CN113046576A - High-purity lithium, extraction method and application of high-purity lithium - Google Patents
High-purity lithium, extraction method and application of high-purity lithium Download PDFInfo
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- CN113046576A CN113046576A CN202110277240.6A CN202110277240A CN113046576A CN 113046576 A CN113046576 A CN 113046576A CN 202110277240 A CN202110277240 A CN 202110277240A CN 113046576 A CN113046576 A CN 113046576A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 159
- 238000000605 extraction Methods 0.000 title claims abstract description 78
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000002699 waste material Substances 0.000 claims abstract description 45
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 7
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Secondary Cells (AREA)
Abstract
High-purity lithium and an extraction method and application of the high-purity lithium comprise the following steps: adding water into the waste powder of the lithium iron phosphate battery to prepare slurry, adding acid and an oxidant to react, and filtering to obtain lithium-containing filtrate and waste residue; adding a chloride solution into the lithium-containing filtrate to obtain a mixed solution, extracting lithium in the mixed solution by using an extracting agent to obtain a back-extracted lithium solution, and evaporating acid and water from the back-extracted lithium solution to prepare high-purity lithium chloride; the method has the advantages of simple process, low cost, high lithium recovery rate and high lithium product purity, and is favorable for promoting the recovery of the lithium iron phosphate battery waste.
Description
Technical Field
The invention relates to the technical field of high-purity lithium extraction, and particularly relates to high-purity lithium, an extraction method of the high-purity lithium and application of the high-purity lithium.
Background
With the rapid development of new energy industry, lithium iron phosphate batteries are being vigorously developed due to the advantages of high working voltage, high energy density, good safety performance, no memory effect and the like. However, the development and utilization of lithium ore resources are gradually limited due to the fact that a large amount of waste batteries reach the scrapping time limit, and the problems that the waste lithium iron phosphate batteries are reasonably recycled and the lithium resources are efficiently recycled are imminent.
At present, the general processing flow of the waste lithium iron phosphate battery is to obtain anode powder through discharging and disassembling, utilize acid dissolution and simultaneously add an oxidant to separate iron phosphate and lithium, and add sodium carbonate to the obtained lithium-containing filtrate to precipitate lithium carbonate (CN103280610A, CN 111206161A). However, the lithium precipitation method by sodium carbonate generally has a lithium precipitation rate of only 80% at one time, and the lithium precipitation mother liquor needs to be recycled for many times, so that the comprehensive recovery rate of lithium can be ensured to be more than 99%, and the product purity cannot be simply improved to a battery level due to the existence of sodium.
The extraction method for extracting lithium is a mature process at present, and the recovery rate and the extraction rate of lithium can reach more than 99 percent by adjusting system parameters. The invention adopts a TBP extraction system (CN1005145B) proposed by Qinghai salt lake research of Chinese academy of sciences, wherein kerosene is used as a diluent, TBP is used as an extraction agent, ferric chloride is used as a co-extraction agent to form LiFeCl4 ferric complex acid salt, the extraction system has attracted extensive attention in the past decades, and is always used for extracting lithium from salt lake brine, and through the improvement of the process, the extraction system can stably run in the long-term use process, and an organic phase can be recycled for a long time (CN111793755A), but the research of applying the extraction system to the lithium extraction from the iron phosphate lithium battery waste at present is relatively less. The university of Zhongnan utilizes the system to process simulated ternary material leachate, the lithium extraction rate can reach 99% but the product purity is unknown (Zhao Tian Yu, non-ferrous metal science and engineering, 2019). Although southwest traffic university utilizes the system to treat lithium iron phosphate battery waste, the lithium recovery rate is only 85%, and no treatment measures are mentioned in the text, such as lithium product purity, a large amount of acid-base wastewater produced in the system, and the like, and the cost is high (Wangzhibo, southwest traffic university, 2019). In addition, an efficient centrifugal extractor (CN110876857A) is selected as extraction equipment, so that the dosage of an extracting agent can be obviously reduced, the occupied area is reduced, and the resource loss is reduced. In summary, the centrifugal extraction machine is used as equipment, and the recovery of lithium in the waste lithium iron phosphate batteries by the extraction method is beneficial to improving the situation of the recovery method of the waste lithium iron phosphate batteries and the shortage of the equipment.
Disclosure of Invention
In order to solve the technical problems, the invention provides high-purity lithium, an extraction method and application of the high-purity lithium, the process is simple, the cost is low, the lithium recovery rate is high, the lithium product purity is high, and the recovery of lithium iron phosphate battery waste is facilitated.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for extracting high-purity lithium comprises the following steps:
adding water into the waste powder of the lithium iron phosphate battery to prepare slurry, adding acid and an oxidant to react, and filtering to obtain lithium-containing filtrate and waste residue; adding a chloride solution into the lithium-containing filtrate to obtain a lithium-containing mixed solution, extracting lithium in the lithium-containing mixed solution by using an extracting agent to obtain a back-extracted lithium solution, and evaporating acid and water from the back-extracted lithium solution to prepare high-purity lithium chloride.
The invention provides a method for extracting high-purity lithium, which has the advantages of simple process, low cost, high lithium recovery rate and high lithium product purity, and is beneficial to promoting the recovery of lithium iron phosphate battery waste.
Further, adding water into the lithium iron phosphate battery waste powder at the temperature of 25-100 ℃ for slurrying, adding acid and an oxidant, reacting for 2-5h under the temperature of 25-100 ℃, and filtering to obtain lithium-containing filtrate and waste residue.
Further, the acid is concentrated hydrochloric acid.
Further, H in acid+With Li in the lithium iron phosphate waste+The molar ratio is 0.5-3: 1.
Further, the oxidant is one or more of sodium chlorate, sodium hypochlorite or hydrogen peroxide.
Further, the molar ratio of the oxidant to lithium ions in the lithium iron phosphate is 0.5-3: 1.
Further, the lithium-containing filtrate and the chloride salt solution are proportioned to form a mixed solution, and the concentration of chloride ions in the mixed solution is more than or equal to 6M.
Further, the chloride salt is one or more of magnesium chloride, sodium chloride or potassium chloride.
Further, the extracting agent comprises 50-100% of tributyl phosphate, 0-50% of kerosene and ferric trichloride according to volume fraction, and the mass concentration of the ferric trichloride is 0.2-0.5 mol/L.
Further, the lithium stripping solution comprises: hydrochloric acid and lithium chloride.
Further, acid and water generated by evaporating the lithium stripping solution can be recycled in the steps of the extraction method of high-purity lithium.
Further, the extracting agent can circularly extract lithium in the mixed solution after the processes of extraction, washing, back extraction and water washing.
Further, after the extractant extracts lithium in the lithium-containing mixed solution to obtain a lithium back-extraction solution, and when an extractant residual solution still remains, the extractant residual solution is concentrated to obtain a concentrated solution and water, and the concentrated solution is mixed with a chloride solution to be used for preparing the lithium-containing mixed solution in a recycling manner.
Furthermore, the concentration of chloride ions in the concentrated solution is more than or equal to 8M.
The invention also provides application of the extraction method of any high-purity lithium as the waste recovery of the lithium iron phosphate battery.
The invention also provides high-purity lithium which is prepared by any one of the extraction methods of the high-purity lithium.
The invention provides high-purity lithium and an extraction method and application of the high-purity lithium, and the extraction method has the following beneficial effects:
1) the invention provides a method for extracting high-purity lithium and application thereof, and the method abandons the conventional scheme of precipitating lithium by sodium carbonate in the process of recovering lithium iron phosphate battery waste, adopts a high-efficiency extraction system, can greatly improve the recovery rate of lithium, can directly obtain a high-purity lithium product with the purity of more than 99 percent, does not contain other metal ions, and has considerable economic value;
2) the invention provides high-purity lithium and an extraction method and application of the high-purity lithium, wherein the extraction agent residual liquid, the evaporated acid, the evaporated water and the extraction agent in an extraction system can be recycled, so that the discharge of hazardous wastes is reduced, and the method is economic and environment-friendly;
3) the invention provides high-purity lithium and an extraction method and application of the high-purity lithium, and a high-efficiency centrifugal extractor is used as extraction equipment for extracting lithium from lithium iron phosphate battery waste, so that the using amount of an extracting agent can be obviously reduced, the occupied area is reduced, and the resource loss is reduced.
Drawings
FIG. 1 is a flow chart of a method for extracting high purity lithium according to the present invention.
Detailed Description
In order to better understand the purpose, structure and function of the present invention, the following describes a method for extracting high purity lithium and its application in further detail with reference to the accompanying drawings.
As shown in fig. 1, a method for extracting high purity lithium includes the following steps:
s1, slurrying, namely adding water into the waste powder of the lithium iron phosphate battery at the temperature of 25-100 ℃ to slurry;
s2 leaching, adding a proper amount of acid and oxidant, maintaining the temperature, reacting for 2-5h, leaching to obtain a lithium-containing filtrate and a waste residue mixed solution,
s3, filtering, namely filtering the lithium-containing filtrate and the waste residue mixed solution to obtain lithium-containing filtrate and waste residue;
s4 preparing lithium-containing mixed solution, mixing the lithium-containing filtrate with chloride solution to form lithium-containing mixed solution,
s5, extracting, namely extracting lithium in the lithium-containing mixed solution by using an extracting agent to obtain a back-extraction lithium solution;
s6, circularly obtaining an extracting agent, wherein the extracting agent can circularly extract lithium in the mixed solution to obtain a lithium stripping solution after the processes of extraction, washing, stripping and washing;
s7, evaporating acid and water, and evaporating acid and water to obtain the back extraction lithium solution to obtain the high-purity lithium chloride.
The acid in step S2 is concentrated hydrochloric acid, H in the acid+With Li in the lithium iron phosphate waste+The molar ratio is 0.5-3:1, the oxidant is one or more of sodium chlorate, sodium hypochlorite or hydrogen peroxide, and the molar ratio of the oxidant to lithium ions in the lithium iron phosphate is 0.5-3: 1.
Step S4, mixing the lithium-containing filtrate with a chloride solution to form a mixed solution, wherein the concentration of chloride ions in the mixed solution is more than or equal to 6M; the chloride salt is one or more of magnesium chloride, sodium chloride or potassium chloride.
In the step S5, the extractant is composed of 50-100% of tributyl phosphate, 0-50% of kerosene and ferric trichloride according to volume fraction, and the mass concentration of the ferric trichloride is 0.2-0.5 mol/L.
The lithium stripping solution in the step S7 is composed of hydrochloric acid and lithium chloride; and (3) the evaporated water of the lithium back-extraction solution can be circularly added into the step S1 to carry out slurrying on the lithium iron phosphate battery waste powder, and the evaporated acid of the lithium back-extraction solution can be circularly added into the oxidant added in the step S2 to react and leach the lithium-containing filtrate and waste residue mixed solution.
When the extractant in the step S6 extracts lithium in the lithium-containing mixed solution and after the obtained lithium back-extraction solution, an extractant residual solution remains, the extractant residual solution is concentrated to obtain a concentrated solution and water, the concentration of chloride ions in the concentrated solution is greater than or equal to 8M, the concentrated solution can be mixed with a chloride salt solution to participate in the reaction in the step S4 in a circulating manner to prepare a lithium-containing mixed solution, and the water can be used in the slurrying reaction in the step S1 in a circulating manner.
Example 1
A method for extracting high-purity lithium comprises the following steps:
1kg of lithium iron phosphate battery waste powder (containing 3.51% of lithium) is added with 4L of water for slurrying at the temperature of 25 ℃, 500mL of concentrated hydrochloric acid and 500mL of hydrogen peroxide are added for reaction for 2 hours, and lithium-containing filtrate and waste residue are obtained by filtering; mixing the lithium-containing filtrate with a 4M magnesium chloride solution to form a mixed solution, wherein the mixed solution contains 6M chloride ions; extracting lithium in the mixed solution by taking a high-efficiency centrifugal extractor as extraction equipment, specifically extracting the lithium in the mixed solution by using an extracting agent, evaporating acid and water to obtain a back-extraction lithium solution to prepare high-purity lithium chloride, circularly adding the evaporated water of the back-extraction lithium solution into waste powder of a lithium iron phosphate battery for slurrying, and circularly adding the evaporated acid of the back-extraction lithium solution into a cooperatively added oxidant to leach a lithium-containing filtrate and waste residue mixed solution; concentrating the residual liquid of the extracting agent, mixing the concentrated residual liquid with a chloride solution, and further preparing a lithium-containing mixed solution to continuously participate in extraction; the extractant is recycled. The purity of the obtained lithium chloride reaches 99.5 percent, and the concentration of lithium in the residual water after extraction is lower than 5 x 10^-3M, the extraction rate of lithium is higher than 99.5%.
In this example 1, the extraction system comprises: extraction 4 grades, washing 4 grades, back extraction 4 grades, washing 4 grades, adopt multistage countercurrent mode operation, promptly: the moving direction of the feed liquid is opposite to that of the extracting agent, the extracting agent is added from the last stage and then is used as the extracting agent of the previous stage, and the countercurrent extraction is carried out step by step according to the rule. The extractant comprises 70 percent of tributyl phosphate, 30 percent of kerosene and 0.3mol/L of ferric chloride according to volume fraction.
Example 2
A method for extracting high-purity lithium comprises the following steps:
1kg of lithium iron phosphate battery waste powder (containing 3.78% of lithium) is added with 3L of water for slurrying at 50 ℃, 700mL of concentrated hydrochloric acid and 2L of sodium hypochlorite are added for reaction for 5 hours, and lithium-containing filtrate and waste residue are obtained by filtering; mixing the lithium-containing filtrate with 8M potassium chloride solution to form a mixed solution, wherein the mixed solution contains 7M chloride ions; extracting lithium in the mixed solution by taking a high-efficiency centrifugal extractor as extraction equipment, specifically extracting the lithium in the mixed solution by using an extracting agent, evaporating acid and water to obtain a back-extraction lithium solution to prepare high-purity lithium chloride, circularly adding the evaporated water of the back-extraction lithium solution into waste powder of a lithium iron phosphate battery for slurrying, and circularly adding the evaporated acid of the back-extraction lithium solution into a cooperatively added oxidant to leach a lithium-containing filtrate and waste residue mixed solution; concentrating the extraction residual liquid, mixing the concentrated extraction residual liquid with a chloride solution, and further preparing a lithium-containing mixed solution to continuously participate in extraction; the extractant is recycled. The purity of the obtained lithium chloride reaches 99.8 percent, and the concentration of lithium in the residual water after extraction is lower than 10^-4M, the extraction rate of lithium is higher than 99.9%.
In this example 2, the extraction system comprises: extraction 6 grades, washing 9 grades, stripping 6 grades, washing 4 grades, adopt multistage countercurrent mode operation, promptly: the moving direction of the feed liquid is opposite to that of the extracting agent, the extracting agent is added from the last stage and then is used as the extracting agent of the previous stage, and the countercurrent extraction is carried out step by step according to the rule. The extractant comprises 75 percent of tributyl phosphate, 25 percent of kerosene and 0.35mol/L of ferric chloride according to volume fraction.
Example 3
A method for selectively extracting high-purity lithium from lithium iron phosphate battery waste comprises the following steps:
1kg of lithium iron phosphate battery waste powder (containing 3.67 percent of lithium) is added with 5L of water for slurrying at the temperature of 100 ℃, 500mL of concentrated hydrochloric acid and 600mL of sodium chlorate are added for reaction for 4 hours, and lithium-containing filtrate and waste residue are obtained by filtering; mixing the lithium-containing filtrate with a 6M sodium chloride solution to form a mixed solution, wherein the mixed solution contains 5M chloride ions; extracting lithium in the mixed solution by taking a high-efficiency centrifugal extractor as extraction equipment, specifically extracting the lithium in the mixed solution by using an extracting agent, evaporating acid and water to obtain a back-extraction lithium solution to prepare high-purity lithium chloride, circularly adding the evaporated water of the back-extraction lithium solution into waste powder of a lithium iron phosphate battery for slurrying, and circularly adding the evaporated acid of the back-extraction lithium solution into a cooperatively added oxidant to leach a lithium-containing filtrate and waste residue mixed solution; concentrating the extraction residual liquid, mixing the concentrated extraction residual liquid with a chloride solution, and further preparing a lithium-containing mixed solution to continuously participate in extraction; the extractant is recycled. The purity of the obtained lithium chloride reaches 99.6 percent, and the concentration of lithium in the extraction residual water is lower than 3 x 10^-3M, the extraction rate of lithium is higher than 99.8%.
In this example 3, the extraction system comprises: extraction 5 grades, washing 4 grades, stripping 5 grades, washing 4 grades, adopt multistage countercurrent mode operation, promptly: the moving direction of the feed liquid is opposite to that of the extracting agent, the extracting agent is added from the last stage and then is used as the extracting agent of the previous stage, and the countercurrent extraction is carried out step by step according to the rule. The extractant composition comprises the following components in percentage by volume: 65% of tributyl phosphate, 35% of kerosene and 0.4mol/L of ferric chloride.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all modifications and equivalents falling within the scope of the appended claims. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The method for extracting high-purity lithium is characterized by comprising the following steps of:
adding water into the waste powder of the lithium iron phosphate battery to prepare slurry, adding acid and an oxidant to react, and filtering to obtain lithium-containing filtrate and waste residue; adding a chloride solution into the lithium-containing filtrate to obtain a lithium-containing mixed solution, extracting lithium in the lithium-containing mixed solution by using an extracting agent to obtain a back-extracted lithium solution, and evaporating acid and water from the back-extracted lithium solution to prepare high-purity lithium chloride.
2. The method for extracting high-purity lithium according to claim 1, wherein the lithium iron phosphate battery waste powder is slurried with water at 25-100 ℃, added with acid and oxidant, kept at 25-100 ℃, reacted for 2-5h, and filtered to obtain lithium-containing filtrate and waste residue.
3. The method for extracting high-purity lithium according to claim 1, wherein the acid is concentrated hydrochloric acid, and the oxidant is one or more of sodium chlorate, sodium hypochlorite and hydrogen peroxide.
4. The method for extracting high-purity lithium as claimed in claim 3, wherein H is contained in acid+With Li in the lithium iron phosphate waste+The molar ratio is 0.5-3:1, and the molar ratio of the oxidant to lithium ions in the lithium iron phosphate is 0.5-3: 1.
5. The method for extracting high-purity lithium according to claim 1, wherein the lithium-containing filtrate and the chloride solution are proportioned to form a mixed solution, the concentration of chloride ions in the mixed solution is more than or equal to 6M, and the chloride is one or more of magnesium chloride, sodium chloride or potassium chloride.
6. The method for extracting high-purity lithium according to claim 1, wherein the extractant comprises, in terms of volume fraction: 50-100% of tributyl phosphate, 0-50% of kerosene and ferric trichloride, wherein the mass concentration of the ferric trichloride is 0.2-0.5 mol/L.
7. The method for extracting high-purity lithium according to claim 1, wherein the lithium stripping solution comprises: hydrochloric acid and lithium chloride, and the acid and water obtained by evaporating the lithium stripping solution can be recycled in the step of the extraction method of high-purity lithium.
8. The method for extracting high-purity lithium according to claim 1, wherein the extractant is capable of circularly extracting lithium in the mixed solution after the processes of extraction, washing, back extraction and water washing.
9. Use of the method for extracting high purity lithium according to any one of claims 1 to 8 as a waste material for lithium iron phosphate batteries.
10. High purity lithium, characterized in that it is produced according to the extraction process of high purity lithium according to any one of claims 1 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109921087A (en) * | 2019-01-29 | 2019-06-21 | 深圳市泰力废旧电池回收技术有限公司 | A kind of integrated conduct method of waste lithium iron phosphate battery |
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| CN107069132A (en) * | 2016-12-19 | 2017-08-18 | 天齐锂业股份有限公司 | A kind of method for reclaiming waste lithium iron phosphate positive electrode |
| WO2018192122A1 (en) * | 2017-04-18 | 2018-10-25 | 中科过程（北京）科技有限公司 | Method for mixed acid leaching and recovery of positive electrode materials of waste lithium ion batteries |
| CN109536741A (en) * | 2017-12-16 | 2019-03-29 | 虔东稀土集团股份有限公司 | A kind of extracting process of elemental lithium |
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| CN107069132A (en) * | 2016-12-19 | 2017-08-18 | 天齐锂业股份有限公司 | A kind of method for reclaiming waste lithium iron phosphate positive electrode |
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