CN108854537B - Process for separating lithium isotope by liquid-liquid extraction - Google Patents
Process for separating lithium isotope by liquid-liquid extraction Download PDFInfo
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Abstract
The invention provides a process for separating lithium isotopes by liquid-liquid extraction. Specifically, the process comprises the following steps: continuous countercurrent running of the organic and aqueous phases: the lithium-containing organic phase after the lithium saponification section sequentially passes through an extraction separation C1 section, an extraction separation C2 section and a phase inversion section; the lithium-containing water phase after the phase inversion section sequentially passes through a buffer H2 section, an extraction separation C2 section, an extraction separation C1 section and a buffer H1 section; the buffer H1 segment and the buffer H2 segment are adopted, so that the abundances of the lithium-6 enriched product P1 and the lithium-7 enriched product P2 are conveniently regulated and controlled, and two enriched products enriched with lithium-6 and lithium-7 can be obtained simultaneously. The invention has reasonable and simple flow design and convenient operation, can effectively buffer and control the fluctuation of flow and realize the high-efficiency separation and enrichment of the lithium isotope.
Description
Technical Field
The invention relates to isotope separation in the field of chemical industry, in particular to a process for separating lithium isotopes by liquid-liquid extraction.
Background
Lithium (Li) has two natural isotopes in nature, namely7Li (lithium-7) and6li (lithium-6), accounting for 92.48% and 7.52%, respectively. After separation, enrichment and concentration, the two isotopes respectively have different important applications in the field of nuclear materials. In the thorium-based molten salt reactor,7li is an indispensable molten salt coolant, since6The thermal neutron absorption cross section of Li is very high, reaching 941barns, while7Li is only 0.033barns, so the molten salt heap pair7Isotopic abundance requirement of Li>99.995 percent. At the same time, high purity7Li is commonly used to adjust the pH of the primary coolant in pressurized water reactors, in fusion reactors7Li also acts as a heat carrier for heat conduction. On the other hand, in the case of a liquid,6li is a fuel in a nuclear fusion reactor, wherein6Isotopic abundance requirement of Li>30 percent. Lithium isotopes are indispensable strategic materials and energy materials no matter thorium-based molten salt reactors or nuclear fusion reactors.
The method for separating lithium isotopes includes a physical method (such as an electromagnetic method, a molecular distillation method, a gas diffusion method and the like) and a chemical method (such as an electromigration method, an electrolysis method, a lithium amalgam exchange method, a solvent extraction exchange method and the like) (Shouchuan and the like, nuclear chemistry and radiology, 1991, 13, 1). in isotope separation, a physical method is favorable for heavy isotopes, while for light isotopes, the chemical method has high efficiency, the physical method has low efficiency and large investment, lithium isotopes belong to light isotopes, and lithium has no gaseous compounds, so that the physical method is only in an exploration stage for separating lithium isotopes.
Disclosure of Invention
The invention aims to provide a process for separating lithium isotopes by liquid-liquid extraction.
In a first aspect of the present invention, there is provided a process for separating lithium isotopes by liquid-liquid extraction, the process comprising the steps of:
(1) continuous countercurrent running of the organic and aqueous phases:
the lithium-containing organic phase after the lithium saponification section sequentially passes through an extraction separation C1 section, an extraction separation C2 section and a phase inversion section;
the lithium-containing water phase after the phase inversion section sequentially passes through a buffer H2 section, an extraction separation C2 section, an extraction separation C1 section and a buffer H1 section;
(2) adding lithium-containing feed liquid F between the extraction separation C1 section and the extraction separation C2 section;
adding a regulating solution T into a buffer H2 section;
adding a phase inversion liquid water phase A1 into the phase inversion section;
(3) continuously flowing out part of the aqueous phase in the buffer H1 section to obtain a lithium-6 enriched product P1, and feeding the rest of the aqueous phase into a lithium saponification section;
(4) part of the water phase in the buffer H2 section continuously flows out to obtain a lithium-7 enriched product P2, and the rest part of the water phase enters an extraction separation C2 section.
In another preferred embodiment, in the step (3), the ratio of the flow rate of the aqueous phase P1 flowing out of the buffer H1 section to the flow rate of the aqueous phase flowing into the lithium saponification section is 1:3 to 3500.
In another preferred example, in the step (4), the ratio of the flow rate of the aqueous phase P2 flowing out of the buffer H2 section to the flow rate of the aqueous phase flowing into the extraction separation C2 section is 1:3 to 3500.
In another preferred embodiment, said counter-current operation means that the flow direction of said aqueous phase and said organic phase are opposite.
In another preferred example, the method further includes:
extracting the aqueous phase comprising the lithium element in a lithium saponification section, an extraction separation C1 section and an extraction separation C2 section to load the lithium element with the organic phase; and/or
And in the phase inversion section, performing phase inversion stripping on the organic phase comprising the lithium element.
In another preferred example, the lithium concentration of the loaded organic phase is in the range of 0.01-2 mol/L.
In another preferred embodiment, the extraction separation section C1 and the extraction separation section C2 are respectively formed by cascade connection of a plurality of liquid-liquid separation devices, and preferably, the liquid-liquid separation devices are centrifugal extractors.
In another preferred embodiment, the total number of stages N of the extraction separation C1 stage is in the range of 5-500 stages.
In another preferred embodiment, the total number of stages M of the extraction separation C2 stage is in the range of 5-500 stages.
In another preferred example, the concentration of lithium element in the water phase at the outlet of the phase inversion section is in the range of 0.01-4 mol/L.
In another preferred embodiment, the process further comprises:
the organic phase flowing out from the phase inversion section enters a lithium saponification section for circulation after being saponified by alkali liquor in an alkali saponification section; and/or
Adding alkali liquor A3 into the alkali saponification section; and/or
Discharging aqueous phase a2 from the lithium saponification stage; and/or
The aqueous phase A4 was discharged from the alkaline saponification stage.
In another preferred embodiment, the concentration of lithium ions in the aqueous phase A2 is less than 0.005 mol/L.
In another preferred embodiment, the aqueous phase a4 is free of lithium ions.
In another preferred embodiment, the alkaline solution contains a solute selected from the group consisting of: sodium hydroxide, ammonium hydroxide, potassium hydroxide, cesium hydroxide, or combinations thereof.
In another preferred example, the buffer H1 section comprises a first liquid storage tank, and the buffer H2 section comprises a second liquid storage tank; and the volumes of the first liquid storage tank and the second liquid storage tank are respectively and independently 0.001-80 m3。
In another preferred example, the buffer section H1 and the buffer section H2 respectively further comprise a temperature controller and a flow stabilizer.
In another preferred embodiment, the organic phase contains an extraction effective amount of a compound of formula (I):
in the formula (I), Z is an oxygen atom, a sulfur atom or a substituted aryl group9A substituted nitrogen atom, wherein R9Is a hydrogen atom, C1-6Alkyl-sulfonyl, C1-6Haloalkyl-sulfonyl, phenylsulfonyl or C1-6Alkyl-benzenesulfonyl; r1、R2、R3、R4、R5、R6、R7And R8Each is independentThe site is hydrogen atom, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C3-6Cycloalkyl, halogen or phenyl.
In another preferred embodiment, the organic phase further contains a synergist.
In another preferred embodiment, the synergist comprises: a neutral phosphorus-containing compound, a quaternary ammonium salt compound, a long-chain alkyl quaternary sulfonium salt compound, or a neutral sulfoxide compound.
In another preferred embodiment, the synergist comprises: tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), dibutyl butylphosphonate (DBBP), dibutyl butylphosphonate (BDBP), tetramethylene tetrabutyl diphosphate, trioctylphosphine oxide, 1, 10-phenanthroline, methyl trioctyl ammonium chloride, methyl trinonyl ammonium chloride, methyl tridecyl ammonium chloride, dimethyl di (N-octadecyl) ammonium chloride, methyl dioctyl sulfonium chloride or dioctyl sulfoxide.
In another preferred embodiment, the organic phase further comprises a diluent.
In another preferred embodiment, the diluent comprises: kerosene, octanone, chloroform, carbon tetrachloride, toluene, xylene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, trichlorobenzene, diphenyl ether, or combinations thereof.
In another preferred embodiment, the phase-inversion aqueous phase a1 is an aqueous solution containing a solute selected from the group consisting of: HCl, H2SO4、HBr、NaCl、NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4Or a combination thereof.
In another preferred example, the concentration of the solute in the phase-inversion liquid aqueous phase A1 is in the range of 0-5 mol/L.
In another preferred embodiment, the conditioning solution T is an aqueous solution containing a solute selected from the group consisting of: sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide, or combinations thereof.
In another preferable example, the concentration of the solute in the regulating solution T is in a range of 0.1-18 mol/L.
In another preferred embodiment, the process further comprises: the temperature range of the system is controlled to be 0-80 ℃.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time to develop a liquid-liquid extraction separation process capable of efficiently and conveniently separating lithium isotopes. The process has reasonable and simple flow design and convenient operation, can effectively buffer and control the fluctuation of flow, realizes the high-efficiency separation and enrichment of the lithium isotope, and simultaneously obtains the lithium-7 isotope enriched product and the lithium-6 isotope enriched product. The process is environment-friendly and has high operation safety. The organic phase can be recycled, the cost of the separation and enrichment of the lithium isotope is obviously reduced, and the economic benefit is considerable.
Extraction separation process
The extraction separation process mainly comprises the following process sections: a lithium saponification section, a buffering H1 section, an extraction separation C1 section, an extraction separation C2 section, a buffering H2 section and a phase inversion section.
In the process of isotope enrichment, the single-stage (single-time) separation coefficient of an extraction system is small, and the multi-stage accumulation separation and enrichment of lithium isotopes can be realized only by adopting a specific extraction process (comprising a cascade extraction process section, a phase inversion process section, a saponification process section, a buffer adjustment process section and the like), so that a high-abundance lithium isotope product is finally obtained.
As shown in fig. 1, in the extraction process of the present invention, each process segment has different functions, and the effective combination of the process segments can realize the extraction and enrichment of lithium isotopes.
Buffer H1 segment:
(a) and regulating and controlling the abundance values of enriched products P1 and P2. The liquid reservoir in buffer H1 retains a portion of the lithium-6 enriched product. Under the condition of fixing the total number of stages (the total number of equipment) of the extraction separation C1 stage and the extraction separation C2 stage, the volume of the storage tank can regulate and control the abundance values of enriched products P1 and P2, thereby facilitating the operation flow and the diversity adjustability of the produced products. The volume of the liquid storage tank is 0.001-80 m3。
(b) Has the functions of buffering and storing liquid and stabilizing the fluctuation of flow rate.
(c) The lithium-6 enriched product can be conveniently obtained. Corresponding lithium-6 enriched water phase products can automatically flow out from the liquid storage tank, large pulse and fluctuation of the flow of the whole extraction system are not caused, and the operation is convenient.
(d) Preferably, a temperature controller can be added in the process section according to an actual extraction system, so that the temperature can be conveniently controlled, and the control range is 0-80 ℃. Preferably, a flow stabilizer can be added for adjusting the flow and stabilizing the fluctuation of the flow. Control of alkalinity and concentration may also be performed.
Buffer H2 segment:
(a) and regulating and controlling the abundance values of enriched products P1 and P2. The liquid reservoir in buffer H2 retains a portion of the lithium-7 enriched product. Under the condition of fixing the total number of stages (the total number of equipment) of the extraction separation C1 stage and the extraction separation C2 stage, the volume of the storage tank can regulate and control the abundance values of enriched products P1 and P2, thereby facilitating the operation flow and the diversity adjustability of the produced products. The volume of the liquid storage tank is 0.001-80 m3。
(b) Has the functions of buffering and storing liquid and stabilizing the fluctuation of flow rate.
(c) The lithium-7 enriched product can be conveniently obtained. Corresponding lithium-7 enriched water phase products can automatically flow out from the liquid storage tank, large pulse and fluctuation of the flow of the whole extraction system are not caused, and the operation is convenient.
(d) The addition and the uniform mixing of the regulating solution (T) are convenient.
(e) Preferably, a temperature controller can be added in the process section according to an actual extraction system, so that the temperature can be conveniently controlled, and the control range is 0-80 ℃. Preferably, a flow stabilizer can be added for adjusting the flow and stabilizing the fluctuation of the flow. Control of alkalinity and concentration may also be performed.
Lithium saponification stage:
so that the organic phase is loaded with lithium element and the lithium-6 isotope is circularly enriched by reflux. The concentration range of lithium in the loaded organic phase is 0.01-2 mol/L, and equipment such as a reaction kettle, a material mixing and stirring tank, an extraction and separation tower or a centrifugal extractor can be adopted. After the organic phase and the water phase from the buffer H1 section are mixed, stirred and subjected to mass transfer, the lithium element is loaded, and the lithium element continuously and stably enters an extraction separation C1 section.
Extraction separation C1 stage and extraction separation C2 stage:
the method is mainly used for multi-stage extraction, separation and enrichment of lithium isotopes, feed liquid (F) is added from the middle and then enters an aqueous phase in the C1 section of extraction and separation, and compared with an organic phase, the aqueous phase has the capacity of enriching lithium-6 isotopes. Therefore, after multiple separation and enrichment (1-N level), a lithium-6 enriched product (P1) is obtained at the outlet of the buffer H1 section, and the lithium-6 isotopic abundance of the product is greater than that of the feed liquid. On the contrary, the organic phase is enriched with lithium-7 isotope product (P2) at the M level at the tail end of the extraction separation C2 section, and after the phase inversion section, the lithium-7 enriched product can be directly obtained from the water phase of the buffer H2 section. Wherein the lithium-7 isotopic abundance of the enriched product (P2) is greater than that of the feed liquid.
The extraction separation section C1 and the extraction separation section C2 are respectively formed by connecting a plurality of liquid-liquid extraction separation devices in series, and the liquid-liquid extraction separation devices comprise extraction separation towers, mixing clarifying tanks or centrifugal extractors and the like. Preferably, the total number of stages N of the C1 stage of extraction separation is 5-500 stages, and the total number of stages M of the C2 stage of extraction separation is 5-500 stages.
Phase inversion section:
so that the lithium element in the organic phase is transferred to the water phase, and the reflux circulation enrichment of the lithium-7 isotope is ensured. After phase inversion, enabling the concentration range of lithium element at the outlet of the water phase to be 0.01-4 mol/L, and continuously entering a buffer H2 section; the organic phase is repeatedly recycled after no load, and enters an alkali saponification section. The equipment such as a reaction kettle, a material mixing and stirring tank, an extraction and separation tower or a centrifugal extractor and the like can be adopted.
Alkali saponification section:
and (3) carrying out alkali saponification on the blank organic phase. The alkali solution can be sodium hydroxide, ammonium hydroxide, potassium hydroxide, cesium hydroxide, etc.
Organic phase (O):
in the process for separating lithium isotopes by liquid-liquid extraction provided by the invention, the organic phase preferably contains a compound represented by the formula (I):
in the formula (I), Z is an oxygen atom, a sulfur atom or a substituted aryl group9A substituted nitrogen atom, wherein R9Is a hydrogen atom, C1-6Alkyl-sulfonyl, C1-6Haloalkyl-sulfonyl, phenylsulfonyl or C1-6Alkyl-benzenesulfonyl; r1、R2、R3、R4、R5、R6、R7And R8Each independently is a hydrogen atom, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C3-6Cycloalkyl, halogen or phenyl.
In another preferred embodiment, the extraction organic phase further contains a synergist.
In another preferred embodiment, the synergist is a phosphorus-containing compound, a nitrogen-containing compound, an alkyl quaternary sulfonium salt compound or a sulfoxide compound.
In another preferred embodiment, the synergist is a neutral phosphorus-containing compound, a quaternary ammonium salt compound, a long-chain alkyl quaternary sulfonium salt compound or a neutral sulfoxide compound.
In another preferred embodiment, the synergist comprises: tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), dibutyl butylphosphonate (DBBP), dibutyl butylphosphonate (BDBP), tetramethylene tetrabutyl diphosphate, trioctylphosphine oxide, 1, 10-phenanthroline, methyl trioctyl ammonium chloride, methyl trinonyl ammonium chloride, methyl tridecyl ammonium chloride, dimethyl di (N-octadecyl) ammonium chloride, methyl dioctyl sulfonium chloride or dioctyl sulfoxide.
In another preferred embodiment, the organic extraction phase further comprises a diluent.
In another preferred embodiment, the diluent comprises: kerosene, octanone, chloroform, carbon tetrachloride, toluene, xylene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, trichlorobenzene, diphenyl ether, or combinations thereof.
The extractant in the organic phase not only has the function of extracting lithium ions, but also the chemical environment of the combined organic complex is different from that of the lithium ions in the water phase, so that a larger single-stage separation coefficient of the lithium isotope is generated. Unlike the amalgam method, the organic phase extractant in the process is more easily enriched with lithium-7 isotopes, while the aqueous phase is more easily enriched with lithium-6 isotopes. In the multistage series process, the organic phase extractant has good chemical stability, no decomposition for a long time, convenient source and low cost.
Phase-inversion liquid-aqueous phase (a 1):
preferably, the phase inversion aqueous phase a1 is an aqueous solution comprising a solute selected from the group consisting of: HCl, H2SO4、HBr、NaCl、NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4Or a combination thereof. Through the decomposition reaction between the phase inversion liquid water phase and the loaded organic phase, after mass transfer mixing and separation, the water phase contains lithium element, the concentration range of the lithium element is 0.01-4 mol/L, and the organic phase is recycled after no load.
Conditioning liquid (T):
preferably, the conditioning solution is an aqueous solution comprising a solute selected from the group consisting of: sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide, or combinations thereof. The concentration range of solute in the regulating solution T is 0.1-18 mol/L. The pH value of the system is adjusted by adding the regulating solution into the aqueous phase buffer H2 section, so that the extraction system does not migrate and runs stably.
Lithium-containing liquid (F):
preferably, the lithium-containing feed solution is an aqueous solution comprising a solute selected from the group consisting of: LiCl, Li2SO4、LiBr、LiNO3、Li2CO3、LiOH、LiClO4Or a combination thereof, wherein the abundance of the lithium-7 isotope ranges from 40% to 99.97%.
Lithium-6 enriched product (P1):
the lithium-6 enriched product (P1) refers to an extracted and enriched product with a lithium-6 abundance value higher than that of the lithium-containing feed liquid (F). And continuously flowing out part of the aqueous phase in the buffer H1 section to obtain a lithium-6 enriched product, and feeding the rest of the aqueous phase into a lithium saponification section, wherein the ratio of the flow rates of the two is preferably controlled within the range of 1: 3-1: 3500. Preferably, the lithium-6 isotopic abundance of the lithium-6 enriched product (P1) ranges from 0.05% to 99.5%.
Lithium-7 enriched product (P2):
the lithium-7 enriched product (P2) refers to an extracted and enriched product with a lithium-7 abundance value higher than that of the lithium-containing feed liquid (F). And (3) enriching lithium-7 isotopes in an organic phase, after phase inversion, allowing the enriched lithium-7 isotopes to enter a buffer H2 section, continuously flowing out of a part of the aqueous phase in the buffer H2 section to obtain a lithium-7 enriched product, and allowing the rest of the aqueous phase to enter an extraction separation C2 section, wherein the ratio of the flow rates of the two is preferably controlled within a range of 1: 3-1: 3500. Preferably, the lithium-7 isotopic abundance range of the lithium-7 enriched product (P2) is 45% to 99.996%.
Through repeated test verification and continuous optimization, the process of the invention finally realizes the multi-stage separation and enrichment of the lithium isotope and simultaneously obtains a lithium-6 isotope enriched product and a lithium-7 isotope enriched product. As shown in example 3, a lithium-6-enriched product (P1) having an abundance of lithium-6 of 13.20% was obtained, while a lithium-7-enriched product (P2) having an abundance of lithium-7 of 99.03% was obtained; alternatively, as shown in example 4, a lithium-6-enriched product (P1) having an abundance of lithium-6 of 25.46% can be obtained, while a lithium-7-enriched product (P2) having an abundance of lithium-7 of 95.62% can be obtained.
The main advantages of the invention are as follows:
(1) the buffer H1 segment and the buffer H2 segment are adopted, so that the abundance values of enriched products P1 and P2 are conveniently regulated and controlled, and two enriched products enriched in lithium-6 and lithium-7 are obtained simultaneously.
(2) The process of the invention has reasonable and simple design and convenient operation. The flow fluctuation can be effectively buffered and controlled, and the high-efficiency separation and enrichment of the lithium isotopes can be realized.
(3) Green and environment-friendly, and high operation safety. The organic phase can be recycled, the cost of the separation and enrichment of the lithium isotope is obviously reduced, and the economic benefit is considerable.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight.
Example 1
Connecting pipelines according to a process diagram, and adopting 20 centrifugal extractors in the extraction separation C1 section and the extraction separation C2 section. The buffer H1 section contains a first liquid storage tank with a volume of 0.018m3(ii) a The buffer H2 section contains a second liquid storage tank with a volume of 0.001m3。
Organic phase: contains 7-trifluoromethyl-10-hydroxybenzoquinoline, and synergistic agent and diluent.
Phase-inversion liquid-aqueous phase (a 1): aqueous NaCl solution.
Conditioning liquid (T): aqueous sodium hydroxide solution.
Lithium-containing liquid (F): li2SO41.8mol/L of aqueous solution, wherein the abundance of lithium-6 is 7.49 percent, and the abundance of lithium-7 is 92.51 percent.
Adding an organic phase and each aqueous phase through a charging pump, operating the whole extraction process, balancing the system after 156 hours, continuously separating and simultaneously obtaining two enriched products:
the lithium-6 enrichment product (P1) had a lithium-6 abundance value of: 8.27 percent and the stage efficiency of the C1 section of extraction separation is 92 percent; the lithium-7 abundance value of the lithium-7 enriched product (P2) was: 93.70 percent and the stage efficiency of the C2 section of extraction separation is 94 percent.
Example 2
Process flow andthe feed liquid adopts the parameters in the embodiment 1, and the volume of the first liquid storage tank in the buffer H1 section is changed to be 0.040m3. Enriched products with different abundance values from example 1 can be obtained by continuous separation:
the lithium-6 enrichment product (P1) had a lithium-6 abundance value of: 8.03 percent and the stage efficiency of the C1 section of extraction separation is 94 percent; the lithium-7 abundance value of the lithium-7 enriched product (P2) was: 93.90 percent and the stage efficiency of the C2 section of extraction separation is 95 percent.
Example 3
Connecting pipelines according to a process diagram, wherein 45 centrifugal extractors are adopted in the extraction separation section C1, and 160 centrifugal extractors are adopted in the extraction separation section C2. The buffer H1 section and the buffer H2 section contain liquid storage tanks.
Organic phase: contains 10-hydroxybenzoquinoline.
Phase-inversion liquid-aqueous phase (a 1): na (Na)2SO4An aqueous solution.
Conditioning liquid (T): an aqueous solution of potassium hydroxide.
Lithium-containing liquid (F): li2SO42.5mol/L of aqueous solution, wherein the abundance of lithium-6 is 7.49 percent, and the abundance of lithium-7 is 92.51 percent.
Adding an organic phase and each aqueous phase through a charging pump, operating the whole extraction process, and continuously separating and simultaneously obtaining two enriched products after the system is balanced:
the lithium-6 enrichment product (P1) had a lithium-6 abundance value of: 13.20 percent and the stage efficiency of the C1 section of extraction separation is 95 percent; the lithium-7 abundance value of the lithium-7 enriched product (P2) was: 99.03 percent and the stage efficiency of the C2 section of extraction separation is 95 percent.
Example 4
Connecting pipelines according to a process diagram, wherein 160 centrifugal extractors are adopted in the extraction separation section C1, and 45 centrifugal extractors are adopted in the extraction separation section C2. The buffer H1 section and the buffer H2 section contain a liquid storage tank and a temperature controller.
Organic phase: contains 4-ethyl-10-hydroxybenzoquinoline.
Phase-inversion liquid-aqueous phase (a 1): (NH)4)2SO4An aqueous solution.
Conditioning liquid (T): aqueous sodium hydroxide solution.
Lithium-containing liquid (F): LiCl aqueous solution, 3.0mol/L, wherein the abundance of lithium-6 is 7.48 percent, and the abundance of lithium-7 is 92.52 percent. The stage efficiency of the extraction separation was > 95%.
Adding an organic phase and each aqueous phase through a charging pump, operating the whole extraction process, and continuously separating and simultaneously obtaining two enriched products after the system is balanced:
lithium-6 enriched product (P1) the abundance value of lithium-6 was: 25.46 percent and the stage efficiency of the C1 section of extraction separation is 94 percent; the lithium-7 abundance value of the lithium-7 enriched product (P2) was: 95.62 percent and the stage efficiency of the C2 section of extraction separation is 95 percent.
As can be seen from the above examples, the process technology of the present invention has superior extraction separation stage efficiency compared with the process technology of Chinese patent 201310239535X; two enriched products (lithium-6 enriched product P1 and lithium-7 enriched product P2, Chinese patent 201310239535X only reports enriched lithium-7 product) can be obtained simultaneously and continuously; meanwhile, the buffer H1 segment and the buffer H2 segment can conveniently regulate and control the abundance values of enriched products P1 and P2 (in example 1 and example 2).
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (12)
1. A process for separating lithium isotopes by liquid-liquid extraction, the process comprising the steps of:
(1) continuous countercurrent running of the organic and aqueous phases:
the lithium-containing organic phase after the lithium saponification section sequentially passes through an extraction separation C1 section, an extraction separation C2 section and a phase inversion section;
the lithium-containing water phase after the phase inversion section sequentially passes through a buffer H2 section, an extraction separation C2 section, an extraction separation C1 section and a buffer H1 section;
(2) adding lithium-containing feed liquid F between the extraction separation C1 section and the extraction separation C2 section;
adding a regulating solution T into a buffer H2 section;
adding a phase inversion liquid water phase A1 into the phase inversion section;
(3) continuously flowing out part of the aqueous phase in the buffer H1 section to obtain a lithium-6 enriched product P1, and feeding the rest of the aqueous phase into a lithium saponification section;
(4) continuously flowing out part of the water phase in the buffer H2 section to obtain a lithium-7 enriched product P2, and feeding the rest part of the water phase into an extraction separation C2 section;
the organic phase flowing out from the phase inversion section enters a lithium saponification section for circulation after being saponified by alkali liquor in an alkali saponification section.
2. The process of claim 1, further comprising:
extracting the aqueous phase comprising the lithium element in a lithium saponification section, an extraction separation C1 section and an extraction separation C2 section to load the lithium element with the organic phase; and/or
And in the phase inversion section, performing phase inversion stripping on the organic phase comprising the lithium element.
3. The process of claim 1, further comprising:
adding alkali liquor A3 into the alkali saponification section; and/or
Discharging aqueous phase a2 from the lithium saponification stage; and/or
The aqueous phase A4 was discharged from the alkaline saponification stage.
4. The process as claimed in claim 1, wherein said buffer H1 section comprises a first liquid storage tank, and said buffer H2 section comprises a second liquid storage tank; and the volumes of the first liquid storage tank and the second liquid storage tank are respectively and independently 0.001-80 m for carrying out the dry distillation.
5. The process of any one of claims 1 to 4, wherein the organic phase contains an extraction effective amount of a compound of formula (I):
in the formula (I), Z is an oxygen atom, a sulfur atom or a substituted aryl group9A substituted nitrogen atom, wherein R9Is a hydrogen atom, C1-6Alkyl-sulfonyl, C1-6Haloalkyl-sulfonyl, phenylsulfonyl or C1-6Alkyl-benzenesulfonyl; r1、R2、R3、R4、R5、R6、R7And R8Each independently is a hydrogen atom, C1-6Alkyl radical, C1-6Haloalkyl, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C3-6Cycloalkyl, halogen or phenyl.
6. The process of claim 5, wherein the organic phase further comprises a synergist.
7. The process of claim 6, wherein the synergist comprises: a neutral phosphorus-containing compound, a quaternary ammonium salt compound, a long-chain alkyl quaternary sulfonium salt compound, or a neutral sulfoxide compound.
8. The process of claim 6, wherein the synergist comprises: tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), dibutyl butylphosphonate (DBBP), dibutyl butylphosphonate (BDBP), tetramethylene tetrabutyl diphosphate, trioctylphosphine oxide, 1, 10-phenanthroline, methyl trioctyl ammonium chloride, methyl trinonyl ammonium chloride, methyl tridecyl ammonium chloride, dimethyl di (N-octadecyl) ammonium chloride, methyl dioctyl sulfonium chloride or dioctyl sulfoxide.
9. The process of claim 5 wherein the organic phase further comprises a diluent.
10. The process of claim 9 wherein said diluent comprises: kerosene, octanone, chloroform, carbon tetrachloride, toluene, xylene, diethylbenzene, bromobenzene, anisole, nitromethane, 2-methylcyclohexanone, methyl isobutyl ketone, chlorobenzene, dichlorobenzene, trichlorobenzene, diphenyl ether, or combinations thereof.
11. The process of claim 1, wherein said phase-inversion aqueous phase a1 is an aqueous solution comprising a solute selected from the group consisting of: HCl, H2SO4、HBr、NaCl、NH4Cl、NaBr、(NH4)2SO4、Na2SO4、NaNO3、NH4NO3、KCl、K2SO4Or a combination thereof.
12. The process of claim 1, wherein the conditioning solution T is an aqueous solution comprising a solute selected from the group consisting of: sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide, or combinations thereof.
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