CN113265541B - Extraction-electromigration coupling separation and enrichment 6 Method for Li isotope - Google Patents
Extraction-electromigration coupling separation and enrichment 6 Method for Li isotope Download PDFInfo
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Abstract
The invention discloses extraction-electromigration coupling separation and enrichment 6 A method of Li isotope. The method comprises the following steps: uniformly mixing ionic liquid, a diluent and a complexing agent to form an extracted organic phase; then uniformly mixing the extracted organic phase with a lithium salt solution, and collecting a lithium-loaded organic phase after extraction; then, enabling an anode, a cathode, anolyte, catholyte and an isolating membrane to jointly form an electromigration system, wherein the anolyte is an obtained lithium-loaded organic phase, and the isolating membrane is arranged between the anolyte and the catholyte; finally electrifying the electromigration system to obtain enrichment 6 A catholyte of Li. According to the method provided by the invention, under the action of an electric field, the lithium isotope separation effect continuously exists, the enrichment limit of the front end and the tail end of an ion migration flow does not exist, the isolation membrane has no saturation capacity limit, all solution phases can be recycled, and the process is clean and environment-friendly; in addition, the process of the invention has no special requirements on temperature, humidity, air and the like, and sealing is not needed.
Description
Technical Field
The invention belongs to the technical field of lithium isotope separation and enrichment, and particularly relates to extraction-electromigration coupling separation and enrichment 6 A method of Li isotope.
Background
The high-abundance lithium isotope plays an important role in national economy and national defense safety. More than 99.9% abundance 7 LiOH is an acidity regulator for pressurized water reactors, 7 LiBeF is a neutron moderator of a novel molten salt reactor. At an abundance of 30% to 90% 6 Li is an indispensable raw material for fusion reactors and hydrogen bombs, and is also used for various neutron detectors. With the maturity of molten salt reactor and fusion reactor technology, the market at home and abroad will be right in the coming decades 7 Li and 6 the demand for Li will increase day by day. While 7 Li and 6 the natural abundance of Li is 92.5% and 7.5%, respectively, which cannot be directly applied to the above fields and must be subjected to isotope separation.
The separation method of lithium isotope mainly includes lithium amalgam method, laser method, extraction method, electromagnetic method, electrochemical method, etc. The lithium amalgam method is to utilize the difference of the isotopic abundance of lithium amalgam and lithium ion in solution to realize isotopic separation. According to published data, the lithium amalgam method is the only method for the industrial production of lithium isotopes, a large amount of mercury is required, serious environmental hazards exist, and countries in Europe and America are gradually eliminated. The extraction method is characterized in that isotope separation is realized by utilizing the difference of lithium isotope abundance in a water phase and an organic phase, because the separation factor of single-stage extraction is extremely low, the extraction stage number can reach hundreds to thousands of stages in order to meet the requirements of related application fields on the lithium isotope abundance, and a huge amount of liquid phase generated in the extraction process needs to be treated, so that the complicated operation process and the extremely high production cost caused by the method increase the difficulty of the application of the method.
The existing electrochemical methods can be divided intoThree types are as follows: aqueous solution processes, molten salt processes, and organic solvent processes. The aqueous solution method mainly utilizes the difference of electromigration rates of isotope ions in an aqueous solution or a diaphragm to realize separation. The method has the advantages that electrode reactions all occur in aqueous solution, lithium ions generally do not undergo reduction reaction, continuous multi-stage separation is easy to realize, and the environmental protection pressure is small. However, due to the strong hydration of lithium ions in aqueous solution, the difference of the ratio of the electromigration rates of the isotope ions is sharply reduced, the separation factor of lithium isotopes is generally lower, and the current utilization rate of the process is lower. The separation factor of each time is as high as 1.4, but the separation factor is rapidly reduced along with the increase of the proportion of lithium ions migrating to a cathode, and the separation effect disappears when the proportion of the separation factor accounts for nearly 1% of the total amount of lithium ions in a system. Crown ether functionalized polymer membranes are prepared by Wangming Xixia of Tianjin university of industry, and the crown ether functionalized polymer membranes are coupled with an electric field for lithium isotope separation. The molten salt method mainly utilizes the difference of electromigration rates of lithium isotope ions in high-temperature molten salt to realize separation. The method has the advantages of simple and reliable process, easy realization of multi-stage continuous separation, no-water molecular complexation of lithium ions, high single-stage separation factor and high current utilization rate. However, the method has the problems of corrosion of high-temperature molten salt, chlorine gas, metal lithium and the like, and has extremely high requirements on the material of the device. The method controls the cathode atmosphere, and directly oxidizes a small amount of generated lithium metal to avoid the corrosion of the lithium metal to the cathode. Research on mixed molten salt systems such as lithium chloride, lithium bromide and lithium nitrate was carried out successively by the university of Tokyo industries, Japan, and the like, and LiNO was found 3 -NH 4 NO 3 The system obtains the optimal separation effect and obtains a small amount of 94.9 percent abundance 6 Li samples. The Spanish energy and environment research center Barrado et al provides an electrophoretic separation prototype based on lithium iodide fused salt, the device takes quartz as a shell and a lithium lanthanum titanate solid-state ion superconductor as a membrane, and according to the prediction, a single 100-grade continuous separation production line can annual produce 15kg of pure 15kg pure water 6 And (3) Li products. The organic solvent method mainly utilizes the difference of the proportion of lithium isotope in solvent, cathode and anode materialsNow, unlike the two methods described above, in which lithium is generally in an ionic state, lithium ions in the organic solvent method are partially reduced to metal or form an intercalation compound. The method has the advantages of room-temperature operation, mild reaction conditions, basically the same principle, materials and devices as the lithium ion battery, and the lithium ion battery industry can provide a good industrial foundation for the method. But the previous-stage enriched product can not be directly used as the raw material of the next stage, and multi-stage continuous separation is difficult to carry out; most of the used organic solvents are carbonate electrolytes, are sensitive to air and water and need to be closed.
The extraction method has extremely low separation factor of single-stage extraction, so that the extraction stage number can reach hundreds or even thousands of stages in order to meet the requirements of related application fields on the abundance of lithium isotopes, and a huge amount of water phase and organic phase solution with different lithium isotope abundances generated in the extraction process needs to be treated. If the aqueous phase and organic phase solution are not concentrated or stripped, they cannot be used in the next separation step. In addition, a certain amount of organic phase is dissolved in the aqueous phase. The reuse of the aqueous phase and the organic phase is influenced by the concentration, abundance and mutual dissolution of lithium ions, and is extremely difficult. Conventional electrochemical separation techniques: direct electromigration in aqueous solutions, due to the presence of hydration, the mass difference between the hydrated isotope lithium ions is very low, and the corresponding separation factor is also very low. The fused salt electromigration technology has the problems of high-temperature fused salt, gas, metal lithium corrosion and the like, and has extremely high requirements on the material of the device. The separation is realized by utilizing the proportion difference of lithium isotopes in the solvent, cathode and anode materials, the previous-stage enrichment product of the method is mostly a solid compound of metallic lithium or lithium, and cannot be directly used as the raw material of the next stage, and the multistage continuous separation is difficult to carry out; most of the used organic solvents are carbonate electrolytes, are sensitive to air and water and need to be closed. In addition, most of the existing electrochemical separation technologies need batch sample injection, and have obvious isotope separation effects only at the foremost end and the rearmost end of the lithium ion migration flow, and most of the lithium ion migration flow in the middle has no separation effect, so that the current utilization efficiency is low.
Disclosure of Invention
The main purpose of the present invention is to provide an extraction-electromigration coupling separation enrichment 6 A method of Li isotope to overcome the disadvantages of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides extraction-electromigration coupling separation and enrichment 6 A method of Li isotope comprising:
(1) uniformly mixing ionic liquid, a diluent and a complexing agent to form an extracted organic phase;
(2) uniformly mixing the extracted organic phase with a lithium salt solution, and collecting a lithium-loaded organic phase after extraction;
(3) enabling an anode, a cathode, anolyte, catholyte and an isolating membrane to jointly form an electromigration system, wherein the anolyte is the organic phase loaded with lithium obtained in the step (2), and the isolating membrane is arranged between the anolyte and the catholyte;
(4) electrifying the electromigration system to obtain enrichment 6 A catholyte of Li.
Compared with the prior art, the invention has the beneficial effects that:
(1) under the action of an electric field, the lithium isotope separation effect exists continuously, the enrichment limit of the front end and the tail end of an ion migration flow does not exist, the saturation capacity limit does not exist, and even if the proportion of lithium ions migrating to a water phase accounts for more than 90 percent of the total amount of lithium in a system, the obvious isotope separation effect still exists.
(2) In the multi-stage continuous separation process, the extraction process and the electromigration process are alternately carried out, lithium ions in the aqueous phase solution enter the extraction process after reaching a preset concentration, an organic phase obtained by extraction enters the electromigration process, and the lithium ions in the organic phase are regarded as regeneration after being lower than the preset concentration, so that the multi-stage continuous separation process does not need to be additionally processed, and can be simply and conveniently carried out;
(3) all solution phases can be recycled, and the process is clean and environment-friendly;
(4) the process has no special requirements on temperature, humidity, air and the like, and does not need sealing.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solutions of the present invention, which will be clearly and completely described below. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides an extraction-electromigration coupled separation enrichment 6 A method of Li isotope comprising:
(1) uniformly mixing ionic liquid, a diluent and a complexing agent to form an extracted organic phase;
(2) uniformly mixing the extracted organic phase with a lithium salt solution, and collecting a lithium-loaded organic phase after extraction;
(3) enabling an anode, a cathode, anolyte, catholyte and an isolating membrane to jointly form an electromigration system, wherein the anolyte is the organic phase loaded with lithium obtained in the step (2), and the isolating membrane is arranged between the anolyte and the catholyte;
(4) electrifying the electromigration system to obtain enrichment 6 A catholyte of Li.
In some more specific embodiments, the ionic liquid comprises 1-butyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-octyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-hexyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-ethyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-propyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt; any one or a combination of two or more of N-butyl-N-methylpyrrolidbis (trifluorosulfonyl) imide salt, N-butyl-N-methylpiperidinbis (trifluorosulfonyl) imide salt, tetrabutylphosphinbis (trifluorosulfonyl) imide salt, tributylmethylaminobis (trifluorosulfonyl) imide salt, 1-butyl-3-methylimidazolium hexafluorophosphate salt, 1-vinyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-allyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, and 1-benzyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, and is not limited thereto.
Further, the diluent includes any one or a combination of two or more of anisole, dichloromethane, chlorobenzene, dichlorobenzene, toluene, xylene, carbon tetrachloride, dichloroethane, petroleum ether, ethyl acetate, n-butanol, toluene, n-heptane, butyl acetate, isopropyl ether, and isobutanol, without being limited thereto.
Further, the complexing agent includes any one of crown ether compounds and quinoline compounds or a combination of two of them, and is not limited thereto.
In the invention, the complexing agent is neutral molecule, different from the traditional extractant, the extraction process has no special requirement on the extraction rate, and the complexing agent has no special requirement on the extraction rate in the extraction of the organic phase 7 Li has an enrichment effect.
Further, the crown ether compound includes any one or a combination of two or more of aminobenzene 12-crown-4, aminobenzene 15-crown-5, aminobenzene 15-crown-4, aminobenzene 18-crown-6, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formylbenzo-12-crown-4, formylbenzo-15-crown-5, formylbenzo-15-crown-4, and formylbenzo-18-crown-6, and is not limited thereto.
Further, the quinoline compound includes any one or a combination of two or more of 7- (4-ethyl-1-methyloctyl) -8-hydroxyquinoline, benzoquinoline, 4-methyl-10-hydroxybenzoquinoline, 4-nitro-7-ethyl-10-hydroxybenzoquinoline, 3-methanesulfonyl-7-chloro-10-mercaptobenzoquinoline, and 1,10-N, N-4-benzenesulfonylbenzoquinoline, and is not limited thereto.
Further, the compounds in the organic phase and the lithium salt solution are not extracted to form insoluble precipitates.
In some more specific embodiments, the volume ratio of the ionic liquid to the diluent in the step (1) is 1: 1-10.
Furthermore, the concentration of the complexing agent in the extraction organic phase is 0.1-10 mol/L.
In some more specific embodiments, the lithium salt solution comprises a lithium salt and water.
Further, the lithium salt includes any one or a combination of two or more of lithium chloride, lithium bromide, lithium iodide, lithium acetate, lithium sulfate, lithium nitrate, lithium perchlorate, lithium trifluoroacetate, lithium trichloroacetate, lithium bis (trifluoromethanesulfonyl) imide, lithium cyanide, lithium thiocyanate, and lithium hydroxide, and is not limited thereto.
Further, the concentration of lithium ions in the lithium salt solution is 0.1-20 mol/L.
Furthermore, the volume ratio of the extraction organic phase to the lithium salt solution is 1: 0.1-20.
Further, the extraction manner in the step (2) includes any one of stirring and shaking, and is not limited thereto.
Further, the extraction time is 0.5-2 h.
In some more specific embodiments, the catholyte in step (3) includes any one or a combination of two or more of an ammonium salt solution, a metal ion salt solution, and pure water, but is not limited thereto.
Further, the metal ions include any one or a combination of two or more of lithium ions, sodium ions, and potassium ions.
Furthermore, the concentration of ammonium ions and/or metal ions in the catholyte is below 0.1 mol/L.
Further, the material of the isolation film includes any one or a combination of two or more of polypropylene, polyethylene, polytetrafluoroethylene, polyethersulfone, and polyvinylidene fluoride, but is not limited thereto.
Further, the diameter of the pore channel of the isolating membrane is micron-sized and/or submicron-sized.
Furthermore, the isolating membrane can not be dissolved in the solution under the action of the electric field.
In the invention, the anolyte and the catholyte respectively carry out external circulation at constant flow rate, the catholyte with different lithium isotope abundances is periodically collected and respectively stored, and the anolyte and the catholyte are matched with organic phases with different lithium isotope abundances to be used in different electric field application time periods.
Further, the material of the anode includes any one or a combination of two or more of carbon, platinum, glassy carbon, palladium, tungsten, and copper, and is not limited thereto.
Further, the material of the cathode includes any one or a combination of two or more of carbon, platinum, glassy carbon, palladium, tungsten, and copper, and is not limited thereto.
In some more specific embodiments, the electromigration system employs an electric field comprising a DC electric field, and the application time is 0.5h to 120 h.
Further, the application method of the electric field includes any one of an uninterrupted electric field and an intermittent electric field, and is not limited thereto.
Further, the voltage used by the electric field is any one of a fixed value voltage and a periodically and regularly adjusted voltage, and is not limited thereto; the voltage used by the electric field can be constant and the magnitude of the voltage can be regularly adjusted according to a certain rule.
Further, the voltage of the electric field per centimeter distance is 0.5V-4.0V.
In some more specific embodiments, the method for preparing the lithium-loaded organic phase further comprises: by direct dissolution of lithium salts in the organic phase of the extraction or by driving lithium ions into the organic phase of the extraction with an electric field.
Further, the concentration of lithium ions in the anolyte is 0.05mol/L or more.
Further, when the concentration of lithium ions in the anolyte is less than 0.05mol/L, the anolyte may be replaced with a new one.
Further, the anolyte having a lithium ion concentration of less than 0.05mol/L may be reused by a stripping process.
In some more specific embodiments, the method further comprises: enriching the obtained product in the step (4) 6 Applying the catholyte of Li as catholyte to step (3) again, and repeating steps (3) - (4) until the obtained enrichment 6 The lithium ion concentration in the cathode solution of Li reaches more than 2 mol/L.
Further, the step of(4) The obtained lithium ion concentration is enriched by more than 2mol/L 6 The catholyte of Li is applied again to the step (2) as a lithium salt solution, and the steps (2) to (4) are repeated until the obtained enrichment 6 In the catholyte of Li 6 The Li abundance reaches the set value.
Further, the enrichment is carried out 6 The concentration of lithium ions in the Li catholyte is 2mol/L to 10 mol/L.
In the invention, the lithium isotope abundance collected in the catholyte can be influenced by different lithium isotope abundances, different voltages and different collection time periods in the anolyte. In the recycling process of the catholyte, the lithium isotope abundance of the anolyte, the system applied voltage and the acquisition time period are controlled within a certain range, so that the lithium isotope abundance in the recycled catholyte is ensured not to fluctuate too much. If the lithium isotope abundance, voltage or collection time period in the anolyte is changed obviously, the catholyte with corresponding lithium isotope abundance is also adjusted and used.
In some embodiments of the invention, the method may comprise:
preparing a lithium salt aqueous solution, and preparing an organic phase by using a ligand having a selective complexing effect on lithium isotope ions, a lithium ion co-extractant, a conductive enhancer and a diluent;
extracting the lithium salt aqueous solution with the organic phase to obtain a lithium-loaded organic phase;
taking an organic phase loaded with lithium as anolyte, taking an aqueous phase solution containing low-concentration electrolyte as catholyte, and separating the anolyte and the catholyte by a diaphragm so as to construct and form an electromigration separation system;
and applying an electric field to the electromigration separation system to enable lithium ions in the anolyte to migrate to the aqueous phase solution, wherein both the anolyte and the catholyte can use a pump to carry out-of-tank circulation, and the catholyte with different lithium isotope abundances is periodically collected and respectively stored so as to be matched with organic phases with different lithium isotope abundances to be used in different electric field application time periods.
Wherein, when the lithium ion in the organic phase as the anode liquid is low to a certain concentration, the organic phase is regarded as regeneration, and the lithium ion can be used for extracting the lithium salt aqueous solution again to obtain a lithium-loaded organic phase and is continuously used for electromigration separation.
When the concentration of lithium ions in the aqueous solution as the cathode liquid reaches a set concentration, the regenerated organic phase can be used for extracting the lithium ions, and the raffinate can be continuously used as the cathode liquid.
The extraction and electromigration processes can be alternately repeated until the obtained cathode liquid has lithium isotope abundance reaching the set abundance.
For example, in some more specific embodiments of the invention, catholyte may be collected every 4 to 8 hours and stored in a storage tank of corresponding abundance; the stored catholyte can be reused until the concentration of lithium ions reaches 2-10 mol/L, and the lithium-carrying organic phase is used as anolyte for reuse after extraction with fresh or regenerated organic phase. And a small amount of lithium is remained in the depleted anolyte, and the depleted anolyte is regenerated and recycled after back extraction. The process is circulated until the lithium isotope reaches the set abundance.
The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Mixing 1-butyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt and anisole in a volume ratio of 1:1, dissolving monoazabenzo 15-crown-5 to form an extracted organic phase, wherein the concentration of the monoazabenzo 15-crown-5 is 0.1mol/L, and preparing a lithium chloride solution with the lithium ion concentration of 10 mol/L;
(2) fully and uniformly mixing the extracted organic phase with a lithium chloride solution according to the volume ratio of 1:10, oscillating for 1h, and then centrifugally collecting the lithium-loaded organic phase;
(3) taking an organic phase loaded with lithium as an anolyte and 0.01mol/L ammonium chloride solution as a cathodePolar liquid, pure copper electrodes as anode and cathode, polypropylene film as isolating film, electric field voltage of 0.5V per centimeter distance, constant voltage DC, collecting cathode liquid electrified for 0-0.5 h, 6 the abundance of Li is 7.65%;
(4) taking the catholyte finally obtained in the step (3) as the catholyte again, and repeating the operation in the step (3) to collect lithium ions emigrated from the lithium-loaded organic phase until the concentration of the lithium ions in the catholyte reaches 2 mol/L; then, extracting the catholyte with the lithium ion concentration reaching 2mol/L by using a lithium-free organic phase to obtain a lithium-loaded organic phase, and continuously repeating the extraction and electromigration processes; after 20 cycles, in the catholyte 6 The abundance of Li reaches 10.15%.
Example 2
(1) Mixing 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and dichloromethane in a volume ratio of 1:10, dissolving 4-methyl-10-hydroxybenzoquinoline to form an extracted organic phase, wherein the concentration of the monoazabenzo 15-crown-5 is 10mol/L, and preparing a lithium ion solution with the lithium ion concentration of 20mol/L bis (trifluoromethanesulfonyl) imide;
(2) fully and uniformly mixing the extracted organic phase with a lithium bis (trifluoromethanesulfonyl) imide solution according to the volume ratio of 1:20, oscillating for 0.5h, and centrifugally collecting the lithium-loaded organic phase;
(3) taking an organic phase loaded with lithium as anolyte, 0.1mol/L ammonium chloride solution as catholyte, platinum electrodes as an anode and a cathode, a polyethylene film as an isolating film, an electric field voltage of 4.0V per centimeter distance, periodically applying voltage, electrifying and applying pressure for 1h, stopping applying for 1h, collecting catholyte electrified for 8-16 h, 6 the abundance of Li is 7.60%;
(4) taking the catholyte finally obtained in the step (3) as the catholyte again, and repeating the operation in the step (3) to collect lithium ions emigrated from the lithium-loaded organic phase until the concentration of the lithium ions in the catholyte reaches 6 mol/L; then, extracting the catholyte with the lithium ion concentration reaching 6mol/L by using a lithium-free organic phase to obtain a lithium-loaded organic phase, and continuously repeating the extraction and electromigration processes; after 10 cycles, in the catholyte 6 The abundance of Li reaches 8.00%.
Example 3
(1) Mixing 1-butyl-3-methylimidazole hexafluorophosphate and isobutanol according to the volume ratio of 1:5, dissolving formylbenzo-15-crown-5 to form an extracted organic phase, wherein the concentration of the formylbenzo-15-crown-5 is 5mol/L, and preparing a lithium bromide solution with the lithium ion concentration of 0.1 mol/L;
(2) fully and uniformly mixing the extracted organic phase with a lithium bromide solution according to the volume ratio of 1:0.1, oscillating for 2 hours, and centrifugally collecting the lithium-loaded organic phase;
(3) taking an organic phase loaded with lithium as anolyte, pure water as catholyte, a glassy carbon electrode as an anode and a cathode, a polytetrafluoroethylene membrane as an isolating membrane, an electric field voltage of 2.0V per centimeter distance, constant voltage direct current, collecting catholyte electrified for 2d to 3d, 6 the abundance of Li is 7.55%;
(4) taking the catholyte finally obtained in the step (3) as the catholyte again, and repeating the operation in the step (3) to collect lithium ions emigrated from the lithium-loaded organic phase until the concentration of the lithium ions in the catholyte reaches 10 mol/L; then, extracting the catholyte with the lithium ion concentration reaching 10mol/L by using a lithium-free organic phase to obtain a lithium-loaded organic phase, and continuously repeating the extraction and electromigration processes; after 40 cycles, in the catholyte 6 The abundance of Li reaches 9.00%.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (20)
1. Extraction-electromigration coupling separation and enrichment 6 A method of Li isotope characterized by comprising:
(1) uniformly mixing ionic liquid, a diluent and a complexing agent to form an extracted organic phase;
(2) uniformly mixing the extracted organic phase with a lithium salt solution, and collecting a lithium-loaded organic phase after extraction;
(3) enabling an anode, a cathode, anolyte, catholyte and an isolating membrane to jointly form an electromigration system, wherein the anolyte is the organic phase loaded with lithium obtained in the step (2), and the isolating membrane is arranged between the anolyte and the catholyte;
(4) electrifying the electromigration system to obtain enrichment 6 A catholyte of Li.
2. The method of claim 1, wherein: the ionic liquid is selected from 1-butyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-octyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-hexyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-ethyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-propyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt; N-butyl-N-methylpyrrolidine bis (trifluorosulfonyl) imide salt, N-butyl-N-methylpiperidine bis (trifluorosulfonyl) imide salt, tetrabutylphosphine bis (trifluorosulfonyl) imide salt, tributylmethylamine bis (trifluorosulfonyl) imide salt, 1-butyl-3-methylimidazolium hexafluorophosphate salt, 1-vinyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-allyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, 1-benzyl-3-methylimidazolium bis (trifluorosulfonyl) imide salt, or a combination of two or more thereof.
3. The method of claim 1, wherein: the diluent is selected from any one or the combination of more than two of anisole, dichloromethane, chlorobenzene, dichlorobenzene, toluene, xylene, carbon tetrachloride, dichloroethane, petroleum ether, ethyl acetate, n-butanol, n-heptane, butyl acetate, isopropyl ether and isobutanol.
4. The method of claim 1, wherein: the complexing agent is selected from crown ether compounds and/or quinoline compounds;
the crown ether compound is selected from any one or the combination of more than two of aminobenzene 12-crown-4, aminobenzene 15-crown-5, aminobenzene 15-crown-4, aminobenzene 18-crown-6, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formylbenzo-12-crown-4, formylbenzo-15-crown-5, formylbenzo-15-crown-4 and formylbenzo-18-crown-6;
the quinoline compound is selected from any one or the combination of more than two of 7- (4-ethyl-1-methyloctyl) -8-hydroxyquinoline, benzoquinoline, 4-methyl-10-hydroxybenzoquinoline, 4-nitro-7-ethyl-10-hydroxybenzoquinoline, 3-methanesulfonyl-7-chloro-10-mercaptobenzoquinoline and 1,10-N, N-4-benzenesulfonyl benzoquinoline.
5. The method of claim 1, wherein: in the step (1), the volume ratio of the ionic liquid to the diluent is 1: 1-10.
6. The method of claim 1, wherein: the concentration of the complexing agent in the extracted organic phase is 0.1-10 mol/L.
7. The method of claim 1, wherein: the lithium salt solution comprises lithium salt and water; the lithium salt is selected from any one or the combination of more than two of lithium chloride, lithium bromide, lithium iodide, lithium acetate, lithium sulfate, lithium nitrate, lithium perchlorate, lithium trifluoroacetate, lithium trichloroacetate, lithium bis (trifluoromethanesulfonyl) imide, lithium cyanide, lithium thiocyanate and lithium hydroxide; the concentration of lithium ions in the lithium salt solution is 0.1-20 mol/L.
8. The method of claim 1, wherein: in the step (2), the volume ratio of the extracted organic phase to the lithium salt solution is 1: 0.1-20.
9. The method of claim 1, wherein: the extraction time is 0.5-2 h.
10. The method of claim 1, wherein: the catholyte in the step (3) comprises any one or a combination of more than two of ammonium salt solution, metal ion salt solution and pure water; the metal ions are selected from any one or the combination of more than two of lithium ions, sodium ions and potassium ions; the concentration of ammonium ions and/or metal ions in the catholyte is below 0.1 mol/L.
11. The method of claim 1, wherein: the isolation membrane is made of any one or a combination of more than two of polypropylene, polyethylene, polytetrafluoroethylene, polyether sulfone and polyvinylidene fluoride; the diameter of the pore channel of the isolating membrane is micron-sized and/or submicron-sized.
12. The method of claim 1, wherein: the anode is made of any one or a combination of more than two of carbon, platinum, glassy carbon, palladium, tungsten and copper;
the cathode is made of any one or a combination of more than two of carbon, platinum, glassy carbon, palladium, tungsten and copper.
13. The method of claim 1, wherein: the electric field adopted by the electromigration system is selected from a direct current electric field, and the application time is 0.5 h-120 h.
14. The method of claim 13, wherein: the electric field is applied in a mode selected from an uninterrupted electric field and/or a batch type electric field; the strength of the electric field is: the voltage per centimeter distance is 0.5V-4.0V.
15. The method of claim 1, further comprising: by direct dissolution of lithium salts in the organic phase of the extraction or by driving lithium ions into the organic phase of the extraction with an electric field.
16. The method of claim 1, wherein: in the step (3), the concentration of lithium ions in the anolyte is kept above 0.05 mol/L.
17. The method of claim 1, wherein: and (3) after the step (3) is finished, if the lithium ion concentration in the anolyte is lower than 0.05mol/L, using the anolyte as an extraction organic phase for the step (2) again.
18. The method of claim 1, further comprising: enriching the obtained product in the step (4) 6 The catholyte of Li is used as the catholyte to be applied to the step (3) again, and the steps (3) - (4) are repeated until the enrichment is obtained 6 The lithium ion concentration in the cathode solution of Li reaches more than 2 mol/L.
19. The method of claim 1, wherein: enriching the lithium ion concentration obtained in the step (4) above 2mol/L 6 The catholyte of Li is used as the lithium salt solution to be applied to the step (2) again, and the steps (2) - (4) are repeated until the enrichment is obtained 6 In catholyte of Li 6 The Li abundance reaches the set value.
20. The method of claim 1, wherein: said enrichment 6 The concentration of lithium ions in the cathode solution of Li is 2-10 mol/L.
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