CN102992358A - Method for extracting lithium salt from lithium brine - Google Patents
Method for extracting lithium salt from lithium brine Download PDFInfo
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- CN102992358A CN102992358A CN2012100553231A CN201210055323A CN102992358A CN 102992358 A CN102992358 A CN 102992358A CN 2012100553231 A CN2012100553231 A CN 2012100553231A CN 201210055323 A CN201210055323 A CN 201210055323A CN 102992358 A CN102992358 A CN 102992358A
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Abstract
The invention provides a method for extracting lithium salt from lithium brine. The method comprises the following steps: extraction step: adding a co-extracting agent FeCl3 and an extraction agent tributyl phosphate (TBP) to lithium brine to extract lithium so as to obtain an organic phase LiFeCl4.2TBP and a water phase raffinate; reverse extraction step: adding a hydrochloric acid liquor to the organic phase LiFeCl4.2TBP for reverse extraction to obtain organic phase LiFeCl4.2TBP and water phase LiCl; and phase inversion step: inversing phase for the organic phase LiFeCl4.2TBP containing hydrogen ions by a liquor of alkali chloride, alkaline earth chloride or a mixture MCln (n is greater than or equal to 1) as a phase inversion agent to obtain an organic phase M(FeCl4)n.2TBP. According to the method for extracting lithium salt from lithium brine provided by the invention, the production cost of extracting lithium salt can be lowered.
Description
Technical field
The present invention relates to extraction chemistry, chemical technology field, relate in particular to a kind of method of from contain lithium bittern, extracting lithium salts.
Background technology
In recent years, global climate sharply changes, and prospective oil reduces rapidly, and energy dilemma has threatened the stable Sustainable development of human society day by day.As the carrier of storage and the transportation of electric energy, lithium is by internationally recognized preferred kind, and become the new millennium strategy metal that reduces fossil energy consumption, protection of the environment.At present, mobile telephone with the demand of Quilonum Retard just with annual 25% speed increment.Along with the solution of a series of technical bottlenecks of the electrically driven (operated) environmentally friendly vehicle of large capacity lithium, the demand of electric vehicle lithium will be with unprecedented scale development.
Whole world lithium resource mainly concentrates on a few countries such as Bolivia, China, Chile, Argentina, Australia, the U.S., and take salt lake resources as main.Therefore, from salt lake brine, extract the most important thing that lithium has become current various countries' contention energy strategy highland.
How low cost production lithium salts product and improve the salt pan lithium rate of recovery from salt lake brine is the common heat subject of paying close attention to of various countries developer.Solvent extration and membrane separation process are two current technological development direction.
Up to now, patent and the patent application relevant with the Technology of extracting lithium with extraction process from salt lake brine has: Goodenough Robert D invented " having adopted urea, the agent of ketone micro-extraction to extract the method for lithium from the carbonate salt lake " (US3306712A) in (1) 1963 year; (2) 1974 years Atomic Energy Commission invention " extracts the lithium method take beta-diketon and trioctylphosphine oxide (TOPO) as extraction system " (US3793433A) from natural bittern.(CN1005145B), the method is with tributyl phosphate (TBP-sulfonated kerosene-iron trichloride (FeCl in people's inventions " a kind of method of extracting Lithium chloride (anhydrous) from contain lithium bittern " such as the yellow Shi Qiang of Qinghai Yanhu Inst., Chinese Academy of Sciences in (3) 1987 years
3) be extraction system, extraction process extracts lithium from salt lake brine.(4) nineteen ninety Brown Patrick M invention " uses the Fatty Alcohol(C12-C14 and C12-C18) of carbonatoms from 6 to 16 to prepare the method for Quilonum Retard as organic solvent from hang down boron bittern " (US5219550A); (5) Lee of Southern Yangtze University (CN101767804A), the method is with TBP-ionic liquid-FeCl in all inventions " a kind of method of extracting lithium from salt lake brine "
3Be extraction system, the extraction lithium from salt lake brine; (6) (CN101698488A), the method is with TBP-CON-KS-FeCl in Lee of Qinghai Yanhu Inst., Chinese Academy of Sciences hamming invention " utilizing the high Mg/Li ratio salt lake brine to prepare the method for Quilonum Retard "
3Be system, extraction process extracts lithium from salt lake brine.
Separation and Extraction lithium in the salt lake brine of the very suitable China of the extraction system high Mg/Li ratio take tributyl phosphate (TBP) as extraction agent.Although, the seventies in last century, the TBP-sulfonated kerosene extraction system by the invention of Qinghai Salt Lake institute of the Chinese Academy of Sciences had preferably effect of extracting, and 9,000,000 yuan have been invested in the enforcement period of the seventh five-year plan, built 50 tons of lithium chloride pilot plants of annual output in large bavin dawn salt lake, 40 liters of extraction tanks running pilot-scale experiment: the lithium percentage extraction reaches 98.4%, 330 liter of extraction tank running, the lithium percentage extraction reaches 93%, the total yield of lithium obtains qualified Lithium chloride (anhydrous) product greater than 86%, and its purity is 99%.Pilot-scale experiment shows that technical matters is feasible, and technical indicator is good.But what adopt in the technique is the full alkali phase inversion of full acid, and this has just determined that this method need to consume a large amount of soda acids, and requires very high to the acid-proof alkaline of equipment.The soda acid expense accounts for more than 60% of whole lithium cost of goods manifactured, and economic target is too high, is difficult to and external intratype competition.The package deal gasifying device exists lectotype selection and owes rationally, and through engineering approaches research is insufficient, causes that technical process is long, production cost is high, and equipment corrosion is serious, thereby can't further realize industrialization.
TBP-ionic liquid-FeCl
3Extraction system, the extraction lithium (CN101698488A) from salt lake brine, this technology except the thinner sulfonated kerosene being replaced by ionic liquid, the salt lake TBP-of institute sulfonated kerosene-iron trichloride (FeCl that all the other whole parameters are applied mechanically
3) system.Test only is in the little experimental phase, and, because ionic liquid is very expensive medicament, use this medicament to carry out industrialization, product cost can exist bottleneck, and economic target is too high.
Summary of the invention
Problem that can't industrialization for there being the method high cost that extracts lithium salts from contain lithium bittern in the prior art the invention provides a kind of method of extracting lithium salts from contain lithium bittern that can reduce production costs.
The invention provides a kind of method of extracting lithium salts from contain lithium bittern, it comprises:
A kind of method of extracting lithium salts from contain lithium bittern is characterized in that comprising:
Extraction step extracts agent FeCl altogether to containing to add in the lithium bittern
3, extraction agent tributyl phosphate (TBP), carry out extraction of lithium, obtain organic phase LiFeCl
42TBP and water raffinate;
The back extraction step is to organic phase LiFeCl
4Add hydrochloric acid soln among the 2TBP and strip, obtain organic phase HFeCl
42TBP and water LiCl;
The phase inversion step is with alkali metal chloride, alkaline earth metal chloride or the mixture M Cl of the two
n(n 〉=1) solution as the phase inversion agent to containing hydrionic organic phase HFeCl
42TBP carries out phase inversion, obtains organic phase M (FeCl
4)
n2TBP.。
Preferably, the water raffinate that obtains in the described extraction step further is applied in the described phase inversion step as the phase inversion agent.
Preferably, described phase inversion agent MCl
nBe KCl, NaCl, CaCl
2, MgCl
2, BaCl
2In one or more.
Preferably, the reaction conditions in the described phase inversion step is: phase inversion agent MCl
nConcentration=2-10 mole (mol/L); Compare=hydrogeneous organic phase volume/phase inversion agent volume=0.25-10; Reaction times=0.2-12 minute.
Preferably, between described extraction step and back extraction step, further comprise the organic phase LiFeCl that obtains in the described extraction step
42TBP adds the washing step that dilute hydrochloric acid is removed impurity.
Preferably, between described back extraction step and phase inversion step, further comprise and wash sour step, with the organic phase HFeCl of deionized water to generating in the described back extraction step
42TBP washs.
Preferably, further comprise from described back extraction step to water LiCl solution in isolate the step of hydrochloric acid.
Preferably, adopt membrane separation technique from water LiCl solution, to isolate hydrochloric acid.
Preferably, further comprise described water LiCl solution is processed the step that obtains lithium salts.
Preferably, described water LiCl solution removal impurity and dehydration are obtained anhydrous LiCl product.
Preferably, in described water LiCl solution, add the NaOH neutralization, add Na
2CO
3Obtain anhydrous Li after precipitation, washing and the dehydration
2CO
3Product.
Compared to prior art, the present invention extracts lithium salts from contain lithium bittern method adopts alkali metal chloride, alkaline earth metal chloride or the two mixture in the process of phase inversion agent comes alternate base as phase inversion, under the prerequisite that does not consume alkali, realize the phase inversion of organic phase, and the agent of this kind phase inversion the extraction lithium process in can obtain, reduced production cost; In addition, also avoid Fe
3+Hydrolysis, and improved the utilization ratio of organic phase.
Description of drawings
Fig. 1 is the present invention extracts lithium salts from contain lithium bittern schematic flow sheet.
Fig. 2 obtains anhydrous Li from LiCl solution among the present invention
2CO
3The schematic flow sheet of product.
Fig. 3 is the schematic flow sheet that obtains anhydrous LiCl product among the present invention from LiCl solution.
Embodiment
Below in conjunction with accompanying drawing preferred embodiment of the present invention is described in detail, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
See also Fig. 1, the present invention extracts lithium salts from contain lithium bittern step is as follows:
Step S1: carry out pre-treatment to containing lithium bittern.Utilize natural energy or fuel will contain lithium bittern and be concentrated into certain concentration, separate and separate out sodium salt, sylvite, magnesium salts and part of sulfuric acid salt, it contains lithium bittern total chloridion concentration and reaches more than the 6mol/L.There is boron to exist in the lithium bittern if contain, carries out the boron lithium and separate.Certainly, for containing lithium bittern through what decon was processed, step S1 can save.
Step S2: extraction.In Halogen lithium water, add and extract altogether agent FeCl
3, form LiFeCl in the solution
4, and add extraction agent tributyl phosphate (TBP), and carry out extraction of lithium, obtain LiFeCl
42TBP (organic phase).The principle of extraction is: FeCl
3+ Cl
-=FeCl
4 -
Li
++ FeCl
4 -+ 2TBP=LiFeCl
42TBP (organic phase)
In this step, extraction agent is tributyl phosphate (TBP), and adopts thinner to dilute, and forms organic phase solution, and thinner is (sulfonated kerosene, aviation spirit, aromatic hydrocarbon); Extraction conditions is: TBP concentration=40%～100%; Compare=the extraction agent phase volume/contain lithium bittern volume=1.0～5.0; The volumetric molar concentration of the volumetric molar concentration of iron lithium ratio=iron trichloride/contain lithium in the lithium bittern=0.05～3.0; Contain the hydrogen ion concentration of lithium bittern=0.01～0.10 volumetric molar concentration; Reaction times=1512 minute.Among the step S2, except obtaining organic phase LiFeCl
4Outside the 2TBP, also obtain the raffinate of water, its main component is alkali metal chloride, alkaline earth metal chloride or the mixture solution of the two.
Step S3: washing.Adopt dilute hydrochloric acid (HCl) to organic phase LiFeCl
42TBP washs, flush away organic phase LiFeCl
4The bittern of carrying secretly among the 2TBP.Wash conditions: concentration of hydrochloric acid=0.05～2.0 mole; Compare=load organic phases volume/washing composition volume=1.0～20; Reaction times=1～8 minute.Certainly, if organic phase LiFeCl
4The bittern of carrying secretly among the 2TBP is less, and step S3 can save.
Step S4: back extraction.Organic phase LiFeCl after washing
42TBP adds the extraction agent concentrated hydrochloric acid solution and strips, and the lithium back extraction in the load organic phases to aqueous phase, is obtained HFeCl
42TBP (organic phase) and LiCl (water).Its principle is:
LiFeCl
42TBP (organic phase)+H
+(water)=HFeCl
42TBP (organic phase)+Li
+(water)
The reextraction condition is: concentration of hydrochloric acid=2～10 mole (mol/L); Compare=load organic phases volume/hydrochloric acid volume=1.0～20; Reaction times=0.2～12 minute.
Step S5: wash acid.With the organic phase HFeCl of deionized water to generating among the step S4
42TBP washs.Organic phase HFeCl through the concentrated hydrochloric acid back extraction
42TBP can carry the sub-fraction free acid secretly.On the one hand, with free acid H
2O washs both recoverables, can reduce again the consumption of phase inversion process phase inversion agent.If the free acid content of carrying secretly among the step S4 is less, step S5 can save.
Step S6: phase inversion.With alkali metal chloride, alkaline earth metal chloride or the mixture M Cl of the two
nSolution as the phase inversion agent to containing hydrionic organic phase HFeCl
42TBP carries out phase inversion, obtains MFeCl
42TBP (organic phase) and HCl (water) make organic phase recover extracting power.
Its reaction principle is:
NHFeCl
42TBP (organic phase)+MCl
n(water)=M (FeCl
4)
n2TBP (organic phase)+nHCl (water)
The reaction conditions of phase inversion is: alkali metal chloride or alkaline earth metal chloride MCl
nConcentration=2～10 mole (mol/L); Compare=hydrogeneous organic phase volume/phase inversion agent volume=0.25～10; Reaction times=0.2～12 minute.Recover the organic phase M (FeCl of extracting power
4)
n2TBP can further be applied among the step S2 as extraction agent.Among the step S6, can adopt raffinate among the step S2 as the phase inversion agent.
Step S7: isolate the hydrochloric acid in the water LiCl solution.Have a small amount of impurity in the stripping solution, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, with membrane separation technique most of hydrochloric acid is separated.
Step S8: the LiCl solution to water is processed, and obtains lithium salts.
As shown in Figure 2, if the preparation lithium carbonate product will remain small part HCl with the NaOH neutralization and remove the impurity such as magnesium and iron in the lithium chloride solution in the LiCl solution.Then with solution filter, remove impurity and obtain refining lithium chloride solution, in this solution, add yellow soda ash (Na
2CO
3) generation Quilonum Retard (Li
2CO
3) product, its slip is carried out filtration washing, and the oven dry of anhydrating of this filter cake is Quilonum Retard (Li
2CO
3) product, its Li
2CO
3Purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
As shown in Figure 3, if the preparation lithium chloride products will remain small part HCl with the LiOH neutralization and remove magnesium and iron in the lithium chloride solution in the LiCl solution.Then solution evaporation is extremely done, water leaching separation boron magnesium slag adds bariumchloride (BaCl when water logging
2) solution can remove sulfate ion, with the water logging solution filter, remove impurity and obtain refining lithium chloride solution.With the oven dry of ℃ anhydrating of this solution evaporation to 150, and with 250～280 ℃ of dehydrations, cooling is broken up and is Lithium chloride (anhydrous) (LiCl) product, its LiCl purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
From contain lithium bittern, extract the method for lithium salts below in conjunction with some specific embodiment explanation the present invention.
Specific embodiment 1
In a separating funnel, add 1 part of certain salt lake and contain lithium bittern (Mg/Li=1～1630 mol ratios, hydrogen ion concentration=0.01～0.10 volumetric molar concentration), add a certain amount of FeCl
3(concentration to 0.05 in bittern～3.0mol/L) as extracting agent altogether, shake and make it dissolving.Add 1～3 part of extraction agent (comparing O/A=1～3), the content 40～100% (V%) of tributyl phosphate extraction agent in organic phase, vibration extracted less than 10 minutes.After vibration finishes, static layering and phase-splitting.Can obtain the percentage extraction of Li greater than 97% by multi-stage counter current extraction or fractionation extraction process.After extraction, contain lithium organic phase LiFeCl
42TBP adds dilute hydrochloric acid (H according to wash conditions
+Concentration=0.05～2.0mol/L)) except the deentrainment partial impurities.Organic phase LiFeCl after washing
42TBP adds concentrated hydrochloric acid (H according to the reextraction condition
+Concentration=2～10 mole mol/L) solution is stripped, and obtains water LiCl and organic phase HFeCl
42TBP.
Have a small amount of impurity in the water LiCl solution that obtains after the reextraction, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, evaporation concentration stripping workshop or most of hydrochloric acid is separated with membrane separation technique.Residue small part HCl is with the LiOH neutralization and remove magnesium and iron in the lithium chloride solution.Then solution evaporation is extremely done, water leaching separation boron magnesium slag adds bariumchloride (BaCl when water logging
2) solution can remove sulfate ion, with the water logging solution filter, remove impurity and obtain refining LiCl solution.With the oven dry of ℃ anhydrating of this solution evaporation to 150, and in 250～280 ℃ of dehydrations, cooling is broken up and is the Lithium chloride (anhydrous) product, and its LiCl purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
The organic phase HFeCl that obtains after the reextraction
4Free acid deionized water wash among the 2TBP reclaims hydrochloric acid.Contain hydrionic organic phase HFeCl
42TBP alkaline earth metal chloride solution, i.e. MgCl
2Solution (MgCl
2Phase inversion is carried out to organic phase in concentration=4～10mol/L), obtains organic phase Mg (FeCl
4)
22TBP makes organic phase recover extracting power, organic phase Mg (FeCl
4)
22TBP recycles.
Specific embodiment 2
In a separating funnel, add 1 part of certain salt lake and contain lithium bittern (Mg/Li=1～1630 mol ratios, hydrogen ion concentration=0.01～0.10 volumetric molar concentration), add a certain amount of FeCl
3(concentration is to 0.05-3.0mol/L in bittern) shakes and makes it dissolving as extracting agent altogether.Add 1～3 part of extraction agent (comparing O/A=1～3), the content 40～100% (V%) of tributyl phosphate extraction agent in organic phase, vibration extracted less than 10 minutes.After vibration finishes, static layering and phase-splitting.Can obtain the percentage extraction of Li greater than 97% by multi-stage counter current extraction or fractionation extraction process.After extraction, contain lithium organic phase LiFeCl
42TBP adds dilute hydrochloric acid (H according to wash conditions
+Concentration=0.05～2.0mol/L)) except the deentrainment partial impurities.Organic phase LiFeCl after washing
42TBP adds concentrated hydrochloric acid (H according to the reextraction condition
+Concentration=2～10 mole mol/L) solution is stripped, and obtains water LiCl and organic phase HFeCl
42TBP.
Have a small amount of impurity in the water LiCl solution that obtains after the reextraction, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, evaporation concentration stripping workshop or most of hydrochloric acid is separated with membrane separation technique.Residue small part HCl is with the LiOH neutralization and remove magnesium and iron in the lithium chloride solution.Then solution evaporation is extremely done, water leaching separation boron magnesium slag adds bariumchloride (BaCl when water logging
2) solution can remove sulfate ion, with the water logging solution filter, remove impurity and obtain refining LiCl solution.With the oven dry of ℃ anhydrating of this solution evaporation to 150, and with 250～280 ℃ of dehydrations, cooling is broken up and is the Lithium chloride (anhydrous) product, its LiCl purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
The organic phase HFeCl that obtains after the reextraction
4Free acid deionized water wash among the 2TBP reclaims hydrochloric acid.Contain hydrionic organic phase HFeCl
42TBP alkaline earth metal chloride solution, i.e. CaCl
2Solution (CaCl
2Phase inversion is carried out to organic phase in concentration=4～12mol/L), obtains organic phase C a (FeCl
4)
22TBP makes organic phase recover extracting power, organic phase C a (FeCl
4)
22TBP recycles.
Specific embodiment 3
In a separating funnel, add 1 part of certain salt lake and contain lithium bittern (Mg/Li=1～1630 mol ratios, hydrogen ion concentration=0.01～0.10 volumetric molar concentration), add a certain amount of FeCl
3(concentration is to 0.05-3.0mol/L in bittern) shakes and makes it dissolving as extracting agent altogether.Add 1～3 part of extraction agent (comparing O/A=1～3), the content 40～100% (V%) of tributyl phosphate extraction agent in organic phase, vibration extracted less than 10 minutes.After vibration finishes, static layering and phase-splitting.Can obtain the percentage extraction of Li greater than 97% by multi-stage counter current extraction or fractionation extraction process.After extraction, contain lithium organic phase LiFeCl
42TBP adds dilute hydrochloric acid (H according to wash conditions
+Concentration=0.05～2.0mol/L)) except the deentrainment partial impurities.Organic phase LiFeCl after washing
42TBP adds concentrated hydrochloric acid (H according to the reextraction condition
+Concentration=2～10 mole mol/L) solution is stripped, and obtains water LiCl and organic phase HFeCl
42TBP.
Have a small amount of impurity in the water LiCl solution that obtains after the reextraction, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, evaporation concentration stripping workshop or most of hydrochloric acid is separated with membrane separation technique.Residue small part HCl is with the NaOH neutralization and remove the impurity such as magnesium and iron in the LiCl solution.Then with solution filter, remove impurity and obtain refining LiCl solution, in this solution, add yellow soda ash (Na
2CO
3) generation Quilonum Retard (Li
2CO
3) product, its slip is carried out filtration washing, and the filter cake oven dry of anhydrating is Quilonum Retard (Li
2CO
3) product, its Li
2CO
3Purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
Organic phase HFeCl
4Free acid deionized water wash among the 2TBP reclaims hydrochloric acid.Contain hydrionic organic phase HFeCl
4The 2TBP alkali metal chloride solution, namely (phase inversion is carried out to organic phase in NaCl concentration=4～6mol/L) to NaCl solution, obtains organic phase NaFeCl
42TBP makes organic phase recover extracting power, organic phase NaFeCl
42TBP recycles.
Specific embodiment 4
In a separating funnel, add 1 part of certain salt lake and contain lithium bittern (Mg/Li=1～1630 mol ratios, hydrogen ion concentration=0.01～0.10 volumetric molar concentration), add a certain amount of FeCl
3(concentration is to 0.05-3.0mol/L in bittern) shakes and makes it dissolving as extracting agent altogether.Add 1～3 part of extraction agent (comparing O/A=1～3), the content 40～100% (V%) of tributyl phosphate extraction agent in organic phase, vibration extracted less than 10 minutes.After vibration finishes, static layering and phase-splitting.Can obtain the percentage extraction of Li greater than 97% by multi-stage counter current extraction or fractionation extraction process.After extraction, contain lithium organic phase LiFeCl
42TBP adds dilute hydrochloric acid (H according to wash conditions
+Concentration=0.05～2.0mol/L)) except the deentrainment partial impurities.Organic phase LiFeCl after washing
42TBP adds concentrated hydrochloric acid (H according to the reextraction condition
+Concentration=2～10 mole mol/L) solution is stripped, and obtains water LiCl and organic phase HFeCl
42TBP.
Have a small amount of impurity in the water LiCl solution that obtains after the reextraction, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, evaporation concentration stripping workshop or most of hydrochloric acid is separated with membrane separation technique.Residue small part HCl is with the NaOH neutralization and remove the impurity such as magnesium and iron in the LiCl solution.Then with solution filter, remove impurity and obtain refining LiCl solution, in this solution, add yellow soda ash (Na
2CO
3) generation Quilonum Retard (Li
2CO
3) product, its slip is carried out filtration washing, and the filter cake oven dry of anhydrating is Quilonum Retard (Li
2CO
3) product, its Li
2CO
3Purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
The organic phase HFeCl that obtains after the reextraction
4Free acid deionized water wash among the 2TBP reclaims hydrochloric acid.Contain hydrionic organic phase HFeCl
4The 2TBP alkali metal chloride solution, namely (KCl concentration=4mol/L) organic phase is carried out phase inversion obtains organic phase KFeCl to KCl solution
42TBP makes organic phase recover extracting power, organic phase KFeCl
42TBP recycles.
In a separating funnel, add 1 part of certain salt lake and contain lithium bittern (Mg/Li=1～1630 mol ratios, hydrogen ion concentration=0.01～0.10 volumetric molar concentration), add a certain amount of FeCl
3(concentration is to 0.05-3.0mol/L in bittern) shakes and makes it dissolving as extracting agent altogether.Add 1～3 part of extraction agent (comparing O/A=1～3), the content 40～100% (V%) of tributyl phosphate extraction agent in organic phase, vibration extracted less than 10 minutes.After vibration finishes, static layering and phase-splitting.Can obtain the percentage extraction of Li greater than 97% by multi-stage counter current extraction or fractionation extraction process.After extraction, contain lithium organic phase LiFeCl
42TBP adds dilute hydrochloric acid (H according to wash conditions
+Concentration=0.05～2.0mol/L)) except the deentrainment partial impurities.Organic phase LiFeCl after washing
42TBP adds concentrated hydrochloric acid (H according to the reextraction condition
+Concentration=2～10 mole mol/L) solution is stripped, and obtains water LiCl and organic phase HFeCl
42TBP.
Have a small amount of impurity in the water LiCl solution that obtains after the reextraction, its chief component is the impurity such as organism, boron, magnesium, sulfate radical, hydrochloric acid, trace iron, evaporation concentration stripping workshop or most of hydrochloric acid is separated with membrane separation technique.Residue small part HCl is with the NaOH neutralization and remove the impurity such as magnesium and iron in the LiCl solution.Then with solution filter, remove impurity and obtain refining LiCl solution, in this solution, add yellow soda ash (Na
2CO
3) generation Quilonum Retard (Li
2CO
3) product, its slip is carried out filtration washing, and the filter cake oven dry of anhydrating is Quilonum Retard (Li
2CO
3) product, its Li
2CO
3Purity 〉=99% contains lithium bittern to product from raw material, lithium total yield 〉=90%.
The organic phase HFeCl that obtains after the reextraction
4Free acid deionized water wash among the 2TBP reclaims hydrochloric acid.Contain hydrionic organic phase HFeCl
42TBP is with raffinate (MgCl wherein
24～10mol/L, NaCl 0.01～3mol/L, KCl 0.01～2mol/L) carries out phase inversion to organic phase, obtains organic phase M (FeCl
4)
n2TBP makes organic phase recover extracting power, organic phase M (FeCl
4)
n2TBP recycles.
In the present invention, be not limited to NaCl, KCl as the alkali metal chloride of phase inversion agent, other alkali metal chloride such as RuCl, CeCl, FrCl also can be used as the phase inversion agent; Alkaline earth metal chloride is not limited to MgCl
2, CaCl
2, other alkaline earth metal chloride such as BeCl
2, StCl
2, BaCl
2And RaCl
2Also can be used as the phase inversion agent.Because Na, K, Mg, Ca, Ba are higher at the content of occurring in nature, procurement cost is lower, and is therefore preferred, adopts NaCl, KCl, MgCl
2, CaCl
2, BaCl
2In one or more as the phase inversion agent.
Compared to prior art, the present invention extracts lithium salts from contain lithium bittern method adopts alkali metal chloride, alkaline earth metal chloride or the two mixture in the process of phase inversion agent comes alternate base as phase inversion, under the prerequisite that does not consume alkali, realize the phase inversion of organic phase, and the agent of this kind phase inversion the extraction lithium process in can obtain, reduced production cost; In addition, also avoid Fe
3+Hydrolysis, and improved the utilization ratio of organic phase.
Only be preferred case study on implementation of the present invention below, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (11)
1. method of extracting lithium salts from contain lithium bittern is characterized in that comprising:
Extraction step extracts agent FeCl altogether to containing to add in the lithium bittern
3, extraction agent tributyl phosphate (TBP), carry out extraction of lithium, obtain organic phase LiFeCl
42TBP and water raffinate;
The back extraction step is to organic phase LiFeCl
4Add hydrochloric acid soln among the 2TBP and strip, obtain organic phase HFeCl
42TBP and water LiCl;
The phase inversion step is with alkali metal chloride, alkaline earth metal chloride or the mixture M Cl of the two
n(n 〉=1) solution as the phase inversion agent to containing hydrionic organic phase HFeCl
42TBP carries out phase inversion, obtains organic phase M (FeCl
4)
n2TBP.
2. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that the water raffinate that obtains in the described extraction step further is applied in the described phase inversion step as the phase inversion agent.
3. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that described phase inversion agent MCl
nBe KCl, NaCl, CaCl
2, MgCl
2, BaCl
2In one or more.
4. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that the reaction conditions in the described phase inversion step is: phase inversion agent MCl
nConcentration=2～10 mole (mol/L); Compare=hydrogeneous organic phase volume/phase inversion agent volume=0.25～10; Reaction times=0.2～12 minute.
5. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that, between described extraction step and back extraction step, further comprises the organic phase LiFeCl that obtains in the described extraction step
42TBP adds the washing step that dilute hydrochloric acid is removed impurity.
6. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that, between described back extraction step and phase inversion step, further comprises and washes sour step, with the organic phase HFeCl of deionized water to generating in the described back extraction step
42TBP washs.
7. the method for extracting lithium salts from contain lithium bittern according to claim 1 is characterized in that, further comprise from described back extraction step to water LiCl solution in isolate the step of hydrochloric acid.
8. the method for extracting lithium salts from contain lithium bittern according to claim 7 is characterized in that, adopts membrane separation technique to isolate hydrochloric acid from water LiCl solution.
9. according to claim 1 or the 7 described methods of from contain lithium bittern, extracting lithium salts, it is characterized in that, further comprise described water LiCl solution is processed the step that obtains lithium salts.
10. the method for extracting lithium salts from contain lithium bittern according to claim 9 is characterized in that, described water LiCl solution removal impurity and dehydration are obtained anhydrous LiCl product.
11. the method for extracting lithium salts from contain lithium bittern according to claim 9 is characterized in that, adds the NaOH neutralization in described water LiCl solution, adds Na
2CO
3Obtain anhydrous Li after precipitation, washing and the dehydration
2CO
3Product.
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