CN108854537A - A kind of technique of liquid-liquid extraction separation lithium isotope - Google Patents
A kind of technique of liquid-liquid extraction separation lithium isotope Download PDFInfo
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Abstract
The present invention provides a kind of technique of liquid-liquid extraction separation lithium isotope.Specifically, the technique includes：Continuous flow upstream operates organic phase and water phase：Organic phase containing lithium after lithium soap section passes sequentially through C1 sections of extraction and separation, C2 sections of extraction and separation and phase inversion section；Water phase containing lithium after phase inversion section passes sequentially through H1 sections of H2 sections of buffering, C2 sections of extraction and separation, C1 sections of extraction and separation and buffering；Using H2 sections of H1 sections of buffering and buffering, -6 enriched products P1 of lithium and the abundance with -7 enriched products P2 of lithium is easily regulated and controled, two kinds of enriched products of enriching lithium -6 and lithium -7 can be obtained simultaneously.Process design of the invention is rationally succinct, easy to operate, effectively can buffer and control the fluctuation of flow, and that realizes lithium isotope efficiently separates enrichment.
Description
Technical field
The present invention relates to the isotopic separation of chemical field more particularly to a kind of works of liquid-liquid extraction separation lithium isotope
Skill.
Background technique
There are two types of natural isotopes in nature for lithium (Li), i.e.,7Li (lithium -7) and6Li (lithium -6), accounts for respectively
92.48% and 7.52%.Both isotopes after separation and concentration is concentrated, have in each leisure nuclear material field it is important not
Same purposes.In thorium base molten salt reactor,7Li is essential molten salt coolant, due to6The thermal neutron absorption cross section of Li is very high,
Reach 941barns, and7Li is only 0.033barns, so, molten salt reactor pair7The isotope abundance requirement of Li>99.995%.Together
When, high-purity7Li is usually used in adjusting the pH value of primary coolant in presurized water reactor, in fusion reactor7Li is also served as in thermally conductive load
Thermit powder.On the other hand,6Li is the fuel in nuclear fusion stack, wherein6The isotope abundance requirement of Li>30%.Whether thorium base is molten
Salt heap or nuclear fusion stack, lithium isotope are all indispensable strategic material and energy and material.
The method of separation lithium isotope has：Physical method (such as electromagnetic method, molecularly distilled and gaseous diffusion process) and change
Method (such as electromigration, electrolysis method, lithium amalgam exchange process and solvent extraction exchange process) (Xiao Xiao Um etc., nuclear chemistry with put
Penetrate that classes are over, 1991,13,1).In isotopic separation, for heavy isotope physical method than advantageous；And for light same position
Element, then chemical method efficiency is higher, and physical method efficiency is very low, investment is huge.Since lithium isotope belongs to light isotope, and lithium
There is no gaseous compound, therefore physical method for separation lithium isotope only exists in the exploratory stage.In chemical method, the overwhelming majority is ground
The content studied carefully is only limitted to the measurement and raising of single-stage isotope separation factor in laboratory, without the report of multistage process of enriching
Road.Meanwhile in chemical method, elemental lithium is not present gas-liquid chemical exchange method, and consolidate chemical exchange method difficult to realize countercurrently more for liquid
Grade cascade.Using liquid liquid chemical exchange method, the single-stage separation factor α value of the Sudan's I-TOPO system is generally 1.010 or so (Chen Yao
It shines, atomic energy science and technology, 1987,21,433), but the technique of multitple extraction enrichment has not been reported.Lithium amalgam Chemical Exchange
Method has preferably chemical property and chemical process, can fairly large industrialized separation lithium isotope (chemical method separation is together
The plain principle in position, Qiu Ling write, Atomic Energy Press, nineteen ninety, pp 156-181).But the process requirement uses a large amount of mercury,
And the volatile loss of mercury, serious harm is caused to operator and ambient enviroment.Chinese patent 201310239535X report
A kind of technique producing -7 isotope of lithium, can obtain -7 isotope product of lithium of high abundance, but the extraction procedure needs essence
The really concentration of the fluctuation range of control fluid flow and material.
Summary of the invention
The object of the present invention is to provide a kind of techniques of liquid-liquid extraction separation lithium isotope.
The first aspect of the present invention, provides a kind of technique of liquid-liquid extraction separation lithium isotope, and the technique includes step
Suddenly：
(1) continuous flow upstream operating organic phase and water phase：
Organic phase containing lithium after lithium soap section passes sequentially through C1 sections of extraction and separation, C2 sections of extraction and separation and phase inversion section；
Water phase containing lithium after phase inversion section passes sequentially through H2 sections of buffering, C2 sections of extraction and separation, C1 sections of extraction and separation and buffering
H1 sections；
(2) between C1 sections of extraction and separation and C2 sections of extraction and separation, the F of feed liquid containing lithium is added；
It is added in H2 sections of buffering and adjusts liquid T；
Phase inversion liquid water phase A1 is added in phase inversion section；
(3) some aqueous phase buffered in H1 sections flows continually out to obtain -6 enriched products P1 of lithium, and remainder water phase enters lithium
It is saponified section；
(4) some aqueous phase buffered in H2 sections flows continually out to obtain -7 enriched products P2 of lithium, and remainder water phase enters extraction
Take C2 sections of separation.
In another preferred example, described to buffer the water phase P1 flowed out in H1 sections and enter lithium soap in the step (3)
The ratio between water phase flow of section is 1：3~3500.
In another preferred example, described to buffer the water phase P2 flowed out in H2 sections and enter extraction point in the step (4)
The ratio between water phase flow from C2 sections is 1：3~3500.
In another preferred example, the counter-current operation refers to that the flow direction of the water phase and the organic phase is opposite.
In another preferred example, further include in the method：
Organic phase carries out the water phase for including elemental lithium in lithium soap section, C1 sections of extraction and separation and C2 sections of extraction and separation
Extraction is to load elemental lithium；And/or
Phase inversion liquid carries out phase inversion back extraction in phase inversion section, to the organic phase for including elemental lithium.
In another preferred example, after the load lithium concentration range of organic phase in 0.01~2mol/L.
In another preferred example, C1 sections of the extraction and separation and C2 sections of the extraction and separation are respectively by multiple liquid liquid point
It is constituted from equipment cascade arrangement, preferably, the Liquid liquid Separation equipment is centrifugal extractor.
In another preferred example, the range of total series N of C1 sections of the extraction and separation is 5~500 grades.
In another preferred example, the range of total series M of C2 sections of the extraction and separation is 5~500 grades.
In another preferred example, in the water phase of phase inversion section outlet, 0.01~4mol/L of concentration range of elemental lithium.
In another preferred example, the technique further includes：
The organic phase flowed out from phase inversion section after lye is saponified, is recycled in saponification section into lithium soap section；With/
Or
Lye A3 is added in saponification section；And/or
Water phase A2 is discharged from lithium soap section；And/or
Water phase A4 is discharged from saponification section.
In another preferred example, lithium concentration in the water phase A2<0.005mol/L.
In another preferred example, without lithium ion in the water phase A4.
In another preferred example, solute selected from the group below is contained in the lye：Sodium hydroxide, ammonium hydroxide, hydrogen-oxygen
Change potassium, cesium hydroxide, or combinations thereof.
In another preferred example, H1 sections of the buffering include the first wet tank, and described H2 sections of buffering include second
Wet tank；And the volume of first wet tank and second liquid storage tank is each independently 0.001~80m3。
In another preferred example, H2 sections of H1 sections of the buffering and buffering also contain temperature controller and stability of flow respectively
Device.
In another preferred example, the organic phase contains a effective amount of formula (I) compound represented of extraction：
In formula (I), Z is for oxygen atom, sulphur atom or by R9Replaced nitrogen-atoms, wherein R9For hydrogen atom, C1-6Alkane
Base-sulfonyl, C1-6Halogenated alkyl-sulfonyl, benzenesulfonyl or C1-6Alkyl-benzenesulfonyl；R1、R2、R3、R4、R5、R6、R7
And R8It is each independently hydrogen atom, C1-6Alkyl, C1-6Halogenated alkyl, C2-6Alkenyl, C2-6Alkynyl, C1-6Alkoxy, C3-6Cycloalkanes
Base, halogen or phenyl.
In another preferred example, the organic phase also contains synergic reagent.
In another preferred example, the synergic reagent includes：Neutral phosphorus-containing compound, quarternary ammonium salt compound, chain alkyl
Season sulfonium salt compound, or neutral sulfoxide compound.
In another preferred example, the synergic reagent includes：Tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), fourth
Base aminophon (DBBP), dibutylphosphoric acid butyl ester (BDBP), methylene tetrabutyl biphosphonate, trioctyl phosphine oxide, 1,10-
Phenanthroline, methyl tricapryl ammonium chloride, three nonyl ammonium chloride of methyl, three decyl ammonium chloride of methyl, (the N- octadecane of dimethyl two
Base) ammonium chloride, methyl chloride dioctyl sulfonium salt or dioctylsulfoxide (DOSO).
In another preferred example, the organic phase also contains diluent.
In another preferred example, the diluent includes：Kerosene, octanone, chloroform, carbon tetrachloride, toluene, dimethylbenzene,
Diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane, 2- methyl cyclohexanone, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes, hexichol
Ether, or combinations thereof.
In another preferred example, the phase inversion liquid water phase A1 is the aqueous solution comprising solute selected from the group below：HCl,
H2SO4、HBr、NaCl、NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4, or combinations thereof.
In another preferred example, in the phase inversion liquid water phase A1, the concentration range of solute is 0~5mol/L.
In another preferred example, the adjusting liquid T is the aqueous solution comprising solute selected from the group below：Sodium hydroxide, hydrogen
Potassium oxide, cesium hydroxide, ammonium hydroxide, or combinations thereof.
In another preferred example, in the adjusting liquid T, the concentration range of solute is 0.1~18mol/L.
In another preferred example, the technique further includes：Control system temperature range is 0~80 DEG C.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
The present inventor's in-depth study by long-term, develop it is a kind of can efficiently, be conveniently separated lithium isotope
Liquid-liquid extraction separating technology.Technique process design of the invention is rationally succinct, easy to operate, effectively can buffer and control
The fluctuation of flow, that realizes lithium isotope efficiently separates enrichment, while obtaining -7 isotope enrichment product of lithium and -6 isotope of lithium
Enriched products.And the technique is environmentally protective, operational safety is high.Organic phase can be repeatedly circulated, and it is same to significantly reduce lithium
The cost of the plain separation and concentration in position, economic benefits.
Extraction and separation technology
Extraction and separation technology of the invention mainly includes following process section：Lithium soap section, buffering H1 sections, extraction and separation C1
Section, C2 sections of extraction and separation, buffering H2 sections and phase inversion section.
During isotope enrichment, single-stage (single) separation of extraction system is all smaller, needs using specific
Extraction process (including cascade extraction process section, phase transfer process section, saponification process section, buffering adjust process section etc.) is just able to achieve lithium
The multistage accumulation separation and concentration of isotope, the final lithium isotope product for obtaining high abundance.
As shown in Figure 1, in extraction process of the invention, each process section has the function of different, these process sections have
Effect combination, is just able to achieve the extracting and enriching of lithium isotope.
H1 sections of buffering：
(a) regulate and control the Abundances of enriched products P1 and P2.Wet tank in H1 sections of buffering has been detained the enrichment of part lithium -6
Product.Under the conditions of fixed extractor separates C1 sections and extraction and separation C2 sections of total series (total number of equipment), the volume of the storage tank
Size can regulate and control the Abundances of enriched products P1 and P2, facilitate operating process and produce various adjustability of product.The liquid
The volume of body storage tank is 0.001~80m3。
(b) there is the buffering and storage effect to liquid, the fluctuation of regime flow.
(c) facilitate -6 enriched products of acquirement lithium.It can be enriched with water phase product from corresponding lithium -6 is flowed out from wet tank,
Without causing the flow to entire extraction system to have larger pulse and fluctuation, facilitate operation.
(d) preferably, which can add temperature controller, facilitate the control of temperature according to actual extraction system, control
0~80 DEG C of range processed.Preferably, flow stabilizer can also be added, for adjusting the size of flow, the fluctuation of regime flow.
It can also carry out the control of basicity and concentration.
H2 sections of buffering：
(a) regulate and control the Abundances of enriched products P1 and P2.Wet tank in H2 sections of buffering has been detained the enrichment of part lithium -7
Product.Under the conditions of fixed extractor separates C1 sections and extraction and separation C2 sections of total series (total number of equipment), the volume of the storage tank
Size can regulate and control the Abundances of enriched products P1 and P2, facilitate operating process and produce various adjustability of product.The liquid
The volume of body storage tank is 0.001~80m3。
(b) there is the buffering and storage effect to liquid, the fluctuation of regime flow.
(c) facilitate -7 enriched products of acquirement lithium.It can be enriched with water phase product from corresponding lithium -7 is flowed out from wet tank,
Without causing to facilitate operation to the larger pulse of the flow of entire extraction system and fluctuation.
(d) facilitate adjust liquid (T) addition with uniformly mix.
(e) preferably, which can add temperature controller, facilitate the control of temperature according to actual extraction system, control
0~80 DEG C of range processed.Preferably, flow stabilizer can also be added, for adjusting the size of flow, the fluctuation of regime flow.
It can also carry out the control of basicity and concentration.
Lithium soap section：
So that organic phase load elemental lithium, and -6 isotope reflux cycle of lithium is enriched with.Lithium in organic phase after load
Concentration range can be used reaction kettle, ingredient agitator tank, extraction and separation tower or centrifugal extractor etc. and set in 0.01~2mol/L
It is standby.Organic phase is mixed with H1 sections of water phases come out of buffering, is stirred, after mass transfer, loads elemental lithium, and continuous-stable enters extraction point
From C1 sections.
C1 sections and extraction and separation C2 sections of extraction and separation：
It is mainly used for multitple extraction, the separation and concentration of lithium isotope, after feed liquid (F) is added from centre, into extraction and separation
Water phase in C1 sections, compared with organic phase, water phase has the ability of -6 isotope of enriching lithium.Therefore, it is enriched with by separating for several times
(1~N grades) afterwards obtain -6 enriched products of lithium (P1) in H1 sections of outlets of buffering, and -6 isotope abundance of lithium is greater than rich in feed liquid
Degree.Opposite, organic phase is enriched -7 isotope product of lithium (P2) in C2 sections of M grades of ends of extraction and separation, after phase inversion section,
Can -7 enriched products of lithium directly be obtained from H2 sections of buffering of water phase.Wherein -7 isotope abundance of lithium of enriched products (P2) is greater than
- 7 isotope abundance of lithium of feed liquid.
C1 sections and extraction and separation C2 sections of extraction and separation are made of multiple liquid-liquid extraction separation equipment cascade arrangements respectively, liquid liquid
Extraction and stripping apparatus includes extraction and separation tower, mixer-settler or centrifugal extractor etc..Preferably, wherein extraction and separation C1 sections
The range of total series N be 5~500 grades, the range of C2 sections of extraction and separation of total series M is 5~500 grades.
Phase inversion section：
So that the elemental lithium phase inversion in organic phase into water phase, guarantees the reflux cycle enrichment of -7 isotope of lithium.After phase inversion,
Water phase exports 0.01~4mol/L of concentration range of elemental lithium, continuously enters H2 sections of buffering；Repetitive cycling benefit after organic phase is unloaded
With into saponification section.The equipment such as reaction kettle, ingredient agitator tank, extraction and separation tower or centrifugal extractor can be used.
Saponification section：
Blank organic phase is carried out saponification.Lye can be sodium hydroxide, ammonium hydroxide, potassium hydroxide, cesium hydroxide
Deng.
Organic phase (O)：
In a kind of technique of liquid-liquid extraction separation lithium isotope provided by the invention, preferably contain formula (I) in organic phase
Compound represented：
In formula (I), Z is for oxygen atom, sulphur atom or by R9Replaced nitrogen-atoms, wherein R9For hydrogen atom, C1-6Alkane
Base-sulfonyl, C1-6Halogenated alkyl-sulfonyl, benzenesulfonyl or C1-6Alkyl-benzenesulfonyl；R1、R2、R3、R4、R5、R6、R7
And R8It is each independently hydrogen atom, C1-6Alkyl, C1-6Halogenated alkyl, C2-6Alkenyl, C2-6Alkynyl, C1-6Alkoxy, C3-6Cycloalkanes
Base, halogen or phenyl.
In another preferred example, the extraction organic phase also contains synergic reagent.
In another preferred example, the synergic reagent be phosphorus-containing compound, nitrogenous compound, alkyl quaternary sulfonium salt compound or
Person's sulfoxide compound.
In another preferred example, the synergic reagent is neutral phosphorus-containing compound, quarternary ammonium salt compound, chain alkyl season sulfonium
Salt compound or neutral sulfoxide compound.
In another preferred example, the synergic reagent includes：Tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), fourth
Base aminophon (DBBP), dibutylphosphoric acid butyl ester (BDBP), methylene tetrabutyl biphosphonate, trioctyl phosphine oxide, 1,10-
Phenanthroline, methyl tricapryl ammonium chloride, three nonyl ammonium chloride of methyl, three decyl ammonium chloride of methyl, (the N- octadecane of dimethyl two
Base) ammonium chloride, methyl chloride dioctyl sulfonium salt or dioctylsulfoxide (DOSO).
In another preferred example, the extraction organic phase also contains diluent.
In another preferred example, the diluent includes：Kerosene, octanone, chloroform, carbon tetrachloride, toluene, dimethylbenzene,
Diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane, 2- methyl cyclohexanone, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes, hexichol
Ether, or combinations thereof.
Extractant in organic phase not only acted as extraction lithium ion effect, in combination at organic complex and water
Lithium ion chemical environment in phase is different, to produce biggish lithium isotope single-stage separation factor.It is different from amalgam process
It is that organic extractant phase agent is easier to -7 isotope of enriching lithium in this technique, and water phase is easy to -6 isotope of enriching lithium.It is gone here and there in multistage
During connection, organic extractant phase agent chemical stability is good, does not decompose for a long time, convenient sources are at low cost.
Phase inversion liquid water phase (A1)：
Preferably, phase inversion liquid water phase A1 is the aqueous solution comprising solute selected from the group below：HCl,H2SO4、HBr、NaCl、
NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4, or combinations thereof.Pass through phase inversion liquid water phase and load
The reaction of decomposing of organic phase, after mass transfer mixing, separation, water phase contains elemental lithium, concentration range in 0.01~4mol/L,
It is recycled after organic phase is unloaded.
It adjusts liquid (T)：
Preferably, adjusting liquid is the aqueous solution comprising solute selected from the group below：Sodium hydroxide, potassium hydroxide, cesium hydroxide,
Ammonium hydroxide, or combinations thereof.The concentration range for adjusting solute in liquid T is 0.1~18mol/L.Added by buffering H2 sections in water phase
Enter and adjusts liquid, the pH value of regulation system, so that extraction system material does not migrate, steady running.
Feed liquid containing lithium (F)：
Preferably, feed liquid containing lithium is the aqueous solution comprising solute selected from the group below：LiCl,Li2SO4、LiBr、LiNO3、
Li2CO3、LiOH、LiClO4Or combinations thereof, wherein the abundance range of -7 isotope of lithium is 40%~99.97%.
- 6 enriched products of lithium (P1)：
- 6 enriched products of lithium (P1) refer to that the higher extraction of -6 abundance of lithium in -6 Abundances ratio feed liquid containing lithium (F) of lithium is rich
Product after collection.It flows continually out to obtain -6 enriched products of lithium from some aqueous phase in H1 sections of buffering, remainder water phase enters lithium soap
Change section, preferably, the ratio range 1 of both control flow:3~1:3500.Preferably, the lithium -6 of -6 enriched products of lithium (P1) is same
The plain abundance range in position is 0.05%~99.5%.
- 7 enriched products of lithium (P2)：
- 7 enriched products of lithium (P2) refer to that the higher extraction of -7 abundance of lithium in -7 Abundances ratio feed liquid containing lithium (F) of lithium is rich
Product after collection.- 7 isotope of organic phase enriching lithium, after phase inversion, -7 isotope of enriching lithium enters H2 sections of buffering, then from buffering
Flow continually out to obtain -7 enriched products of lithium in some aqueous phase in H2 sections, remainder water phase enters C2 sections of extraction and separation, more excellent
, the ratio range 1 of both control flow:3~1:3500.Preferably, -7 isotope abundance of lithium of -7 enriched products of lithium (P2)
Range is 45%~99.996%.
It by multiple validation trial and continues to optimize, using technique of the invention, finally realizes lithium isotope
Multi-stage separation enrichment, while obtaining -7 isotope enrichment product of -6 isotope enrichment product of lithium and lithium.As described in Example 3,
- 6 abundance of lithium can be obtained and be 13.20% -6 enriched products of lithium (P1), while it is rich to obtain the lithium -7 that -7 abundance of lithium is 99.03%
Collect product (P2)；Or as described in Example 4, -6 enriched products of lithium (P1) that -6 abundance of lithium is 25.46% can be obtained, simultaneously
Obtain -7 enriched products of lithium (P2) that -7 abundance of lithium is 95.62%.
Main advantages of the present invention are as follows：
(1) using H2 sections of H1 sections of buffering and buffering, the Abundances of enriched products P1 and P2 have easily been regulated and controled, have obtained simultaneously
Two kinds of enriched products of enriching lithium -6 and lithium -7.
(2) process design of the invention is rationally succinct, easy to operate.The fluctuation of flow effectively can be buffered and control,
That realizes lithium isotope efficiently separates enrichment.
(3) environmentally protective, operational safety is high.Organic phase can be repeatedly circulated, and significantly reduce lithium isotope point
Cost from enrichment, economic benefits.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
Embodiment 1
According to artwork connecting line, C1 sections and extraction and separation C2 sections of extraction and separation use 20 centrifugal extractors altogether.It is slow
It rushes in H1 sections containing the first wet tank, volume 0.018m3；Contain second liquid storage tank in H2 sections of buffering, volume is
0.001m3。
Organic phase：Contain 7- Trifluoromethyl-1 0- hydroxy benzo quinoline and synergic reagent and diluent.
Phase inversion liquid water phase (A1)：NaCl aqueous solution.
It adjusts liquid (T)：Sodium hydrate aqueous solution.
Feed liquid containing lithium (F)：Li2SO4Aqueous solution, 1.8mol/L, wherein -6 abundance of lithium is 7.49%, and -7 abundance of lithium is
92.51%.
Organic phase and each water phase is added by charge pump, runs entire extraction process, system reaches flat after 156 hours
Weighing apparatus, continuous separation simultaneously obtain two kinds of enriched products simultaneously：
- 6 Abundances of lithium of -6 enriched products of lithium (P1) are：8.27%, the stage efficiency 92% that C1 sections of extraction and separation；Lithium -7 is rich
Collection product (P2) -7 Abundances of lithium be：93.70%, the stage efficiency 94% that C2 sections of extraction and separation.
Embodiment 2
Process flow and feed liquid are all made of the parameter in embodiment 1, and the first wet tank only changed in H1 sections of buffering holds
Product is 0.040m3.It can continuously separate and obtain the different enriched products with Abundances in embodiment 1：
- 6 Abundances of lithium of -6 enriched products of lithium (P1) are：8.03%, the stage efficiency 94% that C1 sections of extraction and separation；Lithium -7 is rich
Collection product (P2) -7 Abundances of lithium be：93.90%, the stage efficiency 95% that C2 sections of extraction and separation.
Embodiment 3
According to artwork connecting line, C1 sections of extraction and separation use 45 centrifugal extractors, and C2 sections of extraction and separation use 160
Platform centrifugal extractor.Contain wet tank in H2 sections of H1 sections of buffering and buffering.
Organic phase：Contain 10- hydroxy benzo quinoline.
Phase inversion liquid water phase (A1)：Na2SO4Aqueous solution.
It adjusts liquid (T)：Potassium hydroxide aqueous solution.
Feed liquid containing lithium (F)：Li2SO4Aqueous solution, 2.5mol/L, wherein -6 abundance of lithium is 7.49%, and -7 abundance of lithium is
92.51%.
Organic phase and each water phase is added by charge pump, runs entire extraction process, after system reaches balance, continuous point
From and simultaneously obtain two kinds of enriched products：
- 6 Abundances of lithium of -6 enriched products of lithium (P1) are：13.20%, the stage efficiency 95% that C1 sections of extraction and separation；Lithium -7
- 7 Abundances of lithium of enriched products (P2) are：99.03%, the stage efficiency 95% that C2 sections of extraction and separation.
Embodiment 4
According to artwork connecting line, C1 sections of extraction and separation use 160 centrifugal extractors, and C2 sections of extraction and separation use 45
Platform centrifugal extractor.Contain wet tank and temperature controller in H2 sections of H1 sections of buffering and buffering.
Organic phase：Contain 4- ethyl -10- hydroxy benzo quinoline.
Phase inversion liquid water phase (A1)：(NH4)2SO4Aqueous solution.
It adjusts liquid (T)：Sodium hydrate aqueous solution.
Feed liquid containing lithium (F)：LiCl aqueous solution, 3.0mol/L, wherein -6 abundance of lithium is 7.48%, and -7 abundance of lithium is
92.52%.The stage efficiency of extraction and separation>95%.
Organic phase and each water phase is added by charge pump, runs entire extraction process, after system reaches balance, continuous point
From and simultaneously obtain two kinds of enriched products：
The Abundances of -6 enriched products of lithium (P1) lithium -6 are：25.46%, the stage efficiency 94% that C1 sections of extraction and separation；Lithium -7
- 7 Abundances of lithium of enriched products (P2) are：95.62%, the stage efficiency 95% that C2 sections of extraction and separation.
By above embodiments, it can be seen that, technology of the invention is compared with Chinese patent 201310239535X, tool
There is the stage efficiency of superior extraction and separation；It can simultaneously, continuously obtain two kinds of enriched products (- 6 enriched products P1 of lithium and lithium -7
Enriched products P2, Chinese patent 201310239535X only report -7 product of enriching lithium)；Meanwhile buffering H1 sections and H2 sections of buffering
The Abundances of enriched products P1 and P2 can easily be regulated and controled (in embodiment 1 and embodiment 2).
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of technique of liquid-liquid extraction separation lithium isotope, which is characterized in that the technique includes step：
(1) continuous flow upstream operating organic phase and water phase：
Organic phase containing lithium after lithium soap section passes sequentially through C1 sections of extraction and separation, C2 sections of extraction and separation and phase inversion section；
Water phase containing lithium after phase inversion section passes sequentially through H1 sections of H2 sections of buffering, C2 sections of extraction and separation, C1 sections of extraction and separation and buffering；
(2) between C1 sections of extraction and separation and C2 sections of extraction and separation, the F of feed liquid containing lithium is added；
It is added in H2 sections of buffering and adjusts liquid T；
Phase inversion liquid water phase A1 is added in phase inversion section；
(3) some aqueous phase buffered in H1 sections flows continually out to obtain -6 enriched products P1 of lithium, and remainder water phase enters lithium soap
Section；
(4) it buffers some aqueous phase in H2 sections to flow continually out to obtain -7 enriched products P2 of lithium, remainder water phase enters extraction point
From C2 sections.
2. the method as described in claim 1, which is characterized in that further include in the method：
Organic phase extracts the water phase for including elemental lithium in lithium soap section, C1 sections of extraction and separation and C2 sections of extraction and separation
To load elemental lithium；And/or
Phase inversion liquid carries out phase inversion back extraction in phase inversion section, to the organic phase for including elemental lithium.
3. technique as described in claim 1, which is characterized in that the technique further includes：
The organic phase flowed out from phase inversion section after lye is saponified, is recycled in saponification section into lithium soap section；And/or
Lye A3 is added in saponification section；And/or
Water phase A2 is discharged from lithium soap section；And/or
Water phase A4 is discharged from saponification section.
4. technique as described in claim 1, which is characterized in that described H1 sections of buffering include the first wet tank, described
H2 sections of buffering include second liquid storage tank；And the volume of first wet tank and second liquid storage tank is each independently
0.001~80m3。
5. the technique as described in Claims 1 to 4 is any, which is characterized in that the organic phase contains a effective amount of formula of extraction
(I) compound represented：
In formula (I), Z is for oxygen atom, sulphur atom or by R9Replaced nitrogen-atoms, wherein R9For hydrogen atom, C1-6Alkyl-sulphur
Acyl group, C1-6Halogenated alkyl-sulfonyl, benzenesulfonyl or C1-6Alkyl-benzenesulfonyl；R1、R2、R3、R4、R5、R6、R7And R8Respectively
From independently being hydrogen atom, C1-6Alkyl, C1-6Halogenated alkyl, C2-6Alkenyl, C2-6Alkynyl, C1-6Alkoxy, C3-6Naphthenic base, halogen
Or phenyl.
6. technique as claimed in claim 5, which is characterized in that the organic phase also contains synergic reagent；Preferably, described
Synergic reagent includes：Neutral phosphorus-containing compound, quarternary ammonium salt compound, chain alkyl season sulfonium salt compound, or neutral sulfoxide chemical combination
Object.
7. technique as claimed in claim 6, which is characterized in that the synergic reagent includes：It is tributyl phosphate (TBP), three pungent
Base phosphine oxide (TOPO), dibutyl-butylphosphonate (DBBP), dibutylphosphoric acid butyl ester (BDBP), methylene tetrabutyl biphosphonate,
Trioctyl phosphine oxide, 1,10- phenanthroline, methyl tricapryl ammonium chloride, three nonyl ammonium chloride of methyl, three decyl ammonium chloride of methyl,
Dimethyl two (N- octadecyl) ammonium chloride, methyl chloride dioctyl sulfonium salt or dioctylsulfoxide (DOSO).
8. technique as claimed in claim 5, which is characterized in that the organic phase also contains diluent；Preferably, described
Diluent includes：Kerosene, octanone, chloroform, carbon tetrachloride, toluene, dimethylbenzene, diethylbenzene, bromobenzene, methyl phenyl ethers anisole, nitromethane, 2-
Methyl cyclohexanone, methylisobutylketone, chlorobenzene, dichloro-benzenes, trichloro-benzenes, diphenyl ether, or combinations thereof.
9. technique as described in claim 1, which is characterized in that the phase inversion liquid water phase A1 is comprising solute selected from the group below
Aqueous solution：HCl,H2SO4、HBr、NaCl、NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4, or
A combination thereof.
10. technique as described in claim 1, which is characterized in that the adjusting liquid T is the water comprising solute selected from the group below
Solution：Sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide, or combinations thereof.
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| CN114989086A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海有机化学研究所 | Method for preparing fluorine-containing benzoquinoline heterocyclic compound |
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