CN109260950A - A kind of method for separating and concentrating of lithium isotope - Google Patents
A kind of method for separating and concentrating of lithium isotope Download PDFInfo
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Abstract
The invention discloses a kind of method for separating and concentrating of lithium isotope, it is comprising steps of S1, preparation extraction organic phase: using crown ether derivative shown in following formula A or formula B as extractant, extractant is mixed with hydrophobic ionic liquid and diluent, obtains extraction organic phase；S2, it prepares aqueous phase extracted: water-soluble lithium salts being configured to lithium salt solution, as aqueous phase extracted；S3, will extraction organic phase and aqueous phase extracted be sufficiently mixed extraction after carry out split-phase, obtain load organic phases and raffinate；S4, by load organic phases at a temperature of 400 DEG C~1000 DEG C calcination 30min~200min, obtain slag phase；S5, slag phase is dissolved with water, and is separated by solid-liquid separation, obtained6Li pregnant solution；S6, with6Li pregnant solution is as aqueous phase extracted, and repeat the above steps S3~S5.The present invention is based on crown ether-like extraction systems to provide a kind of completely new process without back extraction operation, is a kind of quickly superposition cross-flow multi-stage cascade separation method, the method for enriching separation and concentration lithium isotope.
Description
Technical field
The invention belongs to lithium isotope separation and concentration technology fields, it relates in particular to which a kind of separation of lithium isotope is rich
Set method.
Background technique
Nuclear Power Development is placed on highly important status by China, meanwhile, China is also international controlled thermonuclear fusion plan
(ITER) project is primarily involved in unit, and country successively starts correlation engineering project thus.Such as, 2002, Ministry of Nuclear Industry west
Nan Wuliyanjiuyuan builds up " No. two A of state's circulator ", pre- by carrying out the key projects technologies such as novel divertor, superconducting magnet
It grinds, ETR Engineering Test Reactor design, investigation of materials and its critical component beforehand research, provides skill for design-build deuterium tritium corrosion chamber
Art and physical basis.2006, Hefei Inst. of Plasma Physics, Chinese Academy of Sciences, which has built up in the world, while to be had complete by first
The nuclear fusion experimental device of superconducting magnet and active cooling structure.According to " controlled nuclear fusion " engineering progress, scientist is optimistically
Nuclear fusion power generation will can be achieved in estimation within 30~50 years futures.2011, China formally started " the following advanced nuclear fission-again
The relevant item of thorium base molten salt reactor nuclear power system ".Fusion reactor, the key reaction being related to be D+T →4He+n, i.e. deuterium
(D) huge energy can be released when and tritium (T) aggregates into helium (He) core.The resource of deuteron (D) on earth is extremely abundant, and
Existing amount is few in nature for another raw material tritium (T).
There are two kinds of stable isotopes in nature for lithium (Li)6Li and7Li, their natural abundance (refer to6Li and7Li's
Natural percentage contents) it is 7.42% and 92.58% respectively.Both isotopes all have of crucial importance in nuclear energy source domain
Effect.Wherein, thermal neutron absorption cross section is up to 940b's6Li can be generated after neutron (n) bombardment fission tritium and helium (6Li+n→T
+4He), so certain abundance6Li can be used as the raw material and other purposes of nuclear fusion；And thermal neutron absorption cross section is only 0.037b
's7Li has important role to the regulation of nuclear process and the maintenance of equipment.
Currently, there are many kinds of the single-stage separation methods of lithium isotope chemical method and physical method can be divided into, wherein chemical method packet
Include lithium amalgam exchange process, ion exchange chromatography, extraction etc.；Physical method includes electromagnetic method, electron transfer, molecular distillation and swashs
Light separation etc..Physical method is not suitable for being applied to because of the features such as production equipment valuableness and working condition are harsh, energy consumption is high but yield is small
Industrialized production.Lithium amalgam method separation lithium isotope haves the shortcomings that very big, and a large amount of mercury metal tapes have been used in separation process
Carry out ecological environmental and safety problems, the states such as America and Europe have been turned off some factories with lithium amalgam method separation lithium isotope.Since
Pedersen discovery crown ether compound can have complexing work with alkali metal ion according to its cavity size selectivity within 1976
It is used to, the related isotopic separation research based on crown ether mainly has solvent liquid-liquid extraction method and ion exchange chromatography.But
It is, on the one hand, these are all the exploration levels for resting on single-stage system to the technique study of lithium isotope separation and concentration, and separation is rich
Collect limited efficacy；On the other hand, the general technology of the solvent liquid-liquid extraction method based on crown ether is also the process of extracting-back extraction, but
It is that, current study show that can be carried out back extraction to the lithium isotope in enrichment phase with the hydrochloric acid solution of high concentration, continuous back extraction is at least
Five times could be to lithium isotope in load organic phases6Li carries out relatively complete recycling, and reverse-extraction method is utilized to be separated in single-stage extraction
There is biggish advantage, it is renewable to achieve the purpose that recycle organic phase, reduce separation costs.But applying to multistage extraction
When taking separation, since pH value has a great impact (such as J.Xiao et al.Journal of to lithium isotope extraction and separation
Molecular Liquids.2016,223:1032-1038), i.e., it not can be carried out extraction and separation in acid condition.
During the separation and concentration of lithium isotope, lithium isotope6The every raising 0.1% of the abundance of Li is all extremely difficult
's.Such as stone Cheng Long (C.Shi et al.Journal of Molecular Liquids.2016,224:662-667) utilizes
It is extractant that dibenzo 14, which is preced with four (DB14C4), when lithium chloride (LiCl) is water phase, only can by extracting-back extraction method
It will6The relative abundance of Li is increased to 7.634% from 7.563%, only improves only 0.071%.
Summary of the invention
To solve the above-mentioned problems of the prior art, the present inventor is carrying out lithium based on crown ether-like extraction system
It is found during the separation and concentration of isotope, extracts the load organic phases of acquisition after the hydrochloric acid solution of high concentration is stripped,
It obtains6Acidity is presented in Li pregnant solution, can not further extract directly as aqueous phase extracted.And if this with sodium hydroxide
Alkaline matter, which is neutralized, adjusts pH to neutrality, on the one hand can introduce heteroion；On the other hand, by adjusting pH's6Li
Pregnant solution is used as aqueous phase extracted again, of the invention when fresh extraction organic phase progress next stage extraction and separation being added thereto
There is thick white solid after finding oscillation in an experiment in inventor, and the organic phase in system is destroyed, can not carry out down
The experiment of one step；This discovery with above-mentioned " pH has a significant impact to lithium isotope extraction and separation, not can be carried out extraction in acid condition
Take separation " research discovery conclusion be also perfectly in harmony.Therefore under the premise of being based on crown ether-like extraction system, it is necessary to seek
It looks for one kind that can recycle to lithium isotope, does not bring lithium isotope in the load organic phases of heteroion into also6The recycling side of Li
Method.
For this purpose, the method for separating and concentrating provides one kind the present invention provides a kind of method for separating and concentrating of lithium isotope
The completely new process without back extraction operation based on crown ether-like extraction system.
In order to achieve the above object of the invention, present invention employs the following technical solutions:
A kind of method for separating and concentrating of lithium isotope, comprising steps of
S1, extraction organic phase is prepared: using crown ether derivative shown in following formula A or formula B as extractant, by the extraction
Agent is mixed with hydrophobic ionic liquid and diluent, obtains extraction organic phase；
Wherein, the value of n is 0,1,2；R be selected from hydrogen atom, dialkyl amido, alkyl amino, amino, hydroxyl, alkoxy,
Amide groups, ester group, phenyl, acyl group, aldehyde radical, carboxyl, sulfonyl, cyano, any one in nitro；
S2, it prepares aqueous phase extracted: water-soluble lithium salts being configured to lithium salt solution, as aqueous phase extracted；
S3, extraction: the extraction organic phase and the aqueous phase extracted are sufficiently mixed extraction according to the volume ratio of 1~4:1~5
Split-phase is carried out after taking, and obtains load organic phases and raffinate；
S4, calcination: calcination 30min~200min, acquisition at a temperature of 400 DEG C~1000 DEG C by the load organic phases
Slag phase；
It is S5, water-soluble: to dissolve the slag phase with water, and be separated by solid-liquid separation, obtained6Li pregnant solution；
S6, with described6Li pregnant solution repeats the above steps S3~S5 at least 2 times as aqueous phase extracted.
Further, the method for separating and concentrating further comprises the steps of:
Q, using the raffinate as aqueous phase extracted, repeat the above steps S3.
Further, in the step S1, the concentration of the extractant is 0.05mol/L~2mol/L.
Further, R is selected from hydrogen atom, dialkyl amido, alkyl amino, amino, hydroxyl, alkoxy, amide groups, ester
Any one in base, phenyl.
Further, cation shown in hydrophobic ionic liquid anion as shown in following formula C and following formula D
Composition:
Further, in the step S1, the ratio between volume of the hydrophobic ionic liquid and the diluent is 1:9
~3:1.
Further, the diluent be selected from methyl phenyl ethers anisole, chloroform, kerosene, methylene chloride, 1,2- dichloroethanes, n-hexane,
Normal heptane, carbon tetrachloride, toluene, dimethylbenzene, diethylbenzene, bromobenzene, any one in nitrobenzene.
Further, Li in the lithium salt solution+Concentration be 0.1mol/L~4mol/L；And/or the water-soluble lithium
Salt is selected from least one of lithium chloride, lithium bromide, lithium iodide, trifluoroacetic acid lithium, bis- (fluoroform sulphonyl) imine lithiums.
Further, in the step S3,5min is shaken after the extraction organic phase and the aqueous phase extracted being mixed
~80min is sufficiently to extract, then is centrifuged 1min~10min and carries out split-phase.
Further, in the step S4, with 1 DEG C/min~15 DEG C/min heating rate by the load organic phases
Calcination is carried out at a temperature of being warming up to 400 DEG C~1000 DEG C.
Further, in the step S5, the slag is dissolved not less than the ultrapure water of 18.25 Ω cm with resistivity
Phase.
The present invention is based on crown ether-like extraction systems to provide a kind of completely new process without back extraction operation, should
Operation of the process by recycling " extraction-calcination-is water-soluble " several times, that is, can reach separation welfare lithium isotope6The mesh of Li
, it is a kind of quickly superposition cross-flow multi-stage cascade separation method, method for enriching separation and concentration lithium isotope, makes based on hat
The method for separating and concentrating of ether extration system is not limited to multitple extraction-multistage back extraction technique.The method for separating and concentrating is by upper
The continuous operation for stating 3 times " extraction-calcination-is water-soluble ", can make6The abundance of Li is promoted at least 7.86%, is higher than the prior art
Mean level, separation and concentration effect is good.Also, this kind is by calcination by the lithium isotope in load organic phases6Li is again
The method being transferred in aqueous solution, caused single-stage is stripped effect when also can avoid the general transfer by reverse-extraction method in the prior art
Rate is low to cause lithium isotope6Li loss is big, and multistage back extraction cause the pH of the aqueous solution generated it is too low can not be extracted again,
The problem of needing lye to adjust and necessarily introduce impurity；By lithium isotope in load organic phases by way of calcination6Li is not only
It is recycled, and calcination will not make subsequent water-soluble generation6Heteroion is not brought into Li pregnant solution, in addition, this method
Without using any pH adjusting agent, to not influence to acquisition6Li pregnant solution is further extracted.
Specific embodiment
Hereinafter, detailed description of the present invention embodiment in future.However, it is possible to implement this hair in many different forms
It is bright, and the present invention should not be construed as limited to the specific embodiment illustrated here.On the contrary, provide these embodiments be for
Explanation the principle of the present invention and its practical application, to make others skilled in the art it will be appreciated that of the invention is various
Embodiment and the various modifications for being suitable for specific intended application.
Term " first ", " second " etc. herein can be used to describe various substances although will be appreciated that, these
Substance should not be limited by these terms.The substance area that these terms are only used to obtain a substance and another same operation
It separates.
Based in the prior art based on the separation and concentration lithium isotope of crown ether-like extraction system6The method of Li only has multistage extraction
Take-this is a kind of for multistage back extraction, the more single drawback of process, the present inventor sends out in long-term correlative study
It is existing, the separation and concentration lithium isotope based on crown ether-like extraction system6The method of Li also can avoid can will be through extracting using reverse-extraction method
It takes in the load organic phases of acquisition6Li is transferred in water phase, higher to obtain an abundance6Li aqueous solution；For this purpose, providing
A kind of method for separating and concentrating of completely new lithium isotope.
The method for separating and concentrating is a kind of superposition cross-flow multi-stage cascade of circulate operation based on " extraction-calcination-is water-soluble "
Separation method；Itself specifically include the following steps:
In step sl, extraction organic phase is prepared.
Extraction step in the method for separating and concentrating is carried out based on following crown ether-like extraction system.
Specifically, in the extraction organic phase, specifically include that using the crown ether derivative that following formula A or formula B are indicated as
The hydrophobic ionic liquid of cation composition shown in extractant, the anion as shown in following formula C and following formula D and dilute
Release agent.
Wherein, in formula A, the value of n is 0,1,2.R is selected from hydrogen atom, dialkyl amido, alkyl amino, amino, hydroxyl
Base, alkoxy, amide groups, ester group, phenyl, acyl group, aldehyde radical, carboxyl, sulfonyl, cyano, any one in nitro；It preferably is selected from
These electron-donating groups of hydrogen atom, dialkyl amido, alkyl amino, amino, hydroxyl, alkoxy, amide groups, ester group, phenyl.
The specific structure of extractant represented by above-mentioned formula A is as shown in table 1 below.
The specific structure of the extractant shown in formula A of table 1
It is worth noting that above-mentioned hydrophobic ionic liquid is a kind of both conducts in method for separating and concentrating of the invention
Synergic reagent is the ionic liquid at room temperature of green solvent again.
Further, diluent can selected from methyl phenyl ethers anisole, chloroform, kerosene, methylene chloride, 1,2- dichloroethanes, n-hexane,
Normal heptane, carbon tetrachloride, tetrachloro-ethylene, toluene, dimethylbenzene, diethylbenzene, bromobenzene, any one in nitrobenzene.
More specifically, above-mentioned extractant is mixed with hydrophobic ionic liquid and diluent, it is organic can be obtained extraction
Phase；It is preferred that in the extraction organic phase, the concentration for controlling extractant is 0.05mol/L~2mol/L, hydrophobic ionic liquid with
The ratio between volume of diluent is 1:9~3:1.
In step s 2, aqueous phase extracted is prepared.
Specifically, water-soluble lithium salts is configured to lithium salt solution, that is, is used as aqueous phase extracted.
It is worth noting that because being only capable of quantitative determination Li for the test of lithium content at present+Total amount, i.e., can not be right6Li
With7Li is quantitative determined, and the relative amount (i.e. abundance) of the two can be only measured, therefore, in prepared lithium salt solution, Li+
Concentration for lithium isotope6The separation and concentration effect of Li has no too much influence, i.e., in the lithium salt solution of any concentration, generally
Follow6Li and7The natural abundance of Li is distributed, i.e., and respectively 7.42% and 92.58%.
It is general to prepare wherein Li in method for separating and concentrating of the invention+Concentration be 0.1mol/L~4mol/L, preferably
Condition can be met for the lithium salt solution of 1mol/L；Also, water-soluble lithium salts is selected from lithium chloride, lithium bromide, lithium iodide, trifluoro second
At least one of sour lithium, bis- (fluoroform sulphonyl) imine lithiums.
In step s3, extraction organic phase and aqueous phase extracted are sufficiently mixed after extraction and carry out split-phase, it is organic to obtain load
Phase and raffinate.
Specifically, control is 1~4:1~5 compared to (extraction the ratio between organic phase and the volume of aqueous phase extracted).
Preferably, in above-mentioned extraction process, can will extraction organic phase and aqueous phase extracted mix after concussion 5min~80min with
Sufficiently extraction, then 1min~10min is centrifuged to carry out abundant split-phase, it is low to reduce yield caused by due to split-phase is not thorough.
In step s 4, calcination 30min~200min, acquisition at a temperature of 400 DEG C~1000 DEG C by load organic phases
Slag phase.
Preferably, load organic phases can be warming up to 400 DEG C~1000 DEG C with 1 DEG C/min~15 DEG C/min heating rate
At a temperature of carry out calcination.
In step s 5, slag phase is dissolved with water, and is separated by solid-liquid separation, obtained6Li pregnant solution.
Preferably, the ultrapure water with resistivity not less than 18.25 Ω cm dissolves slag phase.
In this way, the lithium that can be generally 7.51% by natural abundance is same by the operation of primary " extraction-sintering-is water-soluble "
Position element6The abundance of Li is promoted to 7.70% or so.
For this purpose, in order to further be enriched with lithium isotope6Li also needs to carry out following step:
In step s 6, with6Li pregnant solution repeats the above steps S3~S5 at least 2 times as aqueous phase extracted.
That is, obtained with above-mentioned steps S5 first6Li pregnant solution is matched as aqueous phase extracted, by it with step S1
The extraction organic phase that system obtains carries out being sufficiently mixed extraction according to the volume ratio of 1~5:1~4, and split-phase again, and gained load has
Machine mutually carries out calcination again, and slag phase obtained by calcination again can be water-soluble, obtains second6Li pregnant solution, as aqueous phase extracted,
And so on, the operation of 3 times " extraction-calcination-is water-soluble " is carried out altogether, it can be by lithium isotope6The abundance of Li is promoted at least
7.86%, it has been higher than the level of the prior art.
It is worth noting that being based on lithium isotope7The application of Li, is enriched with it and is equally played a significant role.For this purpose,
The above-mentioned raffinate obtained through step S3 split-phase is a lithium isotope in fact7The relatively higher aqueous solution of Li abundance, therefore
Can be using the raffinate as another aqueous phase extracted, it is separated again with the extraction organic phase that above-mentioned steps S1 prepares acquisition should
Lithium isotope in raffinate6Li, to realize lithium isotope in the raffinate obtained again7The enrichment again of Li.I.e. originally
The method for separating and concentrating of invention further includes step Q: using raffinate as aqueous phase extracted, repeat the above steps S3.Also, by raffinate
Liquid is as new aqueous phase extracted again to lithium isotope therein7It is obtained negative after Li carries out separation and concentration in raffinate
Being loaded with machine mutually still can carry out the water-soluble operation of above-mentioned calcination-, with further separation and concentration lithium isotope6Li improves the rate of recovery.
It will illustrate the method for separating and concentrating of above-mentioned lithium isotope of the invention, but ability by specific embodiment below
It is the specific example of above-mentioned method for separating and concentrating that field technique personnel, which will be appreciated that following embodiments only, and being not used in restriction, it is complete
Portion.
Embodiment 1
The present embodiment has carried out the lamination cross-flow lock out operation of three-stage cascade, that is, has carried out the behaviour of " extraction-calcination-is water-soluble "
Make three times.
The first order:
7mL aqueous phase extracted (0.5mol/L lithium chloride solution) first is added in the centrifuge tube of 50mL with liquid-transfering gun, adds
(extractant is phendioxin 5- crown ether -5 (B15C5) to the extraction organic phase of 7mL, hydrophobic ionic liquid is 1- ethyl -3- methyl miaow
Double trifluoromethanesulfonimide salt ([the EMIm] [NTf of azoles2]), diluent be methyl phenyl ethers anisole, the concentration of extractant is 0.05mol/L,
The volume ratio of hydrophobic ionic liquid and diluent is 3:7), it is placed on constant temperature oscillator and acutely shakes 40min, after the completion of concussion
Being transferred on supercentrifuge makes the complete split-phase of two-phase, obtains the first load organic phases and the first raffinate.
First load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination；Muffle furnace is set
(20 DEG C are warming up to 200 DEG C of used time 36min to heating and cooling program, and in 200 DEG C of holding 30min, 200 DEG C are warming up to 800 DEG C of used times
60min is warming up to 800 DEG C of used times holding 120min at 800 DEG C, and 800 DEG C cool to 300 DEG C of used time 50min, later natural cooling
To room temperature), obtain the first slag phase.
The first slag phase in platinum crucible is washed several times with the ultrapure moisture of 5mL, obtains first6Li pregnant solution；The first order
Enrichment abundance reached 7.74%.
The second level:
To first6The above-mentioned extraction organic phase of 5mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
40min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the second load organic phases and the second raffinate
Liquid.
Second load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the second slag phase.
With the second slag phase in 5mL milli-Q water platinum crucible, second is obtained6Li pregnant solution；The enrichment of the second level
Abundance reaches 7.84%.
The third level:
To second6The above-mentioned extraction organic phase of 5mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
40min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains third load organic phases and third raffinate
Liquid.
Third load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program obtains third slag phase.
With the third slag phase in 5mL milli-Q water platinum crucible, third is obtained6Li pregnant solution；The enrichment of the third level
Abundance reaches 7.97%.
Embodiment 2
The present embodiment has carried out the lamination cross-flow lock out operation of three-stage cascade, that is, has carried out the behaviour of " extraction-calcination-is water-soluble "
Make three times.
The first order:
10mL aqueous phase extracted (2mol/L lithium chloride solution) first is added in the centrifuge tube of 50mL with liquid-transfering gun, adds
(extractant is phendioxin 5- crown ether -5 to the extraction organic phase of 10mL, hydrophobic ionic liquid is 1- butyl -3- methylimidazole double three
Fluoromethane sulfimide salt ([BMIm] [NTf2]), diluent be methyl phenyl ethers anisole, the concentration of extractant is 0.4mol/L, hydrophobicity from
The volume ratio of sub- liquid and diluent is 2:3), it is placed on constant temperature oscillator and acutely shakes 60min, height is transferred to after the completion of concussion
Make the complete split-phase of two-phase on fast centrifuge, obtains the first load organic phases and the first raffinate.
First load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination；Muffle furnace is set
(20 DEG C are warming up to 200 DEG C of used time 36min to heating and cooling program, and in 200 DEG C of holding 30min, 200 DEG C are warming up to 800 DEG C of used times
60min, in 800 DEG C of holding 120min, 800 DEG C cool to 300 DEG C of used time 50min, later cooled to room temperature), obtain the
One slag phase.
The first slag phase in platinum crucible is washed several times with the ultrapure moisture of 10mL, obtains first6Li pregnant solution；The first order
Enrichment abundance reach 7.71%.
The second level:
To first6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the second load organic phases and the second raffinate
Liquid.
Second load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the second slag phase.
With the second slag phase in 10mL milli-Q water platinum crucible, second is obtained6Li pregnant solution；The enrichment of the second level
Abundance reaches 7.83%.
The third level:
To second6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains third load organic phases and third raffinate
Liquid.
Third load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program obtains third slag phase.
With the third slag phase in 10mL milli-Q water platinum crucible, third is obtained6Li pregnant solution；The enrichment of the third level
Abundance reaches 7.94%.
Embodiment 3
The present embodiment has carried out the cascade lamination cross-flow lock out operation of Pyatyi, that is, has carried out the behaviour of " extraction-calcination-is water-soluble "
Make five times.
The first order:
10mL aqueous phase extracted (3mol/L lithium iodide solution) first is added in the centrifuge tube of 50mL with liquid-transfering gun, adds
(extractant is phendioxin 5- crown ether -5 to the extraction organic phase of 10mL, hydrophobic ionic liquid is 1- ethyl-3-methylimidazole double three
Fluoromethane sulfimide salt, diluent are methyl phenyl ethers anisole, and the concentration of extractant is 0.5mol/L, hydrophobic ionic liquid and diluent
Volume ratio be 1:4), be placed on constant temperature oscillator and acutely shake 60min, be transferred on supercentrifuge after the completion of concussion and make two
Mutually complete split-phase obtains the first load organic phases and the first raffinate.
First load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination；Muffle furnace is set
(20 DEG C are warming up to 200 DEG C of used time 36min to heating and cooling program, and in 200 DEG C of holding 30min, 200 DEG C are warming up to 800 DEG C of used times
60min is warming up to 800 DEG C of used times holding 120min at 800 DEG C, and 800 DEG C cool to 300 DEG C of used time 50min, later natural cooling
To room temperature), obtain the first slag phase.
The first slag phase in platinum crucible is washed several times with the ultrapure moisture of 10mL, obtains first6Li pregnant solution.；This first
The enrichment abundance of grade has reached 7.71%.
The second level:
To first6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the second load organic phases and the second raffinate
Liquid.
Second load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the second slag phase.
With the second slag phase in 10mL milli-Q water platinum crucible, second is obtained6Li pregnant solution；The enrichment of the second level
Abundance reaches 7.80%.
The third level:
To second6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains third load organic phases and third raffinate
Liquid.
Third load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program obtains third slag phase.
With the third slag phase in 10mL milli-Q water platinum crucible, third is obtained6Li pregnant solution；The enrichment of the third level
Abundance reaches 7.90%.
The fourth stage:
To third6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 4th load organic phases and the 4th raffinate
Liquid.
4th load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program obtains the 4th slag phase.
With the 4th slag phase in 10mL milli-Q water platinum crucible, the 4th is obtained6Li pregnant solution；The enrichment of the fourth stage
Abundance reaches 7.97%.
Level V:
To the 4th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 5th load organic phases and the 5th raffinate
Liquid.
5th load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program obtains the 5th slag phase.
With the 5th slag phase in 10mL milli-Q water platinum crucible, the 5th is obtained6Li pregnant solution；The enrichment of the level V
Abundance reaches 8.14%.
Embodiment 4
The present embodiment has carried out ten grades of cascade lamination cross-flow lock out operation, that is, has carried out the behaviour of " extraction-calcination-is water-soluble "
Make ten times.
The first order:
20mL aqueous phase extracted (the bis- trifluoromethanesulfonimide lithium solution of 3.5mol/L) first are added to 50mL's with liquid-transfering gun
In centrifuge tube, adding the extraction organic phase of 10mL, (extractant is phendioxin 5- crown ether -5, hydrophobic ionic liquid is 1- fourth
The double trifluoromethanesulfonimide salt of base -3- methylimidazole, diluent are methyl phenyl ethers anisole, and the concentration of extractant is 1mol/L, hydrophobicity
The volume ratio of ionic liquid and diluent is 3:7), it is placed on constant temperature oscillator and acutely shakes 60min, be transferred to after the completion of concussion
Make the complete split-phase of two-phase on supercentrifuge, obtains the first load organic phases and the first raffinate.
First load organic phases are transferred to platinum crucible, and is placed in Muffle furnace and carries out calcination；Muffle furnace liter is set
(20 DEG C are warming up to 300 DEG C of used time 56min to cooling process, and in 300 DEG C of holding 30min, 300 DEG C are warming up to 900 DEG C of used times
100min, in 900 DEG C of holding 120min, 900 DEG C cool to 200 DEG C of used time 70min, later cooled to room temperature), obtain the
One slag phase.
With the first slag phase in 20mL milli-Q water platinum crucible, first is obtained6Li pregnant solution；The enrichment of the first order
Abundance reaches 7.70%.
The second level:
To first6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the second load organic phases and the second raffinate
Liquid.
Second load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the second slag phase.
With the second slag phase in 20mL milli-Q water platinum crucible, second is obtained6Li pregnant solution；The enrichment of the second level
Abundance reaches 7.796%.
The third level:
To second6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains third load organic phases and third raffinate
Liquid.
Third load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain third slag phase.
With the third slag phase in 10mL milli-Q water platinum crucible, third is obtained6Li pregnant solution；The enrichment of the third level
Abundance reaches 7.866%.
The fourth stage:
To third6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 4th load organic phases and the 4th raffinate
Liquid.
4th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 4th slag phase.
With the 4th slag phase in 10mL milli-Q water platinum crucible, the 4th is obtained6Li pregnant solution；The enrichment of the fourth stage
Abundance reaches 7.939%.
Level V:
To the 4th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 5th load organic phases and the 5th raffinate
Liquid.
5th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 5th slag phase.
With the 5th slag phase in 10mL milli-Q water platinum crucible, the 5th is obtained6Li pregnant solution；The enrichment of the level V
Abundance reaches 8.01%.
6th grade:
To the 5th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 6th load organic phases and the 6th raffinate
Liquid.
6th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 6th slag phase.
With the 6th slag phase in 10mL milli-Q water platinum crucible, the 6th is obtained6Li pregnant solution；6th grade of enrichment
Abundance reaches 8.071%.
7th grade:
To the 6th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 7th load organic phases and the 7th raffinate
Liquid.
7th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 7th slag phase.
With the 7th slag phase in 10mL milli-Q water platinum crucible, the 7th is obtained6Li pregnant solution；7th grade of enrichment
Abundance reaches 8.145%.
8th grade:
To the 7th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 8th load organic phases and the 8th raffinate
Liquid.
8th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 8th slag phase.
With the 8th slag phase in 10mL milli-Q water platinum crucible, the 8th is obtained6Li pregnant solution；8th grade of enrichment
Abundance reaches 8.215%.
9th grade:
To the 8th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the 9th load organic phases and the 9th raffinate
Liquid.
9th load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the 9th slag phase.
With the 9th slag phase in 10mL milli-Q water platinum crucible, the 9th is obtained6Li pregnant solution；9th grade of enrichment
Abundance reaches 8.305%.
Tenth grade:
To the 9th6The above-mentioned extraction organic phase of 10mL is added in Li pregnant solution, is placed on constant temperature oscillator and acutely shakes
60min, being transferred on supercentrifuge after the completion of concussion makes the complete split-phase of two-phase, obtains the tenth load organic phases and the tenth raffinate
Liquid.
Tenth load organic phases are transferred in platinum crucible, and is placed in Muffle furnace and carries out calcination, are arranged with above-mentioned
Muffle furnace heating and cooling program, obtain the tenth slag phase.
With the tenth slag phase in 10mL milli-Q water platinum crucible, the tenth is obtained6Li pregnant solution；Tenth grade of enrichment
Abundance reaches 8.39%.
In the present embodiment, there are still portions into the tenth raffinate for the first raffinate that the above-mentioned first order is obtained to the tenth grade
Divide lithium isotope6Li can be mixed or separately as aqueous phase extracted, separately take fresh above-mentioned extraction organic phase, carry out again
Extraction, further separates lithium isotope6Li and lithium isotope7Li。
Although the present invention has shown and described referring to specific embodiment, it should be appreciated by those skilled in the art that:
In the case where not departing from the spirit and scope of the present invention being defined by the claims and their equivalents, can carry out herein form and
Various change in details.
Claims (11)
1. a kind of method for separating and concentrating of lithium isotope, which is characterized in that comprising steps of
S1, prepare extraction organic phase: using crown ether derivative shown in following formula A or formula B as extractant, by the extractant and
Hydrophobic ionic liquid and diluent mixing, obtain extraction organic phase；
Wherein, the value of n is 0,1,2；R is selected from hydrogen atom, dialkyl amido, alkyl amino, amino, hydroxyl, alkoxy, amide
Base, ester group, phenyl, acyl group, aldehyde radical, carboxyl, sulfonyl, cyano, any one in nitro；
S2, it prepares aqueous phase extracted: water-soluble lithium salts being configured to lithium salt solution, as aqueous phase extracted；
S3, extraction: after the extraction organic phase and the aqueous phase extracted are sufficiently mixed extraction according to the volume ratio of 1~4:1~5
Split-phase is carried out, load organic phases and raffinate are obtained；
S4, calcination: by the load organic phases at a temperature of 500 DEG C~1000 DEG C calcination 30min~200min, obtain slag
Phase；
It is S5, water-soluble: to dissolve the slag phase with water, and be separated by solid-liquid separation, obtained6Li pregnant solution；
S6, with described6Li pregnant solution repeats the above steps S3~S5 at least 2 times as aqueous phase extracted.
2. method for separating and concentrating according to claim 1, which is characterized in that the method for separating and concentrating further comprises the steps of:
Q, using the raffinate as aqueous phase extracted, repeat the above steps S3.
3. method for separating and concentrating according to claim 1 or 2, which is characterized in that in the step S1, the extractant
Concentration be 0.05mol/L~2mol/L.
4. method for separating and concentrating according to claim 3, which is characterized in that R is selected from hydrogen atom, dialkyl amido, alkyl
Amino, amino, hydroxyl, alkoxy, amide groups, ester group, any one in phenyl.
5. method for separating and concentrating according to claim 1 or 2, which is characterized in that the hydrophobic ionic liquid is by following
Cation composition shown in anion shown in formula C and following formula D:
6. method for separating and concentrating according to claim 5, which is characterized in that in the step S1, the hydrophobicity from
The ratio between volume of sub- liquid and the diluent is 1:9~3:1.
7. method for separating and concentrating according to claim 1 or 2, which is characterized in that the diluent is selected from methyl phenyl ethers anisole, chlorine
Imitative, kerosene, methylene chloride, 1,2- dichloroethanes, n-hexane, normal heptane, carbon tetrachloride, toluene, dimethylbenzene, diethylbenzene, bromobenzene,
Any one in nitrobenzene.
8. method for separating and concentrating according to claim 1 or 2, which is characterized in that Li in the lithium salt solution+Concentration be
0.1mol/L~4mol/L；And/or the water-soluble lithium salts is selected from lithium chloride, lithium bromide, lithium iodide, trifluoroacetic acid lithium, double
At least one of (fluoroform sulphonyl) imine lithium.
9. method for separating and concentrating according to claim 1 or 2, which is characterized in that in the step S3, by the extraction
5min~80min is shaken sufficiently to extract after organic phase and aqueous phase extracted mixing, then is centrifuged 1min~10min and is divided
Phase.
10. method for separating and concentrating according to claim 1 or 2, which is characterized in that in the step S4, with 1 DEG C/min
The load organic phases are warming up at a temperature of 400 DEG C~1000 DEG C and carry out calcination by the heating rate of~15 DEG C/min.
11. method for separating and concentrating according to claim 1 or 2, which is characterized in that in the step S5, with resistivity
Ultrapure water not less than 18.25 Ω cm dissolves the slag phase.
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