CN105536536B - A kind of extraction system for extracting lithium isotope - Google Patents
A kind of extraction system for extracting lithium isotope Download PDFInfo
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- CN105536536B CN105536536B CN201510952278.3A CN201510952278A CN105536536B CN 105536536 B CN105536536 B CN 105536536B CN 201510952278 A CN201510952278 A CN 201510952278A CN 105536536 B CN105536536 B CN 105536536B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/24—Separation by extracting by solvent extraction
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Abstract
The present invention provides a kind of extraction system for extracting lithium isotope, including：The volume ratio of extractant, hydrophobic ionic liquid and diluent, the hydrophobic ionic liquid and the diluent is 1~15:1~10；The extractant is 0.05~2.5mol/L in the concentration of the extraction organic phase；The extractant is that the hat of benzo 15 5 and its derivative or benzo 14 are preced with least one of 4 and its derivative.It is of the invention compared with existing crown ether and pure ion liquid system, have the advantages that cost is low and industrial operation strong adaptability.
Description
Technical field
The present invention relates to the separation of extraction and separation technology field, especially lithium isotope.
Background technology
At present, the separation method of domestic and international lithium isotope has many kinds, mainly includes lithium amalgam method, extraction, ion and hands over
Change chromatography, fractional crystallization and fractional precipitation, electromagnetic method, fused salt electrolysis process, electron transfer, molecularly distilled and separation by laser
Deng.Up to the present, in the world can industrialized production separation lithium isotope there was only lithium amalgam method, other most of lithium isotopes
Method only rests on the laboratory research stage.However, need to use substantial amounts of mercury in the technique of lithium amalgam method separation lithium isotope, it is right
The mankind and environment produce serious threat, are originated which greatly limits lithium amalgam method as following nuclear fusion stack generating lithium isotope
Prospect.The developed countries such as America and Europe are just progressively closing the factory that existing lithium amalgam method separates lithium isotope, and secret open
Open up the research of the lithium isotope separation method of green high-efficient.
Crown ether extraction method mainly uses neutral chelating extractant crown ether in extraction process to isotope6Li and7Li chela
The difference of performance is closed, a kind of chemical exchange method that isotope is exchanged and is enriched with is realized exchanging link.From Jepson in the U.S.
Reported in the meeting of separation science and technology and liquid-liquid extraction lithium isotope is carried out using macrocyclic polyether, and find its single-stage point
From coefficient and lithium amalgam method after, the substantial amounts of research work on crown ether extraction lithium isotope system, which is carried out, gets up, but
Be lithium in the crown ether extraction system reported distribution coefficient it is smaller.Therefore, from the point of view of single-stage separation factor, crown ether system extraction
It is very promising separation method to take separation lithium isotope.
The research of liquid-liquid extraction separation lithium isotope has：Fang Shengqiang exists《Nuclear and radiochemistry》On " the 4- first delivered
Base Benzo15crown5 derivatives separate the ability of lithium isotope " and " the liquid-liquid extraction method separating Li of 4- tert-butyl groups Benzo15crown5 derivatives 5 is same
Have involved in position element ", but it tests data display, and distribution coefficient is very low (far smaller than 1), it is meant that its single-stage extraction
Efficiency is unfavorable for extract and separate also by very little.
Chinese patent CN 1186506A disclose a kind of preparation method of water-soluble polymer, are directed to a kind of poly-
The water-soluble polymer of 15-crown-5 is grafted with vinyl alcohol, and the structure of 15- crown-s 5 of pendant does not contain power supplying groups benzene
Ring, its lithium isotope separating capacity is relatively weak.Patent CN 103768945A describe a kind of sol-gel materials extract and separate
The solid phase extraction method of isotope, makes sol-gel formation mesoporous materials using ionic liquid, and load benzo-crown ether carries out extraction point
From isotope, though separation is larger, single-stage lithium adsorbance is smaller, and the overall separation effect of lithium isotope is weaker.Patent CN
103386299A discloses a kind of method of similar Solid phase extraction separation isotope, has lithium as carrier loaded using composite membrane
The crown ether or cave ether material of isotopic separation effect carry out lithium isotope separation, and the technology is also known as membrane chromatography technology.
Research for liquid-liquid extraction separated isotopes has：1) to disclose a kind of lithium same by Chinese patent CN 102430338A
The method of the plain extract and separate in position, using miscellaneous nitrogen phenanthrene as main body chelating agent, is mainly complexed in organic phase7Li.2) Chinese patent
CN 103801194A disclose a kind of extractant for separating lithium isotope and using the example of multistage lithium isotope extraction, organic
What is be enriched with phase is also7Li。
But above-mentioned system method has the relatively low and a large amount of use organic solvent of single-stage extraction rate, this to utilize liquid liquid extraction
The industrialization cost of separation lithium isotope is taken to improve and cause certain problem of environmental pollution.By being introduced in the extraction system
Hydrophobic ionic liquid with association's extraction effect, is solve the above problems good while may act as the spe medium of organic phase
Approach.
The content of the invention
To overcome the deficiencies in the prior art, the present invention provides a kind of extraction system for extracting lithium isotope, for utilizing extraction
The lithium isotope of organic extractant phase and separation and concentration in aqueous phase is taken, the extraction organic phase includes：Including：It is extractant, hydrophobic
Property ionic liquid and diluent, the volume ratio of the hydrophobic ionic liquid and the diluent is 1~15:1~10；The extraction
It is 0.05~2.5mol/L in the concentration of the extraction organic phase to take agent；The extractant is Benzo15crown5 derivatives and its derivative
At least one of thing or phendioxin 4- crown-s 4 and its derivative.
Further, the extractant structural formula is as follows：
Wherein, R is alkyl, alkoxy, the phenyl of hydrogen atom or carbon number between 1~20.
Further, the cation in the ionic liquid is alkyl imidazolium cation；Anion in the ionic liquid
Selected from PF6 -、(SO2CF3)2N-、(SO2CF2CF3)2N-And BF4 -In one or more.
Further, the diluent is selected from kerosene, octanone, chloroform, dichloromethane, carbon tetrachloride, tetrachloro-ethylene, first
Benzene, dimethylbenzene, diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane, 2- methyl cyclohexanones, methylisobutylketone, chlorobenzene, dichloro-benzenes, three
At least one of chlorobenzene, diphenyl ether.
Further, the lithium salts is selected from LiCl, LiBr, LiI, Li2SO4、Li3PO4、Li2CO3、LiNO3、LiSCN、
CH3COOLi、CF3COOLi、CHF2COOLi、CH2At least one of FCOOLi or LiOH.
Beneficial effect：
It is an object of the present invention to provide one kind based on neutral chelating extractant crown ether, using hydrophobic ionic liquid as
Synergic reagent and organic phase solvent medium, constitute the separation and concentration that new extraction system carries out lithium isotope, mainly solve existing skill
The single-stage extraction rate of lithium is relatively low during simple crown ether liquid-liquid extraction separation lithium isotope in art and application is a large amount of volatile organic
The Environmental Technology problem of solvent, at the same with the system viscosity of crown ether and pure ion liquid system is big and mass-transfer efficiency low phase ratio, have
Have the advantages that cost is low and industrial operation strong adaptability.
Embodiment
Below, the embodiment of the present invention will be described in detail.
Isotope exchange reaction between LITHIUM ISOTOPE SEPARATION BY CHEMICAL EXCHANGE METHOD, two kinds of liquid phases is represented by：
Wherein, X and Y represents coordination environment of the lithium ion in two-phase respectively, and in such as present invention, X represents aqueous phase, Y and represented
Organic phase.
Single-stage extraction rate (E%) accounts for lithium ion total amount in two-phase to enter the content of the lithium of organic phase during single extraction
Percentage, be represent extraction completeness.It is with experiment condition (as by extraction thing concentration, the acid-base value of solution, extractant
Concentration, property of diluent etc.) change and it is different.
Isotope separation factor (α) represents the effect of lithium isotope single-stage separation, i.e., the abundance ratio of lithium isotope in Y phases
With the business of the abundance ratio of lithium isotope in X phases：
Separation represents the degree that a certain unit lock out operation or a certain separation process separate two kinds of materials.It big
The small complexity for reflecting the separation of two components.Separation is equal to 1, just can not realize separation；Separation deviates from 1 journey
Degree is bigger, shows more to be easily separated.
A kind of method of extract and separate lithium isotope of the present invention, comprises the following steps：
First organic phase is prepared：The extraction organic phase of the present invention is used to extract and the same position of lithium of the separation and concentration in aqueous phase
Element, the extraction organic phase includes：Hydrophobic ionic liquid, diluent and extractant.
By hydrophobic ionic liquid, diluent according to volume ratio be 1~15:1~10 stirs mixing under conditions of closed
Uniformly；Then extractant is added, first organic phase is formed；The concentration for adjusting extractant described in first organic phase is
0.05~2.5mol/L.
Preferably, after hydrophobic ionic liquid and diluent are uniformly mixed under conditions of closed in advance, then will extraction
Take agent to add, form first organic phase.
The extractant is at least one in Benzo15crown5 derivatives and its derivative or phendioxin 4- crown-s 4 and its derivative
Kind.Specifically, the structural formula of extractant may be, for example,：
Wherein R-and it is substituent, represent the confession such as alkyl, alkoxy, the phenyl of hydrogen atom, carbon number between 1~20
Electronics base.
The hydrophobic ionic liquid is synergic reagent.The cation of the hydrophobic ionic liquid is alkyl imidazolium cation,
That is structural formula 5.
Wherein R in the formula of structural formula 51、R2And R3For substituent, they are the alkane of hydrogen atom, carbon number between 1~20
One kind in base, alkenyl, alkynyl or halogen atom F, Br, Cl or I.
The anion of the hydrophobic ionic liquid is PF6 -、(SO2CF3)2N-、(SO2CF2CF3)2N-And BF4 -In one kind
Or it is several, structural formula is shown in 6,7,8,9 respectively.
Diluent：Kerosene, octanone, chloroform, dichloromethane, carbon tetrachloride, tetrachloro-ethylene, toluene, dimethylbenzene, diethylbenzene,
In bromobenzene, methyl phenyl ethers anisole, nitromethane, 2- methyl cyclohexanones, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes, diphenyl ether at least
It is a kind of.
Then, the preparation of the first aqueous phase is carried out：That is, lithium concentration is 0.2~5.0mol/L Aqueous Lithium Salts.It is described
Lithium salts is selected from LiCl, LiBr, LiI, Li2SO4、Li3PO4、Li2CO3、LiNO3、LiSCN、CH3COOLi、CF3COOLi、
CHF2COOLi、CH2At least one of FCOOLi or LiOH.Two kinds of same positions of naturally occurring lithium in these lithium salt solutions
Element6Li and7Li。
Further, by first aqueous phase and first organic phase, (A/O) is 1~2 by volume:1~4 is mixed
The first extraction system is formed, 5~60min is acutely shaken on Kang Shi oscillators, then treats that first extraction system is divided again
Layer, separation obtains the second aqueous phase, Second Organic Phase.Again the method being layered is generally at normal temperatures and pressures using centrifugation point
From or stand method be layered both.Now, two kinds of isotopes of lithium6Li and7Li is enriched with different phase layers respectively,
Specifically,6Li relative enrichments in Second Organic Phase are more,7Li relative enrichments in the second aqueous phase are more.Then lithium is tested
Single-stage extraction rate.
Finally carry out stripping steps：It is according to volume ratio by the Second Organic Phase and 0.01~5mol/L hydrochloric acid solution
1~2:1~4 carries out being mixed to form the second extraction system, violent 5~60min of concussion on Kang Shi oscillators, then treats described the
Two extraction systems are layered again, and separation obtains the 3rd aqueous phase, the 3rd organic phase.It is enriched with the 3rd aqueous phase6Li, realizes lithium
Two kinds of isotopes6Li and7Li separation.Again the method being layered generally at normal temperatures and pressures using centrifuge or
It is that the method stood is layered both.Test stripping efficiency.
In order that obtaining stripping efficiency can greatly improve, stripping steps are carried out again to the 3rd organic phase, obtain the 4th
Organic phase ... so repeats stripping steps five times, collects and is stripped obtained aqueous phase from organic phase every time, re-test back extraction effect
Rate.
Specific embodiment see shown in table 1.
Table 1 is the extractive reaction parameter of embodiment 1~8
As known from Table 1, lithium single-stage extraction rate of the invention reaches more than 20%, or even close to 30%；Distribution coefficient
1 is all higher than, the single-stage extraction rate of lithium is high when separating lithium isotope compared to crown ether extraction simple in the prior art, while with
Crown ether is compared with pure ion liquid system, has the advantages that cost is low and industrial operation strong adaptability.
Claims (4)
1. a kind of extraction system for extracting lithium isotope, it is characterised in that extract organic extractant phase and separation and concentration for utilizing
Lithium isotope in aqueous phase, the extraction organic phase includes：Extractant, hydrophobic ionic liquid and diluent, it is described hydrophobic
Property ionic liquid and the diluent volume ratio be 1~15:1~10；Concentration of the extractant in the extraction organic phase
For 0.05~2.5mol/L；The extractant is Benzo15crown5 derivatives and its derivative or phendioxin 4- crown-s 4 and its derivative
At least one of.
2. the extraction system of lithium isotope is extracted according to claim 1, it is characterised in that the extractant structural formula is such as
Under：
Wherein, R is alkyl, alkoxy, the phenyl of hydrogen atom or carbon number between 1~20.
3. according to claim 1 extract lithium isotope extraction system, it is characterised in that in the ionic liquid sun from
Son is alkyl imidazolium cation；Anion in the ionic liquid is selected from PF6 -、(SO2CF3)2N-、(SO2CF2CF3)2N-And BF4 -
In one or more.
4. according to claim 1 extract lithium isotope extraction system, it is characterised in that the diluent be selected from kerosene,
Octanone, chloroform, dichloromethane, carbon tetrachloride, tetrachloro-ethylene, toluene, dimethylbenzene, diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane,
At least one of 2- methyl cyclohexanones, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes, diphenyl ether.
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| CN106179273A (en) * | 2016-08-10 | 2016-12-07 | 清华大学 | A kind of adsorbent for lithium isotope separation and its preparation method and application |
| CN108854534B (en) * | 2017-05-15 | 2020-03-06 | 中国科学院上海有机化学研究所 | Process for extracting and separating lithium isotope by crown ether |
| CN108892158B (en) * | 2018-07-18 | 2021-03-26 | 北京化工大学 | Method for extracting lithium ions by taking non-fluorine non-iron ion liquid as co-extraction agent |
| CN112452150A (en) * | 2019-09-06 | 2021-03-09 | 中国科学院青海盐湖研究所 | Separation and enrichment method of lithium isotope |
| CN110551894A (en) * | 2019-10-17 | 2019-12-10 | 青海民族大学 | Extraction separation system for separating rubidium ions from salt lake brine and use method thereof |
| CN113262637B (en) * | 2020-02-14 | 2023-10-17 | 中国科学院青海盐湖研究所 | Electromigration separation and enrichment 6 Method for producing Li isotopes |
| WO2021159674A1 (en) * | 2020-02-14 | 2021-08-19 | 中国科学院青海盐湖研究所 | Li isotope separation and enrichment method |
| CN111905568B (en) * | 2020-07-15 | 2024-03-12 | 山西大学 | Method for separating lithium isotopes |
| WO2022082324A1 (en) | 2020-10-19 | 2022-04-28 | Pontificia Universidad Católica | Solid-liquid extraction process for recovering ions of interest from solid materials |
| CN112657336B (en) * | 2020-12-03 | 2023-10-17 | 郑州大学 | Stable isotope floating extraction precise separation method |
| CN114832654A (en) * | 2022-04-25 | 2022-08-02 | 苏州思脉新材料科技有限公司 | Porous membrane for cleaning and filtering in semiconductor manufacturing process and production method thereof |
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| JPH01184027A (en) * | 1988-01-14 | 1989-07-21 | Agency Of Ind Science & Technol | Separation of lithium isotope |
| JP3020146B2 (en) * | 1997-06-30 | 2000-03-15 | 工業技術院長 | Lithium isotope separating agent and method for separating lithium isotope using the same |
| CN102430338B (en) * | 2011-12-16 | 2014-08-13 | 江南大学 | Method for extracting and separating lithium isotope aqueous solution |
| CN103768945A (en) * | 2014-02-27 | 2014-05-07 | 江南大学 | Method for extraction separating of lithium isotope by virtue of sol-gel material |
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