S100 includes: leaching by means of a multi-stage semi-closed cycle, as an example and not by way of limitation, leaching by means of a two-stage semi-closed cycle, leaching by means of a three-stage semi-closed cycle or leaching by means of a two-stage semi-closed cycle; as a specific embodiment, two-stage semi-closed cycle leaching is adopted, wherein the first stage is cycled for 1-5 times, the first-stage lithium leaching rate is 65-85%, the second stage is cycled for 6-15 times, the second-stage lithium leaching rate is 10-20%, and the lithium content in the leached lithium hydroxide leaching process stage is 8-12 g/L.
On the basis of step S100, S200 includes:
introducing carbon dioxide into the lithium bicarbonate leaching process section to perform carbonization reaction to generate lithium bicarbonate, controlling the carbonization temperature to be 15-45 ℃ and the carbonization time to be 1-5 h;
respectively conveying the second part of the lithium-containing mother liquor and the first leaching filter cake to a lithium bicarbonate leaching process section for leaching treatment, and controlling the solid-to-liquid ratio of the first leaching filter cake to the second part of the lithium-containing mother liquor to be 1: and 2-20, obtaining a third mixture after leaching treatment, and performing filter pressing treatment on the third mixture to separate a leachate containing lithium bicarbonate through filter pressing, wherein the leachate containing lithium bicarbonate comprises residual lithium hydroxide and lithium bicarbonate.
Specifically, the step of the leaching process in step S200 includes: leaching by means of a multi-stage semi-closed cycle, as an example and not by way of limitation, leaching by means of a two-stage semi-closed cycle, leaching by means of a three-stage semi-closed cycle or leaching by means of a two-stage semi-closed cycle; as a specific embodiment, two-stage semi-closed cycle leaching is adopted, wherein the first-stage carbonization leaching solution is recycled for 2-8 times, the first-stage lithium content is 6-9 g/L, the first-stage lithium leaching rate is 10-40%, the second-stage carbonization leaching solution is recycled for 15-30 times, the second-stage lithium content is 6-9 g/L, and the second-stage lithium leaching rate is 5-20%. After twice leaching in the lithium hydroxide process section, twice leaching in the lithium bicarbonate process section and four times of semi-closed-circuit leaching, the leaching rate of lithium is as high as more than 95%.
Specifically, the step of filter-pressing treatment in step S200 includes: the third mixture can be subjected to filter pressing by adopting an ultrafiltration membrane, and macromolecular substances and solid substances in the third mixture are intercepted, because LiHCO in the third mixture3Does not reach the solubility and does not retain LiHCO3. And (3) transferring the leachate containing the lithium bicarbonate out to a 2# buffer barrel at the front end of the neutralization lithium precipitation process section for later use.
Step S300, including:
the volume ratio of the lithium hydroxide leaching solution to the leaching solution containing lithium bicarbonate is 2.0-1.0: 1, carrying out neutralization and lithium precipitation reaction to generate lithium carbonate crystals and 2-4 g/L lithium-containing mother liquor.
The lithium-containing mother liquor is subjected to filter pressing treatment to remove suspended matters, colloids, large organic molecules, grease and the like, and then is returned to the lithium hydroxide leaching process section and the lithium bicarbonate leaching process section again, so that the water balance of a leaching system is realized.
After step S100, the method further includes:
in order to prevent the water quantity required for neutralizing the lithium hydroxide leachate and the leachate containing lithium bicarbonate from exceeding the neutralization matching range and break the water balance, lithium-rich treatment can be performed on one part of the lithium hydroxide leachate, the lithium-rich treatment mode can be distillation or reverse circulation, the lithium content can be enriched from 6-8 g/L to 10-15 g/L to form lithium-rich water, the lithium-rich water can be directly sold after being barreled, and the main component in the lithium-rich water is lithium hydroxide. As an embodiment, for example, the design value of the mass ratio of the water content in the leaching solution containing lithium bicarbonate to the water content in the leaching solution containing lithium hydroxide is 5: 4-8, and the actual production ratio can reach 5: 9-10, lithium enrichment treatment can be carried out on part of the lithium hydroxide leaching solution, and the water balance of the system is prevented from being damaged. The new water supply amount in the lithium extraction unit can be saved by more than 98 percent every year.
Step S400, including:
the flue gas purification unit 200 further comprises an intermediate product batching process section, and the filter pressing aqueous solution is reused in the intermediate product batching process section to form a water circulation of the flue gas purification unit 200, so that the fresh water supplement amount is saved, and no wastewater is discharged.
According to the method for recycling the water of the waste lithium ion battery, the lithium hydroxide and the lithium bicarbonate are leached by an acid-free leaching process, the leaching process is simple, a large amount of waste water can be avoided, the water circulation can be fully utilized, and the new water supplement amount can be greatly reduced every year.
The method for recycling the water of the waste lithium ion battery further comprises the following steps:
and an aqueous medium cooling unit 300 is adopted to cool the lithium leaching and extracting unit and the flue gas recovery unit. The water circulation and the water waste heat are fully utilized in the water medium cooling unit 300, and the effects of water saving and environmental protection are achieved.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents and improvements made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The utility model provides a retrieve old and useless lithium ion battery water cyclic utilization system which characterized in that includes: the lithium extraction unit comprises a lithium extraction leaching unit and a flue gas purification unit communicated with the lithium extraction leaching unit;
the lithium extraction unit is used for purifying and separating lithium ions and comprises a lithium bicarbonate leaching process section, a lithium hydroxide leaching process section, a neutralization lithium precipitation process section and a filter pressing purification process section, wherein the lithium bicarbonate leaching process section and the lithium hydroxide leaching process section are respectively communicated with the neutralization lithium precipitation process section, neutralization lithium precipitation reaction is carried out in the neutralization lithium precipitation process section to obtain lithium carbonate crystal precipitation liquid, then the lithium carbonate crystal precipitation liquid is subjected to filter pressing through the filter pressing purification process section to separate lithium-containing mother liquid, and the lithium-containing mother liquid is respectively conveyed to the lithium bicarbonate leaching process section, the lithium hydroxide leaching process section and the flue gas purification unit, wherein the lithium hydroxide leaching process section is used for reacting a first part of lithium-containing mother liquid to obtain a lithium hydroxide leaching liquid and a first leaching filter cake; the lithium bicarbonate leaching process section is used for reacting a second part of lithium-containing mother liquor to obtain a leaching solution containing lithium bicarbonate; the flue gas purification unit is used for purifying flue gas, recycling water vapor in the flue gas, leaching fluorine-containing compounds in the flue gas by using a third part of lithium-containing mother liquor,
the lithium bicarbonate leaching process section is used for introducing carbon dioxide into the lithium bicarbonate leaching process section to generate lithium bicarbonate through a carbonization reaction, wherein the carbonization temperature of the lithium bicarbonate leaching process section is 15-45 ℃, and the carbonization time is 1-5 h;
the lithium bicarbonate leaching process section is also used for performing leaching treatment and pressure filtration treatment on a second part of lithium-containing mother liquor and the first leaching filter cake to obtain a leaching solution containing lithium bicarbonate, and the solid-liquid mass ratio of the first leaching filter cake to the second part of lithium-containing mother liquor in the lithium bicarbonate leaching process section is 1: 2 to 20.
2. The system for recycling the recovered waste lithium ion battery water according to claim 1, further comprising an aqueous medium cooling unit for cooling the leaching lithium extraction unit and the flue gas purification unit.
3. The system for recycling recovered waste lithium ion battery water according to claim 1, wherein the leaching lithium extraction unit further comprises a lithium rich process section in communication with the lithium hydroxide leaching process section for increasing the lithium content.
4. The method for recycling the water of the recycled waste lithium ion battery adopts the system for recycling the water of the recycled waste lithium ion battery in claim 1, and is characterized by comprising the following steps of:
conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage to carry out hydration reaction and leaching treatment on the material containing lithium oxide, and leaching and separating out a lithium hydroxide leaching solution;
conveying the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process section to carry out carbonization reaction and leaching treatment on the material containing lithium carbonate, and leaching and separating to obtain a leaching solution containing lithium bicarbonate;
mixing the lithium hydroxide leachate and the leachate containing lithium bicarbonate to perform neutralization and lithium precipitation reaction, performing pressure filtration on a lithium carbonate crystal precipitation liquid obtained by the reaction to separate lithium-containing mother liquor and lithium carbonate, and recycling the lithium-containing mother liquor to a lithium hydroxide leaching process section and a lithium bicarbonate leaching process section;
and conveying the third part of the lithium-containing mother liquor to a flue gas purification unit to react with fluoride to generate a lithium fluoride aqueous solution, and performing filter pressing on the lithium fluoride aqueous solution to separate lithium fluoride and the filter pressing aqueous solution.
5. The method for recycling water in waste lithium ion batteries according to claim 4, wherein the step of delivering the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage for hydration and leaching of the material containing lithium oxide to separate a lithium hydroxide leachate comprises the steps of: and leaching the material containing lithium oxide by adopting multi-stage semi-closed cycle, wherein the lithium content of the lithium-containing mother liquor is 2-4 g/L, and the lithium content in the leached lithium hydroxide leachate is 8-12 g/L.
6. The method for recycling water in waste lithium ion batteries according to claim 4, wherein the step of delivering the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage for carrying out hydration reaction and leaching treatment on the material containing lithium oxide to leach and separate out the lithium hydroxide leachate comprises:
conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process section to perform ball milling on a material containing lithium oxide, generating lithium hydroxide through hydration reaction, leaching the lithium hydroxide, performing filter pressing after the leaching, and performing filter pressing to separate a lithium hydroxide leaching solution and a first leaching filter cake.
7. The method for recycling water in waste lithium ion batteries according to claim 6, wherein the step of delivering the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process stage for carrying out carbonization reaction and leaching treatment on a material containing lithium carbonate, and leaching and separating out a lithium bicarbonate leachate comprises:
introducing carbon dioxide into the lithium bicarbonate leaching process section to perform carbonization reaction to generate lithium bicarbonate, controlling the carbonization temperature to be 15-45 ℃ and the carbonization time to be 1-5 h;
respectively conveying the second part of the lithium-containing mother liquor and the first leached filter cake to a lithium bicarbonate leaching process section for leaching treatment, and controlling the solid-liquid mass ratio of the first leached filter cake to the second part of the lithium-containing mother liquor to be 1: and 2-20, performing filter pressing treatment after leaching treatment, and separating a leachate containing lithium bicarbonate through filter pressing.
8. The method for recycling water from waste lithium ion batteries according to claim 4, wherein the step of sending the second part of the lithium-containing mother liquor to a lithium bicarbonate leaching process stage for carbonizing a material containing lithium carbonate and leaching the material to separate a leachate containing lithium bicarbonate comprises the steps of:
and leaching the material containing lithium carbonate by adopting multi-stage semi-closed cycle leaching, wherein the lithium content of the lithium-containing mother liquor is 2-4 g/L, and the lithium content of the leached leaching solution containing lithium bicarbonate is 6-9 g/L.
9. The method for recycling the water in the waste lithium ion batteries according to claim 4, wherein in the step of mixing the lithium hydroxide leachate with the leachate containing lithium bicarbonate to perform neutralization and lithium precipitation reaction, and performing pressure filtration on the mixture obtained by the reaction to separate lithium-containing mother liquor and lithium carbonate, the volume ratio of the lithium hydroxide leachate to the leachate containing lithium bicarbonate is 2.0-1.0: 1, carrying out neutralization and lithium precipitation reaction.
10. The method for recycling water from waste lithium ion batteries according to claim 4, wherein the step of conveying the first part of the lithium-containing mother liquor to a lithium hydroxide leaching process stage for carrying out hydration reaction and leaching treatment on the material containing lithium oxide, and after leaching and separating out the lithium hydroxide leachate, further comprises:
and (3) carrying out lithium enrichment treatment on a part of the lithium hydroxide leaching solution.
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| CN106315629B (en) * | 2016-08-30 | 2018-01-30 | 山东瑞福锂业有限公司 | A kind of technique for preparing pure Lithium Carbonate using battery-level lithium carbonate sinker disposing mother liquor |
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| KR101839460B1 (en) * | 2017-10-24 | 2018-03-16 | 성일하이텍㈜ | High-purity lithium carbonate recovery method from solution Containing Lithium |
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| JP2004196606A (en) * | 2002-12-19 | 2004-07-15 | Nippon Chem Ind Co Ltd | Method for manufacturing high purity lithium carbonate |
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Denomination of invention: A water recycling system and method for recycling waste lithium-ion batteries Effective date of registration: 20231212 Granted publication date: 20220322 Pledgee: Bank of Changsha Co.,Ltd. Zhuzhou branch Pledgor: Hunan Kaidi Zhongneng Technology Co.,Ltd. Registration number: Y2023980071155 |