CN113262637B - Electromigration separation and enrichment 6 Method for producing Li isotopes - Google Patents
Electromigration separation and enrichment 6 Method for producing Li isotopes Download PDFInfo
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Abstract
The invention discloses an electromigration separation and enrichment method 6 A method of Li isotope, the method comprising: uniformly mixing the ionic liquid, the diluent and the complexing agent to form an organic phase which is used as a middle section groove liquid; then, the anode, the cathode, the anolyte, the catholyte, the middle section bath solution, the first isolating membrane and the second isolating membrane together form an electromigration system; the electromigration system is then energized to obtain enrichment 6 A catholyte of Li; the anode liquid comprises lithium salt solution, the first isolating film is arranged between the anode liquid and the middle section liquid, and the second isolating film is arranged between the middle section liquid and the cathode liquid. The method provided by the invention is simple to operate, the separation process only relates to an electromigration process, continuous production can be realized, the separation efficiency is greatly improved, and meanwhile, the electromigration is carried out by using a three-stage method, so that the ionization decomposition of an organic phase is avoided. All solution phases in the invention can be recycled, the process is clean and environment-friendly, and no special requirements on temperature, humidity, air and the like are required.
Description
Technical Field
The invention belongs to the technical field of lithium isotope separation and enrichment, and in particular relates to an electromigrationShift separation enrichment 6 A method of Li isotopes.
Background
The high-abundance lithium isotope plays an important role in national economy and national defense safety. 99.9% or more of abundance 7 LiOH is an acidity regulator of pressurized water reactors, 7 LiBeF is a neutron moderator of the novel fused salt reactor. 30% -90% of abundance 6 Li is an indispensable raw material for fusion reactors and hydrogen bombs, and is also used for various neutron detectors. With the maturation of molten salt reactor and fusion reactor technology, the market pairs at home and abroad in the coming decades are as follows 7 Li and Li 6 The demand for Li will increase. While 7 Li and Li 6 The natural abundance of Li is 92.5% and 7.5%, respectively, and neither can be directly applied to the above fields, and it is necessary to carry out isotope separation.
The separation method of the lithium isotope mainly comprises a lithium amalgam method, a laser method, an extraction method, an electromagnetic method, an electrochemical method and the like. The lithium amalgam method is to use the difference between the abundance of isotopes of lithium amalgam and lithium ions in solution to realize isotope separation. The lithium amalgam method is the only method for industrialized production of lithium isotopes, which needs to use a large amount of mercury, has serious environmental hidden trouble and is phased out by European and American countries. The extraction method is to realize isotope separation by utilizing the difference of lithium isotope abundance in the aqueous phase and the organic phase, and the extraction level can reach hundreds or even thousands of levels in order to meet the requirement of the related application field on lithium isotope abundance due to extremely low separation factor of single-stage extraction, and a huge amount of liquid phase generated in the extraction process needs to be treated, so that the complicated operation process and extremely high production cost are caused to increase the difficulty of the application of the method.
The existing electrochemical methods can be divided into three types: aqueous solution method, molten salt method and organic solvent method. The aqueous solution method mainly utilizes the difference of electromigration rate of isotope ions in aqueous solution or a diaphragm to realize separation. The method has the advantages that the electrode reactions all occur in aqueous solution, the lithium ions generally do not undergo reduction reaction, continuous multistage separation is easy to realize, and the environmental protection pressure is low. However, due to the strong hydration of lithium ions in aqueous solutions, isotope ions undergo electromigrationThe rate ratio difference is drastically reduced. The lithium isotope separation factor is generally low, and furthermore the process current utilization is low. The membrane injected with ionic liquid in the middle layer of Tsuyoshi in the Japanese atomic energy mechanism carries out electrodialysis separation on lithium isotopes in aqueous solution to obtain a single separation factor of 1.4, but the separation factor is rapidly reduced along with the increase of the proportion of lithium ions migrating to a cathode, and when the proportion of the separation factor accounting for the total lithium ions in the system is close to 1 percent, the separation effect is lost. Crown ether functionalized polymer membranes were prepared by Tianjin university of industry, wang Mingxia, etc., and 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 multistage continuous separation, no water molecule 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, metallic lithium and the like, and has extremely high requirements on the material of the device. The method controls the cathode atmosphere to directly oxidize a small amount of generated metal lithium, so as to avoid corrosion of the metal lithium to the cathode. The mixed molten salt system of lithium chloride, lithium bromide, lithium nitrate and the like is developed in succession at university of tokyo industry in japan and the like, and LiNO 3 -NH 4 NO 3 The system obtains the optimal separation effect and obtains a small amount of 94.9 percent of abundance 6 Li sample. The spanish energy and environment research center Barrado et al propose an electrophoresis separation prototype based on lithium iodide fused salt, the device takes quartz as a shell, lithium lanthanum titanate solid ion superconductor as a film, and according to the prediction, a single 100-level continuous separation production line can annual yield 15kg of pure 6 Li products. The organic solvent method mainly utilizes the difference of partition ratio of lithium isotopes in solvent, cathode and anode materials to realize separation, and unlike the two methods in which lithium is in an ionic state, lithium ions in the organic solvent method can be partially reduced into metal or form intercalation compounds. The method has the advantages of being capable of being operated at room temperature, mild in reaction condition, basically the same in principle, materials and devices as the lithium ion battery, and the lithium ion battery industry can provide a good industrial foundation for the method. However, the product of the previous stage of enrichment cannot be directly enrichedAs a raw material of the next stage, multistage continuous separation is difficult to carry out; most of the 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 level can reach hundreds or even thousands in order to meet the requirement of the related application field on lithium isotope abundance, and huge amounts of aqueous phase and organic phase solutions with different lithium isotope abundance generated in the extraction process need to be treated. If the aqueous and organic phase solutions 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 and organic phases is affected by the concentration, abundance and mutual dissolution of lithium ions, with great difficulty. Conventional electrochemical separation techniques: the direct electromigration in the aqueous solution has very low mass difference between lithium ions of the hydrated isotopes due to the existence of hydration, and the corresponding separation factor is also very low. The molten salt electrotransport technology has the problems of high-temperature molten salt, gas and metal lithium corrosion and the like, and has extremely high requirements on the device materials. The organic solution is separated by utilizing the distribution ratio difference of lithium isotopes in solvent, cathode and anode materials, and the product of the previous stage enrichment is mostly metallic lithium or solid compound of lithium, which can not be directly used as the raw material of the next stage, and is difficult to carry out multistage continuous separation; the organic solvents used are also mostly carbonate electrolytes, are sensitive to air and water and require a closed operation. In addition, most of the existing electrochemical separation technologies need batch sample injection, and have obvious isotope separation effects only at the forefront and the extreme ends of lithium ion migration flows, and most of the lithium ion migration flows in the middle have no separation effect, so that the current utilization efficiency is low.
Disclosure of Invention
The main purpose of the invention is to provide an electromigration separation and enrichment method 6 The Li isotope method overcomes the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an electromigration separation enrichment method 6 A method of Li isotope, comprising:
(1) Uniformly mixing the ionic liquid, the diluent and the complexing agent to form an organic phase;
(2) The anode, the cathode, the anolyte, the catholyte, the middle section bath solution, the first isolating membrane and the second isolating membrane together form an electromigration system, wherein the middle section bath solution is the organic phase obtained in the step (1), the anolyte comprises lithium salt solution, the first isolating membrane is arranged between the anolyte and the middle section bath solution, and the second isolating membrane is arranged between the middle section bath solution and the catholyte;
(3) Energizing the electrotransport system to obtain enrichment 6 And (3) cathode liquid of Li.
The principle of the invention is that the complexing agent in the middle section groove liquid organic phase plays the roles of a bridge and a screening agent at the same time, the complexing capability of the complexing agent enables lithium ions to enter the organic phase from the anode water phase in a large amount, and the complexing instability of the complexing agent enables the lithium ions to get rid of complexing agent molecules into the water phase of the cathode under the action of an electric field; when solvated lithium ions in the aqueous phase are complexed with the complexing agent in the organic phase, most of coordinated water molecules of the lithium ions are removed from cavities in the molecular structure of the complexing agent, so that the isotope lithium ions migrated in the organic phase show more obvious quality and speed difference relative to the isotope lithium ions migrated in the aqueous phase, and the isotope separation effect of the system is enhanced.
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 continuously exists, the front end and the tail end of ion migration flow are not limited in lithium isotope enrichment, and the isolation film is not limited in saturated capacity; even if the proportion of lithium ions migrating into the water phase accounts for more than 90% of the total lithium in the system, the isotope separation effect is obvious;
(2) The multistage continuous separation process is simple to operate, the separation process only relates to an electromigration process, the product of the upper stage is directly used as the raw material of the lower stage, and the continuous production can be realized without a phase transfer or concentration process in the middle; in addition, the three-stage method avoids ionization decomposition of the organic phase;
(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;
(5) The electrode liquid adopts aqueous phase solution, and the byproducts are only hydrogen and oxygen;
(6) The separation process has no requirement on the selectivity of the complex to lithium isotopes, and the lithium ions migrating to the catholyte are enriched relative to the anolyte 6 Li。
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
One aspect of an embodiment of the present invention provides an electromigration separation enrichment 6 A method of Li isotope, comprising:
(1) Uniformly mixing the ionic liquid, the diluent and the complexing agent to form an organic phase;
(2) The anode, the cathode, the anolyte, the catholyte, the middle section bath solution, the first isolating membrane and the second isolating membrane together form an electromigration system, wherein the middle section bath solution is the organic phase obtained in the step (1), the anolyte comprises lithium salt solution, the first isolating membrane is arranged between the anolyte and the middle section bath solution, and the second isolating membrane is arranged between the middle section bath solution and the catholyte;
(3) Energizing the electrotransport system to obtain enrichment 6 And (3) cathode liquid of Li.
In some more specific embodiments, the ionic liquid comprises 1-butyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-octyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-hexyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-propyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt; any one or a combination of two or more of N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt, N-butyl-N-methylpiperidine bis (trifluoromethylsulfonyl) imide salt, tetrabutylphosphine bis (trifluoromethylsulfonyl) imide salt, tributylmethylamine bis (trifluoromethylsulfonyl) imide salt, 1-butyl-3-methylimidazole hexafluorophosphate, 1-vinyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-allyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-benzyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, and the like is not limited thereto.
Further, the diluent includes any one or a combination of two or more of anisole, methylene chloride, chlorobenzene, dichlorobenzene, toluene, xylene, carbon tetrachloride, dichloroethane, petroleum ether, ethyl acetate, n-butanol, toluene, n-heptane, butyl acetate, isopropyl ether, and isobutanol, and is not limited thereto.
In some more specific embodiments, the complexing agent includes any one or a combination of two or more of crown ether compounds, crown ether compound derivatives, quinoline compounds, quinoline compound derivatives, hole ether compounds, and hole ether compound derivatives, and is not limited thereto.
In the invention, the complexing agent is a neutral molecule, the complexing agent has coordination effect on lithium isotopes in an organic phase, and the number of coordination water molecules of lithium ions in a complex formed after combination is less than 2.
Further, the method comprises the steps of, the crown ether compound and/or crown ether compound derivative comprises aminobenzo 12-crown-4, aminobenzo 15-crown-5, aminobenzo 15-crown-4, aminobenzo 18-crown-6, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formyl benzo 12-crown-4, formyl benzo 15-crown-5, formyl benzo 15-crown-4, formyl benzo 18-crown-6, aminobenzo 12-crown-4, aminobenzo 15-crown-5, aminobenzo 15-crown-4 aminobenzo 18-crown-6, cyclohexylbenzo 15-crown-5, cyclohexylbenzo 12-crown-4, 4' -di-tert-butyldibenzo-30 crown-10, 4-tert-butylbenzo-18 crown-6, 4-tert-butylbenzo-15 crown-5, 4-tert-butylbenzo-12 crown-4, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formyl benzo 12-crown-4, formyl benzo 15-crown-5, formyl benzo 15-crown-4, any one or a combination of two or more of formyl benzo-18-crown-6, 4-methyl-benzo-15-crown-5, 4-methyl-benzo-12-crown-4, p-tolyloxy biphenyl bridged bisbenzo-15-crown-5 and metallic hetero 12-crown-3, wherein the metal comprises ruthenium and/or rhodium, and is not limited thereto.
Further, the quinoline compound and/or quinoline compound derivative includes any one or a combination of two or more of 7- (4-ethyl-1-methyl octyl) -8-hydroxyquinoline, benzoquinoline, 4-methyl-10-hydroxybenzoquinoline, 4-nitro-7-ethyl-10-hydroxybenzoquinoline, 3-methanesulfonyl-7-chloro-10-mercaptobenzoquinoline, 1,10-N, N-4-benzenesulfonylbenzoquinoline, and is not limited thereto.
Further, the method comprises the steps of, the hole ether compound and/or the hole ether compound derivative comprises a hole ether (2, 2), a hole ether (2, 1), a hole ether (2, 1), a hole ether (3, 3), a hole ether (2, 1) any one or the combination of more than two of hole ether (3,2,3), hole ether (2, 3, 2), n-nitrogen heterocyclic hole ether (2, 1) and n-nitrogen heterocyclic hole ether (2, 3), wherein n is selected from any integer of 1 to 3, and is not limited thereto.
In some more specific embodiments, the volume ratio of the ionic liquid to the diluent in step (1) is from 1:1 to 10.
Further, the concentration of the complexing agent in the organic phase is 0.1mol/L to 10mol/L.
In some more specific embodiments, the anolyte comprises a lithium salt solution, and is not limited thereto.
Further, the lithium salt solution includes 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, and lithium bis (trifluoromethanesulfonyl) imide, and is not limited thereto.
Further, the catholyte comprises any one or more than two of ammonium salt solution, metal ion salt solution and pure water.
Further, the metal ions include any one or a combination of two or more of lithium ions, sodium ions, and potassium ions, and are not limited thereto.
Further, the concentration of ammonium ions and/or metal ions in the catholyte is below 0.1 mol/L.
In some more specific embodiments, the materials of the first isolation film and the second isolation film include any one or a combination of more than two of polypropylene, polyethylene, polytetrafluoroethylene, polyethersulfone and polyvinylidene fluoride, and are not limited thereto.
Further, the diameters of pore passages of the first isolating membrane and the second isolating membrane are micron-sized and/or submicron-sized.
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 electric field employed by the electrotransport system comprises a direct current electric field applied for a period of time ranging from 4 hours to 72 hours.
Further, the application mode 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 constant voltage and a voltage regulated periodically and regularly, and is not limited thereto. The voltage used by the electric field can be constant, and the magnitude of the voltage can be regularly regulated according to a certain rule.
Further, the electric field has a strength of: the voltage over the distance per centimeter is 2V to 50V.
In some more specific embodiments, the concentration of lithium ions in the lithium salt solution is from 0.1mol/L to 20mol/L.
Further, when the concentration of lithium ions in the anolyte is lower than 0.05mol/L, the anolyte is replaced by a new anolyte.
In some more specific embodiments, the method further comprises: enriching the product obtained in the step (3) 6 The catholyte of Li is applied again as catholyte to step (2) and steps (2) to (3) are repeated until enrichment is obtained 6 The concentration of lithium ions in the cathode liquid of Li reaches more than 2 mol/L.
Further, enriching the lithium ion concentration obtained in the step (3) to be more than 2mol/L 6 The catholyte of Li as lithium salt solution is applied again in step (2) as anode solution and steps (2) to (3) are repeated until enrichment is obtained 6 In the catholyte of Li 6 The Li abundance reaches the set value.
Further, the enrichment 6 The concentration of lithium ions in the Li catholyte is 2mol/L to 10mol/L.
Further, the method is a multistage continuous separation process.
In the method, when the new anode liquid is replaced, if the lithium isotope abundance in the new anode liquid is inconsistent with the lithium isotope abundance in the old anode liquid (namely after electromigration), the middle-stage bath liquid needs to be subjected to acid washing regeneration; if the lithium isotopes in the two solutions are consistent in abundance, the two solutions can be directly used.
In the method, the anode liquid and the cathode liquid are respectively circulated externally at constant flow rates, the cathode liquids with different lithium isotope abundances are collected periodically, stored respectively and matched with organic phases with different lithium isotope abundances for use in different electric field application time periods.
For example, in some more specific embodiments of the invention, catholyte may be collected every 4-8 hours and stored in a corresponding abundance tank; the stored catholyte can be reused until the concentration of lithium ions reaches 2mol/L to 10mol/L, and the catholyte can be directly used as lithium salt solution for anode liquid. The above process is cycled back and forth until the lithium isotope reaches the set abundance.
In the above method, when the concentration of the lithium ions in the anolyte is lower than the set concentration, a new lithium salt solution is replaced. According to the separation target, when the lithium ions in the catholyte reach the set concentration, the catholyte can be directly used as the anolyte. If the organic phase needs to be regenerated, an acid solution is used as an anode liquid, an electric field is applied, and all lithium ions in the organic phase are removed.
The technical scheme of the invention is further described in detail below with reference to a plurality of preferred embodiments, the embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
(1) Mixing 1-butyl-3-methylimidazole hexafluorophosphate and isobutanol in a volume ratio of 1:1, dissolving formyl benzo-15-crown-5 to form an organic phase, wherein the concentration of the formyl benzo-15-crown-5 is 0.1mol/L, and preparing a lithium bromide solution with the concentration of lithium ions of 0.1 mol/L;
(2) Taking an organic phase as a middle section bath solution, taking lithium bromide solution as anode solution, taking pure water as cathode solution, taking platinum as anode, taking pure copper as cathode, taking a polytetrafluoroethylene film as an isolating film, taking the electric field voltage of 2.0V per cm distance, collecting the cathode solution electrified for 64-72 h, 6 the abundance of Li is 7.60%;
(3) Taking the catholyte finally obtained in the step (2) as the catholyte again, and repeating the operation of the step (2) to collect the lithium ions which are migrated from the organic phase loaded with lithium until the concentration of the lithium ions in the catholyte reaches 2mol/L; then, replacing a new middle section swimming pool solution, and directly using the collected catholyte as anode liquid; after 10 cycles, in the catholyte 6 The abundance of Li reaches 10.00%.
Example 2
(1) Mixing 1-allyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt and petroleum ether according to a volume ratio of 1:5, dissolving 1,10-N, N-4-benzenesulfonyl benzoquinoline to form an organic phase, wherein the concentration of 1,10-N, N-4-benzenesulfonyl benzoquinoline is 5mol/L, and preparing a lithium iodide solution with the lithium ion concentration of 10mol/L;
(2) Taking an organic phase as a middle section bath solution, taking lithium iodide solution as an anode solution, taking 0.01mol/L potassium chloride solution as a cathode solution, taking graphite as an anode, taking glassy carbon as a cathode, taking a polytetrafluoroethylene film as an isolating film, taking the electric field voltage of 20V per cm distance, collecting the cathode solution electrified for 0-4 h, 6 the abundance of Li is 7.65%;
(3) Taking the catholyte finally obtained in the step (2) as the catholyte again, and repeating the operation of the step (2) to collect the lithium ions which are migrated from the lithium-loaded organic phase until the concentration of the lithium ions in the catholyte reaches 6mol/L; then, replacing a new middle section swimming pool solution, and directly using the collected catholyte as anode liquid; after 20 cycles, in the catholyte 6 The abundance of Li reaches 11.50%.
Example 3
(1) Mixing N-butyl-N-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and xylene according to a volume ratio of 1:10, dissolving hole ether (2, 1) to form an organic phase, wherein the concentration of the hole ether (2, 1) is 10mol/L, and preparing a bis (trifluoromethanesulfonyl) imide lithium solution with the lithium ion concentration of 20 mol/L;
(2) Taking an organic phase as a middle section bath solution, taking a bis (trifluoromethanesulfonyl) imide lithium solution as an anode solution, taking a 0.1mol/L ammonium chloride solution as a cathode solution, taking platinum as an anode, taking pure tungsten as a cathode, taking a polytetrafluoroethylene film as an isolating film, taking the electric field voltage of 50V per cm distance, collecting the cathode solution electrified for 12-16 h, 6 the abundance of Li is 7.68%;
(3) Taking the catholyte finally obtained in the step (2) as the catholyte again, and repeating the operation of the step (2) to collect the lithium ions which are migrated from the organic phase loaded with lithium until the concentration of the lithium ions in the catholyte reaches 10mol/L; then, replacing a new middle section swimming pool solution, and directly using the collected catholyte as anode liquid; after 40 cycles, in the catholyte 6 The abundance of Li reaches 12.00%.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely 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 present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, 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 the scope thereof. 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 (9)
1. Electromigration separation and enrichment 6 A method of Li isotopes, characterized by comprising:
(1) Uniformly mixing the ionic liquid, the diluent and the complexing agent to form an organic phase; the complexing agent is selected from any one or more than two of crown ether compounds, crown ether compound derivatives, quinoline compounds, quinoline compound derivatives, cave ether compounds and cave ether compound derivatives; the crown ether compound and/or crown ether compound derivative is selected from aminobenzo 12-crown-4, aminobenzo 15-crown-5, aminobenzo 15-crown-4, aminobenzo 18-crown-6, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formyl benzo 12-crown-4, formyl benzo 15-crown-5, formyl benzo 15-crown-4, formyl benzo 18-crown-6, aminobenzo 12-crown-4, aminobenzo 15-crown-5, aminobenzo 15-crown-4 aminobenzo 18-crown-6, cyclohexylbenzo 15-crown-5, cyclohexylbenzo 12-crown-4, 4' -di-tert-butyldibenzo-30 crown-10, 4-tert-butylbenzo-18 crown-6, 4-tert-butylbenzo-15 crown-5, 4-tert-butylbenzo-12 crown-4, monoazabenzo 12-crown-4, monoazabenzo 15-crown-5, monoazabenzo 15-crown-4, monoazabenzo 18-crown-6, formyl benzo-12-crown-4, formyl benzo-15-crown-5, formyl benzo-15-crown-4, formyl benzo-18-crown-6, any one or more than two of 4-methyl-benzo-18-crown-6, 4-methyl-benzo-15-crown-5, 4-methyl-benzo-12-crown-4, p-tolyloxy biphenyl bridged bisbenzo-15-crown-5 and metal impurity 12-crown-3, wherein the metal is selected from ruthenium and/or rhodium; the quinoline compound and/or quinoline compound derivative is selected from any one or more than two of 7- (4-ethyl-1-methyl octyl) -8-hydroxyquinoline, benzoquinoline, 4-methyl-10-hydroxybenzoquinoline, 4-nitro-7-ethyl-10-hydroxybenzoquinoline, 3-methanesulfonyl-7-chloro-10-mercapto-benzoquinoline, 1,10-N, N-4-benzenesulfonyl-benzoquinoline; the hole ether compound and/or the hole ether compound derivative is selected from hole ether (2, 2), hole ether (2, 1), hole ether (2, 1), hole ether (3, 3) any one or the combination of more than two of hole ether (3,2,3), hole ether (2, 3, 2), n-nitrogen heterocyclic hole ether (2, 1) and n-nitrogen heterocyclic hole ether (2, 3), wherein n is any integer from 1 to 3; the ionic liquid is selected from 1-butyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt, 1-octyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt, 1-hexyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt, 1-ethyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt and 1-propyl-3-methylimidazole bis (trifluoro sulfonyl) imide salt; any one or a combination of two or more of N-butyl-N-methylpyrrolidine bis (trifluoromethylsulfonyl) imide salt, N-butyl-N-methylpiperidine bis (trifluoromethylsulfonyl) imide salt, tetrabutylphosphine bis (trifluoromethylsulfonyl) imide salt, tributylmethylamine bis (trifluoromethylsulfonyl) imide salt, 1-butyl-3-methylimidazole hexafluorophosphate, 1-vinyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-allyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt, 1-benzyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide salt; the diluent is selected from any one or more than two 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;
(2) The anode, the cathode, the anolyte, the catholyte, the middle section bath solution, the first isolating membrane and the second isolating membrane together form an electromigration system, wherein the middle section bath solution is the organic phase obtained in the step (1), the anolyte is selected from lithium salt solution, the first isolating membrane is arranged between the anolyte and the middle section bath solution, and the second isolating membrane is arranged between the middle section bath solution and the catholyte; the electric field strength adopted by the electromigration system is as follows: the voltage is 2V-50V at each centimeter distance; the catholyte is selected from any one or the combination of two of ammonium salt solution and metal ion salt solution; the metal ions are selected from any one or 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;
(3) Energizing the electrotransport system to obtain enrichment 6 A catholyte of Li;
(4) Enriching the product obtained in the step (3) 6 The catholyte of Li is applied to the step (2) again as the catholyte, and the steps (2) - (3) are repeated until the enrichment is achieved 6 The concentration of lithium ions in the cathode liquid of Li reaches more than 2mol/L;
(5) Enriching the lithium ion concentration obtained in the step (4) to be more than 2mol/L 6 The cathode solution of Li is used as lithium salt solution to be applied in the step (2) as anode solution again, and the steps (2) - (3) are repeated until the enrichment is achieved 6 In the catholyte of Li 6 The Li abundance reaches the set value.
2. The method according to claim 1, characterized in that: in the step (1), the volume ratio of the ionic liquid to the diluent is 1:1-10.
3. The method according to claim 1, characterized in that: the concentration of the complexing agent in the organic phase is 0.1 mol/L-10 mol/L.
4. The method according to claim 1, characterized in that: the anolyte is selected from lithium salt solution; the lithium salt solution comprises lithium salt and water; the lithium salt is selected from any one or 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.
5. The method according to claim 1, characterized in that: the first isolation film and the second isolation film are made of any one or more than two of polypropylene, polyethylene, polytetrafluoroethylene, polyether sulfone and polyvinylidene fluoride;
the diameters of pore passages of the first isolating membrane and the second isolating membrane are in a micron level and/or a submicron level.
6. The method according to claim 1, characterized in that: the anode is made of any one or more than two materials selected from carbon, platinum, glass carbon, palladium, tungsten and copper.
7. The method according to claim 1, characterized in that: the cathode is made of any one or more than two materials selected from carbon, platinum, glass carbon, palladium, tungsten and copper.
8. The method according to claim 1, characterized in that: the electric field adopted by the electrotransport system is selected from a direct current electric field, and the application mode of the electric field is selected from an uninterrupted electric field and/or an intermittent electric field.
9. The method according to claim 1, characterized in that: and (3) the concentration of lithium ions in the anode liquid in the step (2) is 0.1-20 mol/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373341A (en) * | 2010-08-12 | 2012-03-14 | 独立行政法人日本原子力研究开发机构 | Recovering method and devcie of lithium |
| CN103801194A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院上海有机化学研究所 | Extraction agent for separation of lithium isotopes and application thereof |
| CN105536537A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院青海盐湖研究所 | Method for extracting lithium isotope |
| CN109439914A (en) * | 2019-01-08 | 2019-03-08 | 安徽工业大学 | A method of the Selective Separation lithium from waste lithium ion cell anode material extract |
| JP2019141808A (en) * | 2018-02-22 | 2019-08-29 | 国立大学法人弘前大学 | Lithium isotope concentrator, multistage lithium isotope concentrator, and lithium isotope concentration method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5371796A (en) * | 1976-12-06 | 1978-06-26 | Toyama Yakuhin Kougiyou Kk | Method of continuously separating isotope by ion exchange |
| JP5429658B2 (en) * | 2008-07-29 | 2014-02-26 | 独立行政法人日本原子力研究開発機構 | Lithium isotope separation and concentration method and apparatus, and 6Li isotope or 7Li isotope highly concentrated recovery system and recovery method |
| DE102013202976A1 (en) * | 2013-02-22 | 2014-08-28 | Siemens Aktiengesellschaft | Low-temperature process for the production of lithium from poorly soluble lithium salts |
| CN105536536B (en) * | 2015-12-17 | 2017-11-07 | 中国科学院青海盐湖研究所 | A kind of extraction system for extracting lithium isotope |
| CN108060308B (en) * | 2017-12-12 | 2020-01-03 | 中南大学 | Method and device for separating lithium from lithium-containing solution |
| CN109200822A (en) * | 2018-11-16 | 2019-01-15 | 天津工业大学 | A kind of method of field coupling crown ether graft polymers perforated membrane separation lithium isotope |
| CN110106369B (en) * | 2019-05-06 | 2020-10-16 | 清华大学 | Lithium ion solid electrolyte-based lithium element extraction method and device |
-
2020
- 2020-02-14 CN CN202010092601.5A patent/CN113262637B/en active Active
- 2020-08-03 WO PCT/CN2020/106555 patent/WO2021159673A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373341A (en) * | 2010-08-12 | 2012-03-14 | 独立行政法人日本原子力研究开发机构 | Recovering method and devcie of lithium |
| CN103801194A (en) * | 2012-11-05 | 2014-05-21 | 中国科学院上海有机化学研究所 | Extraction agent for separation of lithium isotopes and application thereof |
| CN105536537A (en) * | 2015-12-17 | 2016-05-04 | 中国科学院青海盐湖研究所 | Method for extracting lithium isotope |
| JP2019141808A (en) * | 2018-02-22 | 2019-08-29 | 国立大学法人弘前大学 | Lithium isotope concentrator, multistage lithium isotope concentrator, and lithium isotope concentration method |
| CN109439914A (en) * | 2019-01-08 | 2019-03-08 | 安徽工业大学 | A method of the Selective Separation lithium from waste lithium ion cell anode material extract |
Non-Patent Citations (4)
| Title |
|---|
| Gui Liu, Zhongwei Zhao, Ahmad Ghahreman.Novel approaches for lithium extraction from salt-lake brines: A review.Hydrometallurgy.2019,vol 187全文. * |
| Tsuyoshi Hoshino, Takayuki Terai.High-efficiency technology for lithium isotope separation using an ionic-liquid impregnated organic membrane.Fusion Engineering and Design.2011,vol 86(No 9-11),第2168–2171页. * |
| 杨国华 曾权兴 .稳定同位素分离.原子能出版社,1989,(第1989年4月第一版),第141-142页. * |
| 赵岩 ; 敖银勇 ; 陈建 ; 宋宏涛 ; 黄玮 ; 彭静 ; .基于密度泛函理论研究锂―冠醚复合物的结构和热力学参数.物理化学学报.2016,(第07期),全文. * |
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