WO2021083263A1 - 一种萃取-反萃分离纯化提取锂的方法 - Google Patents

一种萃取-反萃分离纯化提取锂的方法 Download PDF

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WO2021083263A1
WO2021083263A1 PCT/CN2020/124747 CN2020124747W WO2021083263A1 WO 2021083263 A1 WO2021083263 A1 WO 2021083263A1 CN 2020124747 W CN2020124747 W CN 2020124747W WO 2021083263 A1 WO2021083263 A1 WO 2021083263A1
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lithium
liquid
extraction
phase
gas
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French (fr)
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齐涛
朱兆武
张健
林道勇
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中国科学院过程工程研究所
意定(上海)信息科技有限公司
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Priority to KR1020227017474A priority Critical patent/KR20220085822A/ko
Priority to US17/773,593 priority patent/US20220372592A1/en
Priority to AU2020374016A priority patent/AU2020374016B2/en
Priority to JP2022525618A priority patent/JP2023500313A/ja
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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/30—Oximes
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/32—Carboxylic acids
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/37—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing boron, silicon, selenium or tellurium
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/382—Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • 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
    • 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

Definitions

  • the invention relates to the technical field of chemical separation, in particular to a method for extraction-reverse extraction, separation, purification, and extraction of lithium.
  • Lithium is the metal with the smallest density and is widely used in electronics, chemistry, new energy, pharmaceuticals and other fields. Lithium resources are mainly derived from salt lakes, minerals and seawater. With the advancement of the reuse of waste resources in recent years, used lithium batteries have also become Important source. The process of extracting lithium from these raw materials requires multiple purification steps. In the classic process, evaporation and concentration, separation and removal of impurities, deep removal of calcium and magnesium ions are used to obtain a high-purity lithium-containing solution, and then the lithium-containing solution is subjected to precipitation treatment. The lithium carbonate product is obtained.
  • CN108423696A discloses a method for extracting high-purity lithium salt from a lithium-containing solution, which includes the following steps: adding a pH regulator to the lithium-containing solution, adjusting the pH of the solution to be greater than 4; concentrating the lithium-containing solution to a lithium concentration greater than 2g /L of lithium-rich solution; put the ultrasonic device into the lithium-rich solution, add precipitant, and ultrasonically vibrate; filter after the ultrasonic wave, wash and dry the obtained solid phase to obtain a lithium salt.
  • This method needs to concentrate the lithium-containing solution, and the processing volume is small; at the same time, in the process of precipitating lithium, because the lithium-rich solution contains a large amount of sodium and potassium ions, the amount of entrainment in the lithium salt is large, which affects its purity, and prepares higher-purity lithium Salt needs a lot of fresh water to wash, and water consumption is large.
  • the lithium salt has a certain solubility in the water phase, and the mother liquor after precipitation still contains a large amount of lithium, which causes the yield of lithium to decrease.
  • CN104884648A provides a method for extracting lithium from a lithium-containing solution, which specifically includes the following steps: preparing a lithium-containing solution containing carbonate ions; concentrating the lithium-containing solution to a lithium concentration of less than or equal to 2.481 g/L to obtain the first A precipitate; solid-liquid separation of the concentrated lithium-containing solution and the first precipitate; adding a phosphorus supply substance to the concentrated lithium-containing solution to precipitate the dissolved lithium as lithium phosphate; The filtered solution of lithium phosphate is concentrated again to a lithium concentration of less than or equal to 2.481 g/L to obtain a second precipitate; the filtered solution and the second precipitate that are concentrated again are subjected to solid-liquid separation; and Core particles are added to the concentrated filtered solution to precipitate the dissolved lithium as lithium phosphate.
  • the method performs concentration and solid-liquid separation many times, the yield of lithium is low, the process flow is long, and the investment is large, which is not conducive to industrial application.
  • the present invention provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium.
  • the method uses an extraction system containing a composite extractant to extract a lithium-containing solution under high pH conditions. , Realizes the high-efficiency extraction of lithium, and separates it from a large amount of impurity elements such as Na, K, and B; then uses industrial exhaust gas to perform gas-liquid-liquid three-phase reverse extraction through a multi-stage continuous countercurrent process to achieve high-efficiency lithium Back extraction.
  • the method provided by the present invention has large processing capacity, liquid phase recycling, and high total lithium yield; vapor phase recycling achieves zero emission and high utilization rate; industrial tail gas can be used as a three-phase extraction gas source, the cost is greatly reduced, and the environment is protected; At the same time, the process flow is short, the equipment is simple, the investment is small, and it is easy for industrial application.
  • the present invention adopts the following technical solutions:
  • the present invention provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium, which includes the following steps:
  • step (1) The lithium-loaded organic phase obtained in step (1) is subjected to gas-liquid-liquid three-phase reverse extraction to obtain a lithium-loaded stripping solution;
  • step (3) The stripping liquid obtained in step (2) is heat-treated and separated to obtain a lithium product and a separated mother liquor.
  • the composite extraction agent in step (1) includes a neutral extraction agent and a chelating extraction agent
  • the extraction system includes the composite extraction agent and a diluent.
  • the neutral extractant comprises tributyl phosphate TBP, dimethylheptyl methyl phosphate P350, trioctyl phosphine oxide TOPO, trioctyl/hexyl phosphine oxide Cyanex923 and N,N two-(1- Any one or a combination of at least two of methylheptyl)acetamide N503.
  • the chelating extractant comprises 2-hydroxy-5-nonylacetophenone oxime LIX84, dodecylphenyl-methyl- ⁇ -diketone LIX54, 2-hydroxy-5-nonylbenzaldehyde Oxime LIX860 and the same functional group as 2-hydroxy-5-nonylacetophenone oxime LIX84, dodecylphenyl-methyl- ⁇ -diketone LIX54, 2-hydroxy-5-nonylbenzaldehyde oxime LIX860 Any one or a combination of at least two of the extractants.
  • the volume ratio of the neutral extractant to the chelating extractant is 0.2:1 to 2:1.
  • the extraction system further includes a phase modifier.
  • the extraction system comprises a composite extractant, a phase modifier and a diluent; the volume percentage of the composite extractant in the extraction system is 5-30%, and the volume percentage of the phase modifier is 0-10%.
  • the lithium-containing solution in step (1) includes any one or a combination of at least two of lithium ore leachate, lithium precipitation mother liquor, lithium battery waste leachate, and salt lake brine.
  • the concentration of lithium in the lithium-containing solution is 0.25-5 g/L.
  • the concentrations of the main impurity elements sodium, potassium and boron in the lithium-containing solution are independently 10-150 g/L, 0-50 g/L and 0-10 g/L, respectively.
  • the lithium-containing solution also contains metal ions such as rubidium, aluminum, magnesium, cesium, and calcium.
  • the volume ratio of the lithium-containing solution to the organic phase of the extraction system is 0.2:1 to 5:1.
  • the concentration of lithium in the lithium-supporting organic phase in step (1) is 0.5-3 g/L.
  • step (1) further includes washing the lithium-supported organic phase.
  • the washing liquid is water and/or a lithium-containing solution.
  • the gas-liquid-liquid three-phase reverse extraction system in step (2) comprises a first liquid phase, a second liquid phase and a gas phase.
  • the gas in the gas phase contains any one or a combination of at least two of SO 2 , SO 3 , CO 2 or Cl 2.
  • the gas in the gas phase is SO 2 and/or CO 2 .
  • the first liquid phase contains water.
  • the second liquid phase comprises a lithium-supported organic phase.
  • the volume ratio of the first liquid phase to the second liquid phase is 0.05:1 to 2:1.
  • the gas-liquid-liquid three-phase reverse extraction in step (2) adopts a multi-stage continuous countercurrent operation.
  • the gas-liquid-liquid three-phase reverse extraction equipment includes any one of a continuous mixing and clarification tank, an extraction tower or a centrifugal extractor; the number of stages of the gas-liquid-liquid three-phase reverse extraction is 1-10 Adjustable between levels.
  • the concentration of lithium in the stripping solution in step (2) is >5 g/L.
  • the heat treatment method in step (3) includes any one or a combination of at least two of oxidation, evaporative crystallization or thermal decomposition.
  • the temperature of the heat treatment is 60-90°C.
  • the heat treatment time is 0.5-2h.
  • the oxidant used in the oxidation is air, oxygen and ozone gas.
  • the evaporation crystallization adopts MVR or multi-effect evaporation.
  • the thermal decomposition adopts a closed or semi-closed container.
  • the method of separation in step (3) includes any one or a combination of at least two of filtration, suction filtration or centrifugation.
  • the lithium product is lithium sulfate, lithium chloride or lithium carbonate, and the product purity is >96%.
  • the mother liquor separated in step (3) is returned to step (1) and/or returned to the first liquid phase of step (2).
  • the method of extraction-reverse extraction provided by the present invention for separation, purification and extraction of lithium realizes the high-efficiency separation of lithium from impurity ions such as Na, K, and B by using a composite extractant, and then continuous gas-liquid-liquid three-phase continuous back-extraction ,
  • the back extraction rate of lithium is more than 90%, to realize the recycling of liquid and gas phase, the total yield of lithium is more than 83%, and the purity of the obtained lithium product is more than 96%;
  • the method provided by the present invention has large processing capacity, simple process and equipment, small investment, low energy consumption, can realize continuous production, and has high application value.
  • Figure 1 is a process flow diagram of the extraction-reverse extraction separation, purification, and extraction of lithium provided by the present invention
  • FIG 2 is a schematic diagram of the gas-liquid-liquid three-phase reverse extraction equipment provided by the present invention.
  • 1 is an electric stirrer
  • 2 is a gas outlet
  • 3 is a light phase outlet
  • 4 is a stirring tray
  • 5 is an extraction tower Body
  • 6 is a gas distributor
  • 7 is a gas inlet
  • 8 is a heavy phase outlet
  • 9 is a heavy phase inlet
  • 10 is a light phase inlet
  • 11 is a pulse system.
  • the present invention provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium, which includes the following steps:
  • step (2) subjecting the lithium-loaded organic phase obtained in step (1) to gas-liquid-liquid three-phase reverse extraction to obtain a lithium-loaded stripping solution;
  • step (3) The stripping liquid obtained in step (2) is heat-treated and separated to obtain a lithium product and a separated mother liquor.
  • the method provided by the present invention uses an extraction system containing a composite extractant. Under higher pH conditions, lithium is effectively extracted by the composite extractant and enters the loaded organic phase; then the lithium-loaded organic phase passes through the gas-liquid-liquid three
  • acid gas is used as the gas phase.
  • the gas can provide a small amount of H + when dissolved in the liquid phase.
  • the H + contacts with the organic phase loaded with lithium and exchanges with Li + .
  • Li + is back-extracted into the aqueous solution and consumed
  • the H + is replenished through continuous gas reaction, and the Li + back-extracted to the water phase is combined with the anions produced by the gas-liquid reaction to form a lithium-loaded aqueous solution; then heat treatment is performed to obtain a lithium product with higher purity.
  • the composite extraction agent in step (1) includes a neutral extraction agent and a chelating extraction agent
  • the extraction system includes the composite extraction agent and a diluent.
  • the extraction reaction is shown in formula (1):
  • L is Cl - or SO 4 2-; E N neutral extracting agent, HE Ch chelating extractant.
  • the pH is less than 10
  • the inclusion of lithium in the extraction process and the H + produced by HE Ch cannot be effectively neutralized, and lithium cannot be effectively extracted.
  • the pH> 13 the large amount of Na + and K + and the like are also formed NaE Ch HE Ch or KE Ch, lithium can not be efficiently extracted, and Na and K can not be well separated.
  • the neutral extractant comprises tributyl phosphate (TBP), dimethylheptyl methyl phosphate (P350), trioctyl phosphine oxide (TOPO), trioctyl/hexyl phosphine oxide (Cyanex923) and Any one or a combination of at least two of N,N bis-(1-methylheptyl)acetamide (N503), including typical but non-limiting combinations: P350 and N503, TBP and TOPO, TBP, P350 and Cyanex923, P350, Cyanex923 and N503.
  • the chelating extraction agent comprises 2-hydroxy-5-nonylacetophenone oxime (LIX84), dodecylphenyl-methyl- ⁇ -diketone (LIX54), 2-hydroxy-5- Nonylbenzaldehyde oxime (LIX860) and 2-hydroxy-5-nonylacetophenone oxime (LIX84), dodecylphenyl-methyl- ⁇ -diketone (LIX54), 2-hydroxy-5- Nonylbenzaldehyde oxime (LIX860) has any one or a combination of at least two of the extractants with the same functional group, among which typical but non-limiting combinations: LIX54 and LIX84I, LIX54 and LIX860, LIX54, LIX84I and LIX860.
  • the volume ratio of the neutral extractant to the chelating extractant is 0.2:1 to 2:1, for example, it can be 0.2:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.2 :1, 1.5:1, 1.8:1 or 2:1, etc.
  • the extraction system further includes a phase modifier.
  • the extraction system comprises a composite extractant, a phase modifier and a diluent, wherein the volume percentages of the composite extractant and the phase modifier are independently 5-30% and 0-10%, respectively.
  • the volume percentage of the composite extractant can be 5%, 10%, 15%, 20%, 25% or 30%, etc.
  • the volume percentage of the phase modifier can be 0%, 0.5%, 1%, 3%, 5 %, 8%, 9% or 10%, etc.
  • the phase modifier determines whether to add and the volume ratio of addition according to whether the extraction system has "emulsification" problems.
  • the specific types of diluents and phase modifiers are not particularly limited, as long as they are commonly used by those skilled in the art, they are all applicable to the present invention.
  • the diluent is n-dodecane or sulfonated kerosene
  • the phase modifier is dodecanol.
  • the lithium-containing solution in step (1) includes any one or a combination of at least two of lithium ore leachate, lithium precipitation mother liquor, lithium battery waste leachate, and salt lake brine, wherein a typical but non-limiting combination: lithium Ore leachate and lithium sinking mother liquor, salt lake brine, salt lake brine and lithium sinking mother liquor, lithium battery waste leachate, lithium battery waste leachate and lithium sinking mother liquor, etc.
  • the concentration of lithium in the lithium-containing solution is 0.25 to 5 g/L, for example, 0.25 g/L, 0.3 g/L, 0.5 g/L, 0.8 g/L, 1 g/L, 1.5 g/L , 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, 4.8g/L or 5g/L etc.
  • the concentration of the main impurity elements sodium, potassium and boron in the lithium-containing solution are independently 10 to 150 g/L, 0 to 50 g/L and 0 to 10 g/L, for example, the concentration of sodium may be 10 g/L.
  • potassium concentration It can be 0g/L, 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L, 45g/L or 50g/L, etc.; the concentration of boron can be 0g/L L, 1g/L, 2g/L, 3g/L, 5g/L, 7g/L, 9g/L or 10g/L, etc.
  • the lithium-containing solution also contains metal ions such as rubidium, aluminum, magnesium, cesium, and calcium.
  • the volume ratio of the lithium-containing solution to the organic phase is 0.2:1 to 5:1, for example, it may be 0.2:1, 0.3:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1 or 5:1, etc. If the volume ratio is less than 0.2:1, lithium cannot be effectively extracted, and Li, Na and K cannot be separated well; if the volume ratio is greater than 5:1, the single-stage extraction effect of lithium is poor, and the extraction yield of lithium is low .
  • the lithium concentration in the lithium-loaded organic phase in step (1) is 0.5-3g/L, for example, it can be 0.5g/L, 0.8g/L, 1g/L, 1.2g/L, 1.5g/L , 1.8g/L, 2g/L, 2.2g/L, 2.6g/L, 2.8g/L or 3g/L, etc.
  • the lithium-supported organic phase is washed.
  • Na, K, and B are not extracted by the organic extraction system, the extraction process will produce phase entrainment.
  • a small amount of impurities such as Na, K, and B will enter the loaded organic phase with the entrained water and need to be washed to make the impurities wash into the water phase.
  • Lithium is further purified.
  • the washing liquid is water and/or a lithium-containing solution.
  • the gas-liquid-liquid three-phase reverse extraction system in step (2) comprises a first liquid phase, a second liquid phase and a gas phase.
  • the gas in the gas phase contains any one or a combination of at least two of SO 2 , SO 3 , CO 2 and Cl 2 , preferably SO 2 and/or CO 2 .
  • the gases used for stripping, SO 2 and SO 3 are tail gas produced by high-temperature treatment of sulfide ore in metallurgical processes. They are industrially used to prepare by-product sulfuric acid. A catalyst is used to oxidize and convert SO 2 to SO 3 and absorb to prepare sulfuric acid. , The process is complicated and the preparation cost is high.
  • CO 2 is mostly the tail gas of power plants and high-temperature boilers. The lime burning process also produces a large amount of CO 2 tail gas, which is currently discharged after purification treatment to produce greenhouse gases.
  • Cl 2 is a by-product of the chlor-alkali industry. It is currently used in the preparation of hydrochloric acid or the preparation of disinfectants and chlorinated plastics. However, the by-product Cl 2 is seriously surplus in China.
  • the invention adopts industrial production tail gas or discharged greenhouse gas to realize high-efficiency back extraction of lithium, which greatly reduces operating costs and reduces environmental pollution at the same time.
  • the first liquid phase contains water.
  • the second liquid phase comprises a lithium-supported organic phase.
  • the gas used for back extraction can provide a small amount of H + when dissolved in the first liquid phase.
  • H + contacts with the lithium-loaded organic phase and exchanges with Li + .
  • Li + is back-extracted into the aqueous solution and consumed
  • the H + is replenished by continuous gas reaction, and the Li + back-extracted to the water phase combines with the anions produced by the gas-liquid reaction to form a lithium-loaded aqueous solution.
  • the back extraction of lithium is shown in formula (2):
  • nLi ⁇ E N E Ch +G+1/2nH 2 O Li n G(O) 1/2n +nE N +nHE Ch (2)
  • G is the gas used for back extraction.
  • the volume ratio of the first liquid phase to the second liquid phase is 0.05:1 to 2:1, for example, it may be 0.05:1, 0.1:1, 0.5:1, 1:1, 1.5:1, or 2 :1, etc., if the volume ratio is less than 0.05:1, the lithium back extraction effect is poor; the volume ratio is greater than 2:1, the lithium concentration in the back extraction aqueous solution is low, and the lithium recovery rate is low.
  • the gas-liquid-liquid three-phase reverse extraction in step (2) adopts a multi-stage continuous countercurrent operation.
  • the equipment used for the gas-liquid-liquid three-phase reverse extraction includes a continuous mixing and clarification tank, an extraction tower or a centrifugal extractor, and the number of stages of the gas-liquid-liquid three-phase reverse extraction can be between 1 and 10. Tune.
  • the gas-liquid-liquid three-phase reverse extraction device is further preferably an extraction tower, and the size and number of stages of the extraction tower can be adjusted according to actual production process requirements.
  • the gas-liquid-liquid three-phase reverse extraction equipment can achieve a lithium reverse extraction rate of more than 90% by adjusting the number of equipment and/or process parameters.
  • the concentration of lithium in the stripping solution in step (2) is >5g/L, for example, it can be 5.1g/L, 5.2g/L, 5.5g/L, 5.8g/L, 6.0g/L , 6.5g/L, 7.0g/L, 9.0g/L or 10g/L etc.
  • the method of heat treatment in step (3) includes any one or a combination of at least two of oxidation, evaporative crystallization and thermal decomposition, among which a typical but non-limiting combination: thermal decomposition and evaporative crystallization, oxidation and evaporative crystallization .
  • the temperature of the heat treatment in step (3) is 60-90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, etc., if the temperature is lower than At 60°C, the yield of lithium products is low; if the temperature is higher than 90°C, the energy consumption in the heat treatment section increases.
  • the heat treatment time is 0.5-2h, for example, it can be 0.5h, 1h, 1.5h or 2h.
  • the heat treatment is adjusted according to the type of gas used for stripping, and SO 2 gas is used for stripping to obtain a Li 2 SO 3 solution, which is heated and oxidized to form Li 2 SO 4 , and then heated to evaporate and crystallize to obtain Li 2 SO 4 Products; use SO 3 gas back extraction to obtain Li 2 SO 4 , direct evaporation and crystallization to obtain Li 2 SO 4 products; use CO 2 gas back extraction and heating to obtain Li 2 CO 3 products; use Cl 2 back extraction to obtain LiCl products.
  • the oxidant used in the oxidation is air, oxygen and ozone gas.
  • the evaporation crystallization adopts MVR or multi-effect evaporation.
  • the thermal decomposition adopts a closed or semi-closed container.
  • the separation method includes any one or a combination of at least two of filtration, suction filtration and centrifugation, among which a typical but non-limiting combination: centrifugation and filtration, centrifugation and suction filtration.
  • the lithium product is lithium sulfate, lithium chloride or lithium carbonate, and the product purity is >96%, for example, it can be 96.5%, 97%, 98%, or 99%.
  • the mother liquor separated in step (3) is returned to the lithium-containing solution of step (1), and/or returned to the first liquid phase of step (2) to increase the total yield of lithium and realize zero discharge of waste water.
  • the method provided by the present invention includes the following steps:
  • the neutral extractant comprises tributyl phosphate (TBP), dimethylheptyl methyl phosphate (P350), trioctyl phosphine oxide (TOPO), trioctyl/hexyl phosphine oxide (Cyanex923) and N, N Any one or a combination of at least two of bis-(1-methylheptyl)acetamide (N503);
  • the chelating extractant comprises 2-hydroxy-5-nonylacetophenone oxime (LIX84), dodecylphenyl-methyl- ⁇ -diketone (LIX54), 2-hydroxy-5-nonylbenzene Formaldehyde oxime (LIX860) and 2-hydroxy-5-nonylacetophenone oxime (LIX84), dodecylphenyl-methyl- ⁇ -diketone (LIX54), 2-hydroxy-5-nonylbenzaldehyde Oxime (LIX860) any one or a combination of at least two of the extractants with the same functional group;
  • the gas in the gas-liquid-liquid three-phase reverse extraction system contains any one or a combination of at least two of SO 2 , SO 3 , CO 2 and Cl 2;
  • step (3) The stripping liquid obtained in step (2) is heat-treated at 60-90° C. for 0.5-2 h and separated to obtain a lithium product and a separated mother liquor.
  • FIG. 2 The schematic diagram of the gas-liquid-liquid three-phase reverse extraction equipment provided by the present invention is shown in FIG. 2. It shows that the equipment is an extraction tower.
  • the gas phase enters the extraction tower through the bottom gas inlet 7 and enters the extraction tower body 5 through the gas distributor 6 to react with the liquid phase, and unreacted gas is discharged through the top gas outlet 2;
  • a liquid phase enters the extraction tower through the light phase inlet 10 at the bottom of the tower, and is stripped through the tower body.
  • the lithium-containing stripping liquid is discharged through the light phase outlet 3;
  • the second liquid phase enters the tower through the heavy phase inlet 9 at the top of the tower, and After stripping, the reacted solution is discharged through the heavy phase outlet 8.
  • adjust the trays of the tower body to adjust the number of stages.
  • the electric stirrer 1 and the stirring tray 4 make the gas-liquid-liquid three-phase full contact, and the pulse system 11 provides power for the countercurrent of the first liquid phase.
  • This embodiment provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium, which includes the following steps:
  • step (2) Wash the loaded organic phase obtained in step (1) three times with water, and then perform gas-liquid-liquid three-phase reverse extraction in a continuous countercurrent extraction tower.
  • the number of stages of the extraction tower is 3, and CO 2 is used as In the gas phase, water is the first liquid phase of the back extraction, the volume ratio of water to the loaded organic phase is controlled to be 0.15:1, and the pH of the back extraction system is 8 to obtain a back extraction solution with a lithium concentration of 6.5 g/L;
  • step (3) The stripping liquid obtained in step (2) is heat-treated at 60° C. for 2 hours, and filtered with suction to obtain a lithium carbonate product, and the mother liquid after precipitation of lithium carbonate is returned to the stripping section of step (2).
  • This embodiment provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium, which includes the following steps:
  • step (2) Wash the loaded organic phase obtained in step (1) three times with water, and then perform gas-liquid-liquid three-phase reverse extraction in a continuous countercurrent extraction tower.
  • the number of stages of the extraction tower is 3, and SO 2 is used as In the gas phase, water is used as the back extraction liquid phase, and the volume ratio of water to the loaded organic phase is controlled to be 0.1:1, and the pH of the back extraction system is 6 to obtain a back extraction solution with a lithium concentration of 19.5 g/L;
  • step (3) The stripping solution obtained in step (2) is oxidized in air at 80° C. for 1 h, and then MVR is evaporated to obtain a lithium sulfate product.
  • This embodiment provides a method for extraction-reverse extraction, separation, purification, and extraction of lithium, which includes the following steps:
  • step (2) Wash the loaded organic phase obtained in step (1) 4 times with water, and then perform gas-liquid-liquid three-phase reverse extraction in a continuous countercurrent extraction tower.
  • the number of stages of the extraction tower is 3, and CO 2 is used as In the gas phase, water is used as the first liquid phase, the volume ratio of water to the loaded organic phase is controlled to be 0.25:1, and the pH of the stripping system is 9 to obtain a stripping liquid with a lithium concentration of 9.3g/L;
  • step (3) The stripping liquid obtained in step (2) is heat-treated at 80° C. for 0.5 h, filtered to obtain a lithium carbonate product, and the mother liquor is returned to the extraction section of step (1).
  • Example 1 Compared with Example 1, the only difference is that the solution obtained by purifying high-valent metal ions from the lithium battery waste leachate in step (1) is replaced with a mixed solution of lithium ore leachate and lithium precipitation mother liquor, where the concentration of Li is 1.0g/L , The concentration of Na is 20g/L, it also contains a small amount of other impurities, and the volume ratio of the organic phase to the lithium-containing solution is increased to 1:1, and the lithium in the loaded organic phase is 0.99g/L.
  • Example 1 Compared with Example 1, the only difference is that the concentration of the solution obtained by purifying high-valent metal ions from the lithium battery waste leachate in step (1) is replaced with 0.25 g/L, and the extracted lithium battery waste leachate is obtained by purifying high-valent metal ions.
  • the volume ratio of the solution to the organic phase is replaced by 5:1, and the concentration of lithium in the loaded organic phase is 1.18 g/L.
  • Example 1 Compared with Example 1, the only difference is that the volume ratio of the solution obtained by purifying high-valent metal ions from the lithium battery waste leachate in step (1) to the organic phase is replaced with 5:1, the pH is increased to 13, and the lithium in the organic phase is loaded.
  • the concentration is 2.48g/L.
  • Example 1 Compared with Example 1, the only difference is that the volume ratio of water to the loaded organic phase in step (2) is replaced with 0.05:1.
  • Example 1 Compared with Example 1, the only difference is that the volume ratio of TBP to LIX84 in step (1) is replaced with 2:1.
  • Example 1 Compared with Example 1, the only difference is that the volume ratio of the solution obtained by purifying the high-valent metal ions from the lithium battery waste leachate in step (1) to the organic phase is replaced with 5:1.
  • Example 2 Compared with Example 2, the only difference is that the volume ratio of water to the loaded organic phase in step (2) is replaced with 2:1.
  • Example 1 Compared with Example 1, the only difference is that if the composite extractant formed by TBP and LIX84 in step (1) is replaced with a single TBP or LIX84, the extraction rate of Li is less than 10%.
  • Example 1 Compared with Example 1, the only difference is that the gas in the gas-liquid-liquid three-phase reverse extraction in step (2) is replaced with air, the pH after the stripping is 11.2, and the Li stripping rate is less than 20%.
  • the alkali consumption increases, so the actual application economy is poor.
  • the calculation method of the single recovery rate of lithium is:
  • the method provided by the present invention achieves high-efficiency extraction and purification of lithium by using a composite extractant, and the extraction rate of lithium is above 92%.
  • the extraction rate of lithium is above 92%.
  • the extraction rate is more than 90%, the total yield is more than 83%, and the purity of the obtained lithium product is more than 96%.
  • the method has high efficiency and strong industrial feasibility.

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Abstract

一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：(1)采用含复合萃取剂的萃取体系，在pH＝10～13的条件下对含锂溶液进行萃取、分离，得到锂负载有机相；(2)将步骤(1)得到的锂负载有机相进行气-液-液三相反萃，得到负载锂的反萃液；(3)将步骤(2)得到的反萃液进行热处理，分离，得到锂产品以及分离后的母液。本方法通过采用复合萃取剂实现锂与Na、K和B等杂质元素的高效分离，再通过气-液-液三相连续反萃，锂的反萃率为90％以上，总收率为83％以上，得到锂产品的纯度为96％以上；且该方法处理量大，工艺和设备简单，投资小，有效利用工业尾气，节能环保，连续化生产。

Description

一种萃取-反萃分离纯化提取锂的方法
本申请要求于2019年11月1日提交中国专利局、申请号为201911061643.6、发明名称为“一种萃取-反萃分离纯化提取锂的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及化工分离技术领域，具体涉及一种萃取-反萃分离纯化提取锂的方法。
背景技术
锂是密度最小的金属，被广泛的应用于电子、化学、新能源和制药等领域，锂资源主要来源于盐湖、矿物和海水，随着近年来废弃资源再利用的推进，废旧锂电池也成为重要的来源。从这些原料中提取锂的过程需要多个纯化步骤，经典工艺中多采用蒸发浓缩、分离除杂、深度除去钙和镁离子后得到纯度高的含锂溶液，再对含锂溶液进行沉淀处理，得到碳酸锂产品。
CN108423696A公开了一种从含锂溶液中提取高纯锂盐的方法，包括以下步骤：向含锂溶液中加入pH值调节剂，调节溶液pH值大于4；将含锂溶液浓缩为锂浓度大于2g/L的富锂溶液；将超声装置放入富锂溶液中，加入沉淀剂，超声振荡；超声结束后过滤，将得到的固相洗涤并干燥，得到锂盐。该方法需要浓缩含锂溶液，处理量小；同时在沉淀锂的过程中，由于富锂溶液中含有大量的钠、钾等离子，锂盐中夹带量大，影响其纯度，制备纯度较高的锂盐需要大量的淡水洗涤，水耗量大。此外，锂盐在水相中有一定溶解度，沉淀后的母液仍含有大量的锂，造成锂的收率降低。
CN104884648A提供了一种从含锂溶液中提取锂的方法，具体包括下列步骤：制备包含碳酸离子的含锂溶液；将所述含锂溶液浓缩至锂浓度为小于或等于2.481g/L以获得第一沉淀物；对浓缩的所述含锂溶液和所述第一沉淀物进行固液分离；向浓缩后的所述含锂溶液中加入供磷物质，使溶解的锂析出为磷酸锂；将析出所述磷酸锂的过滤溶液再次浓缩至锂浓度为小于或等于2.481g/L以获得第二沉淀物；对再次浓缩的所述过滤溶液和所述第二沉淀物进行固液分离；以及向再次浓缩的所述过滤溶液中加入 核颗粒，使溶解的锂析出为磷酸锂。该方法多次进行浓缩、固液分离，锂的收率较低，工艺流程较长，投资较大，不利于工业化应用。
基于上述文献可知，如何开发一种锂收率高、锂产品纯度高、处理量大、流程短、投资小和易产业化生产的工艺成为目前急需解决的问题。
发明内容
鉴于现有技术中存在的问题，本发明提供了一种萃取-反萃分离纯化提取锂的方法，所述方法采用含有复合萃取剂的萃取体系，在高pH值条件下对含锂溶液进行萃取，实现了锂的高效萃取，并与大量的杂质元素Na、K和B等分离；然后利用工业排放的尾气，通过多级连续逆流过程进行气-液-液三相反萃，实现了锂的高效反萃。本发明提供的方法处理量大，液相循环使用，锂的总收率高；气相循环使用实现零排放，利用率高；可采用工业尾气作为三相反萃气源，成本大大降低，保护环境；同时，工艺流程简短，设备简单，投资小，易于产业化应用。
为达此目的，本发明采用以下技术方案：
本发明提供了一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：
(1)采用含复合萃取剂的萃取体系，在pH＝10～13的条件下对含锂溶液进行萃取、分离，得到锂负载有机相；
(2)将步骤(1)得到的锂负载有机相进行气-液-液三相反萃，得到负载锂的反萃液；
(3)将步骤(2)得到的反萃液进行热处理，分离，得到锂产品以及分离后的母液。
优选地，步骤(1)中所述复合萃取剂包含中性萃取剂和螯合萃取剂，所述萃取体系包含所述复合萃取剂与稀释剂。
优选地，所述中性萃取剂包含磷酸三丁酯TBP、甲基磷酸二甲庚酯P350、三辛基氧化膦TOPO、三辛基/已基氧化膦Cyanex923和N,N二-(1-甲基庚基)乙酰胺N503中的任意一种或至少两种的组合。
优选地，所述螯合萃取剂包含2-羟基-5-壬基苯乙酮肟LIX84、十二烷基苯基-甲基-β-二酮LIX54、2-羟基-5-壬基苯甲醛肟LIX860和与2-羟基-5-壬基苯乙酮肟LIX84、十二烷基苯基-甲基-β-二酮LIX54、2-羟基-5-壬基苯甲醛肟LIX860具有相同官能团的萃取剂中的任意一种或至少两种 的组合。
优选地，所述中性萃取剂与螯合萃取剂的体积比为0.2:1～2:1。
优选地，所述萃取体系还包括相修饰剂。
优选地，所述萃取体系包含复合萃取剂、相修饰剂和稀释剂；所述萃取体系中复合萃取剂的体积百分比为5～30％，相修饰剂的体积百分比为0～10％。
优选地，步骤(1)中所述含锂溶液包括锂矿石浸出液、沉锂母液、锂电池废料浸出液和盐湖卤水中的任意一种或至少两种的组合。
优选地，所述含锂溶液中锂的浓度为0.25～5g/L。
优选地，所述含锂溶液中主要杂质元素钠、钾和硼的浓度独立地分别为10～150g/L，0～50g/L和0～10g/L。
优选地，所述含锂溶液中还含有铷、铝、镁、铯和钙等金属离子。
优选地，所述含锂溶液与萃取体系的有机相的体积比为0.2:1～5:1。
优选地，步骤(1)中所述锂负载有机相中锂的浓度为0.5～3g/L。
优选地，步骤(1)还包括对所述锂负载有机相进行洗涤。
优选地，所述洗涤液为水和/或含锂溶液。
优选地，步骤(2)中所述气-液-液三相反萃体系包含第一液相、第二液相和气相。
优选地，所述气相的气体包含SO 2、SO 3、CO 2或Cl 2中的任意一种或至少两种的组合。
优选地，所述气相的气体为SO 2和/或CO 2。
优选地，所述第一液相包含水。
优选地，所述第二液相包含锂负载有机相。
优选地，所述气-液-液三相反萃控制pH＝6～9。
优选地，所述第一液相与第二液相的体积比为0.05:1～2:1。
优选地，步骤(2)中所述气-液-液三相反萃采用多级连续逆流操作。
优选地，所述气-液-液三相反萃的设备包含连续混合澄清槽、萃取塔或离心萃取器中的任意一种；所述气-液-液三相反萃的级数在1～10级之间可调。
优选地，步骤(2)中所述反萃液中锂的浓度为＞5g/L。
优选地，步骤(3)中所述热处理的方式包括氧化、蒸发结晶或热分解中任意一种或至少两种的组合。
优选地，所述热处理的温度为60～90℃。
优选地，所述热处理的时间为0.5～2h。
优选地，所述氧化所用的氧化剂为空气、氧气以及臭氧气体。
优选地，所述蒸发结晶采用MVR或多效蒸发。
优选地，所述热分解采用封闭或半封闭容器。
优选地，步骤(3)中所述分离的方式包含过滤、抽滤或离心中的任意一种或至少两种的组合。
优选地，所述锂产品为硫酸锂、氯化锂或碳酸锂，产品纯度>96％。
优选地，步骤(3)分离后的母液返回步骤(1)和/或返回步骤(2)的第一液相中。
与现有技术相比，本发明的有益效果为：
(1)本发明提供的萃取-反萃分离纯化提取锂的方法，通过采用复合萃取剂实现锂与Na、K和B等杂质离子的高效分离，再通过气-液-液三相连续反萃，锂的反萃率为90％以上，实现液相和气相的循环使用，锂的总收率为83％以上，得到的锂产品的纯度为96％以上；
(2)本发明提供的方法处理量大，工艺和设备简单，投资小，能耗低，可实现连续化生产，具有较高的应用价值。
附图说明
图1是本发明提供的萃取-反萃分离纯化提取锂的工艺流程图；
图2是本发明提供的气-液-液三相反萃设备示意图，图2中，1是电动搅拌器，2是气体出口，3是轻相出口，4是搅拌塔板，5是萃取塔塔体，6是气体分布器，7是气体入口，8是重相出口，9是重相入口，10是轻相入口，11是脉冲系统。
具体实施方式
本发明提供了一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：
(1)采用含复合萃取剂的萃取体系，在pH＝10～13的条件下对含锂溶液进行萃取、分离，得到锂负载有机相；
(2)将步骤(1)得到的锂负载有机相进行气-液-液三相反萃，得到负载锂 的反萃液；
(3)将步骤(2)得到的反萃液进行热处理，分离，得到锂产品以及分离后的母液。
本发明提供的方法，采用含有复合萃取剂的萃取体系，在较高的pH值条件下，锂被复合萃取剂有效的萃取，进入负载有机相；然后锂负载有机相通过气-液-液三相反萃，使用酸性气体作为气相，所述气体溶于液相可以提供少量的H +，H +与负载锂的有机相接触，并与Li +交换，Li +被反萃到水溶液中，被消耗的H +通过连续的气体反应进行补充，反萃到水相的Li +与气-液反应产生的阴离子结合形成锂的负载水溶液；再通过热处理，得到纯度较高的锂产品。
优选地，步骤(1)中所述复合萃取剂包含中性萃取剂和螯合萃取剂，所述萃取体系包含所述复合萃取剂与稀释剂。在pH＝10～13的条件下，锂与中性萃取剂形成一种夹和物，夹和物被螯合萃取剂萃取，因此实现锂的高效萃取。萃取反应如式(1)所示：
Li nL+nE N+nHE Ch+nOH -＝nLi·E NE Ch+L n-+nH 2O     (1)
式(1)中，L为Cl -或SO 4 2-；E N为中性萃取剂，HE Ch为螯合萃取剂。
由于Na、K和B等离子不与E N形成夹和物，因此不被复合萃取剂萃取，Li与Na、K和B等杂质元素得到很好分离。
本发明中，萃取过程在强碱条件下进行，pH＝10～13，例如可以是，10、11、12或13等。当pH<10时，萃取过程锂形成的夹和物与HE Ch产生的H +不能有效中和，锂不能被有效萃取。当pH>13时，大量Na +和K +等也与HE Ch形成NaE Ch或KE Ch，锂也不能被有效萃取，并且与Na和K不能很好分离。
优选地，所述中性萃取剂包含磷酸三丁酯(TBP)、甲基磷酸二甲庚酯(P350)、三辛基氧化膦(TOPO)、三辛基/已基氧化膦(Cyanex923)和N,N二-(1-甲基庚基)乙酰胺(N503)中的任意一种或至少两种的组合，其中典型但非限制性组合：P350和N503，TBP和TOPO，TBP、P350和Cyanex923，P350、Cyanex923和N503。
优选地，所述螯合萃取剂包含2-羟基-5-壬基苯乙酮肟(LIX84)、十二烷基苯基-甲基-β-二酮(LIX54)、2-羟基-5-壬基苯甲醛肟(LIX860)和与2- 羟基-5-壬基苯乙酮肟(LIX84)、十二烷基苯基-甲基-β-二酮(LIX54)、2-羟基-5-壬基苯甲醛肟(LIX860)具有相同官能团的萃取剂中的任意一种或至少两种的组合，其中典型但非限制性组合：LIX54和LIX84I，LIX54和LIX860，LIX54、LIX84I和LIX860。
优选地，所述中性萃取剂与螯合萃取剂的体积比为0.2:1～2:1，例如可以是0.2:1、0.3:1、0.5:1、0.8:1、1:1、1.2:1、1.5:1、1.8:1或2:1等。
优选地，所述萃取体系还包括相修饰剂。
优选地，所述萃取体系包含复合萃取剂、相修饰剂和稀释剂，其中，所述复合萃取剂和相修饰剂的体积百分比独立地分别为5～30％和0～10％。例如，复合萃取剂的体积百分比可以是5％、10％、15％、20％、25％或30％等；相修饰剂的体积百分比可以是0％、0.5％、1％、3％、5％、8％、9％或10％等，相修饰剂根据萃取体系是否出现“乳化”问题，确定是否加入以及加入的体积比。
本发明中，对稀释剂和相修饰剂的具体种类不做特殊限定，只要是本领域技术人员常用的种类，均适用于本发明。作为本发明的一个具体实施例，所述稀释剂为正十二烷或磺化煤油，相修饰剂为十二烷醇。
优选地，步骤(1)中所述含锂溶液包括锂矿石浸出液、沉锂母液、锂电池废料浸出液和盐湖卤水中的任意一种或至少两种的组合，其中典型但非限制性组合：锂矿石浸出液和沉锂母液，盐湖卤水，盐湖卤水和沉锂母液，锂电池废料浸出液，锂电池废料浸出液和沉锂母液等。
优选地，所述含锂溶液中锂的浓度为0.25～5g/L，例如可以是0.25g/L、0.3g/L、0.5g/L、0.8g/L、1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、4.5g/L、4.8g/L或5g/L等。
优选地，所述含锂溶液中主要杂质元素钠、钾和硼的浓度独立地分别为10～150g/L，0～50g/L和0～10g/L，例如，钠的浓度可以是10g/L、15g/L、20g/L、30g/L、50g/L、80g/L、90g/L、95g/L、100g/L、120g/L、140g/L或150g/L等；钾的浓度可以是0g/L、1g/L、5g/L、10g/L、15g/L、20g/L、30g/L、40g/L、45g/L或50g/L等；硼的浓度可以是0g/L、1g/L、2g/L、3g/L、5g/L、7g/L、9g/L或10g/L等。
优选地，所述含锂溶液中还含有铷、铝、镁、铯和钙等金属离子。
优选地，所述含锂溶液与有机相的体积比为0.2:1～5:1，例如可以是0.2:1、0.3:1、0.5:1、0.8:1、1:1、1.2:1、1.5:1、1.8:1、2:1、2.5:1、3:1、4:1或5:1等。若所述体积比小于0.2:1，锂不能被有效萃取，并且Li与Na和K不能很好分离；体积比大于5:1，锂的单级萃取效果较差，锂的萃取收率偏低。
优选地，步骤(1)中所述锂负载有机相中锂浓度为0.5～3g/L，例如可以是0.5g/L、0.8g/L、1g/L、1.2g/L、1.5g/L、1.8g/L、2g/L、2.2g/L、2.6g/L、2.8g/L或3g/L等。
优选地，所述锂负载有机相进行洗涤。尽管Na、K和B等不被有机萃取体系萃取，但萃取过程会产生相的夹带，少量Na、K和B等杂质随夹带的水进入负载有机相，需要进行洗涤，使杂质洗涤进入水相，锂得到进一步纯化。
优选地，所述洗涤液为水和/或含锂溶液。
优选地，步骤(2)中所述气-液-液三相反萃体系包含第一液相、第二液相和气相。
优选地，所述气相的气体包含SO 2、SO 3、CO 2和Cl 2中的任意一种或至少两种的组合，优选为SO 2和/或CO 2。
本发明中，反萃使用的气体中，SO 2、SO 3多为冶金过程高温处理硫化矿产生的尾气，工业用来制备副产硫酸，采用催化剂将SO 2氧化转化为SO 3，吸收制备硫酸，过程复杂，制备成本高。CO 2多为电厂和高温锅炉尾气，石灰烧制过程也产生大量的CO 2尾气，目前经过净化处理后排放，产生温室气体。Cl 2为氯碱行业的副产品，目前用来制备盐酸或制备消毒液以及氯化塑料行业，但在我国副产Cl 2严重过剩。本发明采用工业生产的尾气，或排放的温室气体实现锂的高效反萃，大大降低了运行成本，同时减轻了环境污染。
优选地，所述第一液相包含水。
优选地，所述第二液相包含锂负载有机相。
本发明中，反萃使用的所述气体溶于第一液相可以提供少量的H +，H +与锂负载有机相接触，并与Li +交换，Li +被反萃到水溶液中，被消耗的H +通过连续的气体反应进行补充，反萃到水相的Li +与气-液反应产生的阴 离子结合形成锂的负载水溶液。锂的反萃取如式(2)所示：
nLi·E NE Ch+G+1/2nH 2O＝Li nG(O) 1/2n+nE N+nHE Ch    (2)
式(2)中，G为反萃所用的气体。
优选地，所述气-液-液三相反萃控制pH＝6～9，例如可以是6、7、8或9等。锂反萃是通过气-液-液连续三相反应实现，过程中生成Li n G(O) 1/2n接近中性或偏碱性，反萃过程体系自动维持在近中性或弱碱性，pH＝6～9之间，不需要加入任何其他试剂进行酸碱度调节。
优选地，所述第一液相与第二液相的体积比为0.05:1～2:1，例如可以是0.05:1、0.1:1、0.5:1、1:1、1.5:1或2:1等，若所述体积比小于0.05:1，锂的反萃效果较差；体积比大于2:1，反萃水溶液中锂浓度偏低，锂回收率低。
优选地，步骤(2)中所述气-液-液三相反萃采用多级连续逆流操作。
优选地，所述气-液-液三相反萃使用的设备包含连续混合澄清槽、萃取塔或离心萃取器，所述气-液-液三相反萃的级数在1～10级之间可调。所述气-液-液三相反萃的设备进一步优选为萃取塔，所述萃取塔的尺寸和级数可根据实际生产过程需要调整。
本发明中，所述气-液-液三相反萃设备通过调整设备数量和/或工艺参数，锂的反萃率均能达到90％以上。
优选地，步骤(2)中所述反萃液中锂的浓度为＞5g/L，例如可以是5.1g/L、5.2g/L、5.5g/L、5.8g/L、6.0g/L、6.5g/L、7.0g/L、9.0g/L或10g/L等。
优选地，步骤(3)中所述热处理的方式包括氧化、蒸发结晶和热分解中任意一种或至少两种的组合，其中典型但非限制性组合：热分解和蒸发结晶，氧化和蒸发结晶。
优选地，步骤(3)中所述热处理的温度为60～90℃，例如可以是60℃、65℃、70℃、75℃、80℃、85℃或90℃等，若所述温度低于60℃，锂产品收率较低；温度高于90℃，热处理工段能耗增大。
优选地，所述热处理的时间为0.5～2h，例如可以是0.5h、1h、1.5h或2h等。
本发明中，所述热处理根据反萃使用的气体种类进行调整，采用SO 2 气体反萃，得到Li 2SO 3溶液，加热氧化后形成Li 2SO 4，再加热蒸发结晶后得到Li 2SO 4产品；采用SO 3气体反萃，得到Li 2SO 4，直接蒸发结晶获得Li 2SO 4产品；采用CO 2气体反萃，加热获得Li 2CO 3产品；采用Cl 2反萃，获得LiCl产品。
优选地，所述氧化所用的氧化剂为空气、氧气以及臭氧气体。
优选地，所述蒸发结晶采用MVR或多效蒸发。
优选地，所述热分解采用封闭或半封闭容器。
优选地，所述分离的方式包含过滤、抽滤和离心中的任意一种或至少两种的组合，其中典型但非限制性组合：离心和过滤、离心和抽滤。
优选地，所述锂产品为硫酸锂、氯化锂或碳酸锂，产品纯度>96％，例如可以是96.5％、97％、98％或99％等。
优选地，步骤(3)分离后的母液返回步骤(1)的含锂溶液中，和/或返回步骤(2)的第一液相中，提高锂的总收率，实现废水零排放。
优选地，本发明提供的方法，包括以下步骤：
(1)将中性萃取剂和螯合萃取剂混合形成复合萃取剂，控制中性萃取剂与螯合萃取剂的体积比为0.2:1～2:1，再加入稀释剂和相修饰剂混合形成萃取体系，控制复合萃取剂和相修饰剂的体积百分比独立地分别为5～30％和0～10％。在pH＝10～13的条件下与锂浓度为0.25～5g/L的溶液进行萃取，控制含锂溶液与有机相的体积比为0.2:1～5:1，然后分离，得到锂浓度为0.5～3g/L的负载有机相；
所述中性萃取剂包含磷酸三丁酯(TBP)、甲基磷酸二甲庚酯(P350)、三辛基氧化膦(TOPO)、三辛基/已基氧化膦(Cyanex923)和N,N二-(1-甲基庚基)乙酰胺(N503)中的任意一种或至少两种的组合；
所述螯合萃取剂包含2-羟基-5-壬基苯乙酮肟(LIX84)、十二烷基苯基-甲基-β-二酮(LIX54)、2-羟基-5-壬基苯甲醛肟(LIX860)和2-羟基-5-壬基苯乙酮肟(LIX84)、十二烷基苯基-甲基-β-二酮(LIX54)、2-羟基-5-壬基苯甲醛肟(LIX860)具有相同官能团的萃取剂中的任意一种或至少两种的组合；
(2)将步骤(1)得到的锂负载有机相进行洗涤，然后在连续逆流萃取塔中进行气-液-液三相反萃，控制反萃体系的pH＝6～9，得到锂浓度＞5g/L的反萃液；
所述气-液-液三相反萃体系中的气体包含SO 2、SO 3、CO 2和Cl 2中的任意一种或至少两种的组合；
(3)将步骤(2)得到的反萃液在60～90℃下进行热处理0.5～2h，分离，得到锂产品以及分离后的母液。
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明提供的萃取-反萃分离纯化提取锂的工艺流程，如图1所示。其显示含锂溶液在pH＝10～13的条件下发生锂的萃取，然后对萃取液进行洗涤除去Na、K和B等杂质，萃取液再通过气-液-液三相进行连续反萃，得到锂的反萃液，再经过热处理，分离后获得锂产品。分离后的母液按循环方式1返回Li萃取步骤，和/或按循环方式2返回Li的反萃步骤，得到循环利用。
本发明提供的气-液-液三相反萃设备示意图，如图2所示。其显示所述设备为萃取塔，气相经塔底气体入口7进入萃取塔，经气体分布器6进入萃取塔塔体5与液相接触反应，未反应的气体经塔顶气体出口2排出；第一液相经塔底轻相入口10进入萃取塔，经塔体进行反萃，含有锂的反萃液经轻相出口3排出；第二液相经塔顶重相入口9进入塔内，发生反萃，反应后的溶液经重相出口8排出。根据实际生产需要，调节塔体的塔板实现级数的调整。电动搅拌器1和搅拌塔板4使得气-液-液三相充分接触，脉冲系统11为第一液相的逆流提供动力。
实施例1
本实施例提供一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：
(1)将TBP和LIX84混合形成复合萃取剂，控制TBP与LIX84的体积比为0.2:1，磺化煤油做稀释剂，复合萃取剂的体积百分比为20％，另外加入体积百分比为5％的十二烷醇作为相修饰剂，在pH＝10的条件下与锂浓度为0.5g/L和钠浓度为10g/L的锂电池废料浸出液净化高价金属离子得到的溶液进行萃取，控制锂电池废料浸出液净化高价金属离子得到的溶液与有机相的体积比为2.2:1，然后分离，得到锂浓度为1g/L的负载有机相；
(2)将步骤(1)得到的负载有机相进行水洗3次，然后在连续逆流萃取塔中进行气-液-液三相反萃，所述萃取塔的级数为3级，使用CO 2作为气相，水为反萃第一液相，控制水与负载有机相的体积比为0.15:1，反萃体系的pH＝8，得到锂浓度6.5g/L的反萃液；
(3)将步骤(2)得到的反萃液在60℃下进行热处理2h，抽滤，得到碳酸锂产品，碳酸锂沉淀后的母液返回步骤(2)的反萃段。
实施例2
本实施例提供一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：
(1)将TOPO和LIX860混合形成复合萃取剂，控制TOPO与LIX860的体积比为1:1，正十二烷为稀释剂，复合萃取剂的体积百分比为25％，在pH＝12的条件下与锂浓度为2g/L、钠浓度为50g/L、钾浓度为25g/L和硼浓度为10g/L的沉锂母液进行萃取，控制沉锂母液与有机相的体积比为1:1，然后分离，得到锂浓度为2g/L的负载有机相；
(2)将步骤(1)得到的负载有机相进行水洗3次，然后在连续逆流萃取塔中进行气-液-液三相反萃，所述萃取塔的级数为3级，使用SO 2作为气相，水作为反萃液相，并控制水与负载有机相的体积比为0.1:1，反萃体系的pH＝6，得到锂浓度19.5g/L的反萃液；
(3)将步骤(2)得到的反萃液在80℃下空气氧化1h，然后MVR蒸发，得到硫酸锂产品。
实施例3
本实施例提供一种萃取-反萃分离纯化提取锂的方法，包括以下步骤：
(1)将Cyanex923和LIX54混合形成复合萃取剂，控制Cyanex923与LIX54的体积比为2:1，磺化煤油为稀释剂，复合萃取剂的体积百分比为15％，在pH＝13的条件下与锂浓度为5g/L、钠浓度为100g/L、钾浓度为50g/L和硼浓度为5g/L的盐湖卤水浓缩溶液进行萃取，控制盐湖卤水浓缩溶液与有机相的体积比为0.2:1，然后分离，得到锂浓度为2.4g/L的负载有机相；
(2)将步骤(1)得到的负载有机相进行水洗4次，然后在连续逆流萃取塔中进行气-液-液三相反萃，所述萃取塔的级数为3级，使用CO 2作为气相，使用水作为第一液相，控制水与负载有机相的体积比为0.25:1，反萃 体系的pH＝9，得到锂浓度9.3g/L的反萃液；
(3)将步骤(2)得到的反萃液在80℃下进行热处理0.5h，过滤，得到碳酸锂产品，母液返回步骤(1)萃取段。
实施例4
与实施例1相比，区别仅在于，将步骤(1)中锂电池废料浸出液净化高价金属离子得到的溶液替换为锂矿石浸出液与沉锂母液的混合溶液，其中Li的浓度为1.0g/L，Na的浓度为20g/L，还含有少量的其他杂质，并采用有机相与含锂溶液的体积比增大为1:1，负载有机相中的锂为0.99g/L。
实施例5
与实施例1相比，区别仅在于，将步骤(1)中的锂电池废料浸出液净化高价金属离子得到的溶液的浓度替换为0.25g/L，萃取的锂电池废料浸出液净化高价金属离子得到的溶液与有机相的体积比替换为5:1，负载有机相中锂的浓度为1.18g/L。
实施例6
与实施例1相比，区别仅在于，将步骤(1)中锂电池废料浸出液净化高价金属离子得到的溶液与有机相的体积比替换为5:1，pH提高到13，负载有机相中锂浓度为2.48g/L。
实施例7
与实施例1相比，区别仅在于，将步骤(2)中水与负载有机相的体积比替换为0.05:1。
实施例8
与实施例1相比，区别仅在于，将步骤(1)中TBP与LIX84的体积比替换为2:1。
实施例9
与实施例1相比，区别仅在于，将步骤(1)中锂电池废料浸出液净化高价金属离子得到的溶液与有机相的体积比替换为5:1。
实施例10
与实施例2相比，区别仅在于，将步骤(2)中水与负载有机相的体积比替换为2:1。
对比例1
与实施例1相比，区别仅在于，将步骤(1)中TBP和LIX84形成的复合萃取剂替换为单独的TBP或LIX84，Li的萃取率均小于10％。
对比例2
与实施例1相比，区别仅在于，将步骤(2)中气-液-液三相反萃中的气体替换为空气，反萃后pH为11.2，Li的反萃率<20％。
对比例3
与实施例1相比，区别仅在于，将步骤(1)中pH＝10替换为pH＝9，Li萃取率35.3％，没有工业实施的经济性。
对比例4
与实施例1相比，区别仅在于，将步骤(1)中pH＝10替换为pH＝14，Li萃取率为75.5％，可能是由于杂质元素Na或K的竞争萃取导致Li萃取率降低，同时提高pH值，碱耗量增大，因此实际应用经济性差。
萃取-反萃分离纯化提取锂方法的评价：
通过将实施例1～8和对比例1～4方法中锂的萃取率、反萃率和锂的总收率进行计算与评价，评价结果如表1所示。
表1实施例1～8和对比例1～4中锂的萃取率、反萃率和锂的总收率
Figure PCTCN2020124747-appb-000001
Figure PCTCN2020124747-appb-000002
本发明中，锂单次回收率的计算方法为：
R 0＝R l×R 2
其中，R 0-锂单次回收率，％；R 1-锂单次萃取率，％；R 2-锂单次反萃率，％。
通过实施例和对比例分析，本发明提供的方法，通过采用复合萃取剂实现锂高效提取和纯化，锂的萃取率在92％以上，通过气-液-液三相连续反萃，锂的反萃率为90％以上，总收率为83％以上，得到的锂产品的纯度为96％以上。该方法效率高、工业可实施性强。
申请人声明，本发明通过上述实施例来说明本发明的特征，但本发明并不局限于上述特征，即不意味着本发明必须依赖上述特征才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用方法的等效替换以及辅助方法的增加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (35)

  1. 一种萃取-反萃分离纯化提取锂的方法，其特征在于，包括以下步骤：
    (1)采用含复合萃取剂的萃取体系，在pH＝10～13的条件下对含锂溶液进行萃取、分离，得到锂负载有机相；
    (2)将步骤(1)得到的锂负载有机相进行气-液-液三相反萃，得到负载锂的反萃液；
    (3)将步骤(2)得到的反萃液进行热处理，分离，得到锂产品以及分离后的母液。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中所述复合萃取剂包含中性萃取剂和螯合萃取剂，所述萃取体系包含所述复合萃取剂与稀释剂。
  3. 根据权利要求2所述的方法，其特征在于，所述中性萃取剂包含磷酸三丁酯TBP、甲基磷酸二甲庚酯P350、三辛基氧化膦TOPO、三辛基/已基氧化膦Cyanex923和N,N二-(1-甲基庚基)乙酰胺N503中的任意一种或至少两种的组合。
  4. 根据权利要求2所述的方法，其特征在于，所述螯合萃取剂包含2-羟基-5-壬基苯乙酮肟LIX84、十二烷基苯基-甲基-β-二酮LIX54、2-羟基-5-壬基苯甲醛肟LIX860和与2-羟基-5-壬基苯乙酮肟(LIX84)、十二烷基苯基-甲基-β-二酮(LIX54)、2-羟基-5-壬基苯甲醛肟(LIX860)具有相同官能团的萃取剂中的任意一种或至少两种的组合。
  5. 根据权利要求2～4任意一项所述的方法，其特征在于，所述中性萃取剂与螯合萃取剂的体积比为0.2:1～2:1。
  6. 根据权利要求1～4任意一项所述的方法，其特征在于，所述萃取体系还包括相修饰剂。
  7. 根据权利要求6所述的方法，其特征在于，所述萃取体系包含复合萃取剂、相修饰剂和稀释剂；所述萃取体系中复合萃取剂的体积百分比为5～30％，相修饰剂的体积百分比为0～10％。
  8. 根据权利要求1所述的方法，其特征在于，步骤(1)中所述含锂溶液包括锂矿石浸出液、沉锂母液、锂电池废料浸出液和盐湖卤水中的任意一 种或至少两种的组合。
  9. 根据权利要求8所述的方法，其特征在于，所述含锂溶液中锂的浓度为0.25～5g/L。
  10. 根据权利要求8所述的方法，其特征在于，所述含锂溶液中主要杂质元素钠、钾和硼的浓度独立地分别为10～150g/L，0～50g/L和0～10g/L。
  11. 根据权利要求8所述的方法，其特征在于，所述含锂溶液中还含有铷、铝、镁、铯和钙等金属离子。
  12. 根据权利要求1或8所述的方法，其特征在于，所述含锂溶液与萃取体系的有机相的体积比为0.2:1～5:1。
  13. 根据权利要求1或8所述的方法，其特征在于，步骤(1)中所述锂负载有机相中锂的浓度为0.5～3g/L。
  14. 根据权利要求1所述的方法，其特征在于，步骤(1)还包括对所述锂负载有机相进行洗涤。
  15. 根据权利要求14所述的方法，其特征在于，所述洗涤用洗涤液为水和/或含锂溶液。
  16. 根据权利要求1所述的方法，其特征在于，步骤(2)中所述气-液-液三相反萃体系包含第一液相、第二液相和气相。
  17. 根据权利要求16所述的方法，其特征在于，所述气相为酸性气体。
  18. 根据权利要求17所述的方法，其特征在于，所述气相的气体包含SO 2、SO 3、CO 2或Cl 2中的任意一种或至少两种的组合。
  19. 根据权利要求18所述的方法，其特征在于，所述气相的气体为SO 2和/或CO 2。
  20. 根据权利要求16所述的方法，其特征在于，所述第一液相包含水。
  21. 根据权利要求16所述的方法，其特征在于，所述第二液相包含锂负载有机相。
  22. 根据权利要求16所述的方法，其特征在于，所述气-液-液三相反萃体系的pH＝6～9。
  23. 根据权利要求16所述的方法，其特征在于，所述第一液相与第二液相的体积比为0.05:1～2:1。
  24. 根据权利要求1所述的方法，其特征在于，步骤(2)中所述气-液- 液三相反萃采用多级连续逆流操作。
  25. 根据权利要求24所述的方法，其特征在于，所述气-液-液三相反萃的设备包含连续混合澄清槽、萃取塔或离心萃取器中的任意一种；所述气-液-液三相反萃的级数在1～10级之间可调。
  26. 根据权利要求1或24所述的方法，其特征在于，步骤(2)中所述反萃液中锂的浓度为＞5g/L。
  27. 根据权利要求1所述的方法，其特征在于，步骤(3)中所述热处理的方式包括氧化、蒸发结晶或热分解中任意一种或至少两种的组合。
  28. 根据权利要求27所述的方法，其特征在于，所述热处理的温度为60～90℃。
  29. 根据权利要求27所述的方法，其特征在于，所述热处理的时间为0.5～2h。
  30. 根据权利要求27所述的方法，其特征在于，所述氧化所用的氧化剂为空气、氧气以及臭氧气体。
  31. 根据权利要求1所述的方法，其特征在于，所述蒸发结晶采用MVR或多效蒸发。
  32. 根据权利要求1所述的方法，其特征在于，所述热分解采用封闭或半封闭容器。
  33. 根据权利要求1所述的方法，其特征在于，步骤(3)中所述分离的方式包含过滤、抽滤或离心中的任意一种或至少两种的组合。
  34. 根据权利要求17或18所述的方法，其特征在于，所述锂产品为硫酸锂、氯化锂或碳酸锂，产品纯度>96％。
  35. 根据权利要求16所述的方法，其特征在于，根据权利要求1～9所述的方法，其特征在于，步骤(3)分离后的母液返回步骤(1)和/或返回步骤(2)的第一液相中。
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