CN112933967B - Separation and enrichment system for lithium isotopes - Google Patents
Separation and enrichment system for lithium isotopes Download PDFInfo
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- CN112933967B CN112933967B CN202110115402.6A CN202110115402A CN112933967B CN 112933967 B CN112933967 B CN 112933967B CN 202110115402 A CN202110115402 A CN 202110115402A CN 112933967 B CN112933967 B CN 112933967B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 95
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 118
- 238000000605 extraction Methods 0.000 claims abstract description 80
- 239000007864 aqueous solution Substances 0.000 claims abstract description 76
- 239000012074 organic phase Substances 0.000 claims abstract description 57
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 55
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 55
- 239000012266 salt solution Substances 0.000 claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000005372 isotope separation Methods 0.000 claims abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 230000000717 retained effect Effects 0.000 abstract description 4
- 239000011521 glass Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000005086 pumping Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 5
- 229910052722 tritium Inorganic materials 0.000 description 5
- 229910000497 Amalgam Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 150000003983 crown ethers Chemical class 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- FNEPSTUXZLEUCK-UHFFFAOYSA-N benzo-15-crown-5 Chemical compound O1CCOCCOCCOCCOC2=CC=CC=C21 FNEPSTUXZLEUCK-UHFFFAOYSA-N 0.000 description 2
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XIWRBQVYCZCEPG-UHFFFAOYSA-N 17-nitro-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene Chemical compound O1CCOCCOCCOCCOC2=CC([N+](=O)[O-])=CC=C21 XIWRBQVYCZCEPG-UHFFFAOYSA-N 0.000 description 1
- CQNGAZMLFIMLQN-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-trien-17-amine Chemical compound O1CCOCCOCCOCCOC2=CC(N)=CC=C21 CQNGAZMLFIMLQN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 crown ether compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000005445 isotope effect Effects 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/24—Separation by extracting by solvent extraction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses aThe separation and enrichment system of the lithium isotopes comprises an organic extraction phase, a lithium salt solution phase, a back extraction solution and a pipe body filled with low-concentration acidic aqueous solution; wherein the organic extraction phase is used for reacting with the lithium salt solution phase to obtain a first enriched organic phase; the pipe body filled with the low-concentration acidic aqueous solution is used for eluting the first enriched organic phase to form a second enriched organic phase; the back extraction liquid is used for back extraction of the first solution to obtain enriched liquid 6 A solution of Li. The lithium isotope separation and enrichment system provided by the invention elutes a first enriched organic phase by arranging a pipe body filled with low-concentration acidic aqueous solution, and the organic phase 7 Li is eluted more into the aqueous solution, 6 the proportion of Li retained in the organic phase is greater, thus allowing the resulting second enriched organic phase to be 6 The abundance of Li is increased.
Description
Technical Field
The invention belongs to the technical field of lithium isotope separation, and particularly relates to a separation and enrichment system of lithium isotopes.
Background
Lithium (Li) exists in nature as two stable isotopes 6 Li and Li 7 Li, their natural abundance (refer to 6 Li and Li 7 Natural relative percentages of Li) are 7.42% and 92.58%, respectively, both isotopes being in the nuclear energy domainAll have extremely important roles. Wherein the thermal neutron absorption cross section reaches 940b 6 Li can generate tritium and helium after being bombarded and fissile by neutron (n) 6 Li+n→T+ 4 He), so of a certain abundance 6 Li can be used as a feedstock for nuclear fusion and other uses; while the thermal neutron absorption cross section is only 0.037b 7 Li plays an important role in the regulation and control of the nuclear reaction process and the maintenance of equipment. The nuclear fusion energy supply is to polymerize deuterium (D) and tritium (T) into helium # 4 He), estimated to be 1kg 6 Li fission generates tritium, and the total energy released during fusion can generate at least 10000 kilowatts which is far greater than the same mass 235 Energy released upon U fission. However, the storage of tritium in nature is extremely limited and tritium production must rely on neutron bombardment 6 Li is generated and added.
Currently, there are various single-stage separation methods of lithium isotopes, which can be classified into chemical methods and physical methods, wherein the chemical methods include a lithium amalgam exchange method, an ion exchange chromatography method, an extraction method, and the like; physical methods include electromagnetic methods, electron transfer, molecular distillation, laser separation, and the like. The physical method is not suitable for industrial production due to the characteristics of expensive production equipment, harsh production conditions, high energy consumption, small yield and the like. The lithium amalgam method for separating lithium isotopes has great disadvantages, and the separation process uses a large amount of mercury metal to bring ecological environment and safety problems, and the Europe and America have closed some factories for separating lithium isotopes by the lithium amalgam method.
Since the 1967 Pedersen et al synthesized a series of crown ether compounds, researchers found that certain crown ethers had a tremendous lithium isotope effect, and had a separation factor comparable to that of lithium amalgam in separating the lithium isotopes, but during the separation and enrichment of the liquid-liquid extraction lithium isotopes of crown ether solvents, 6 it is very difficult to increase the abundance of Li every 0.1%.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a separation and enrichment system of lithium isotopes, which is used for improving 6 The abundance of separation and enrichment of Li.
A separation and enrichment system of lithium isotopes, comprising an organic extraction phase, a lithium salt solution phase, a strip liquor and a tube filled with a low-concentration acidic aqueous solution; wherein,
the organic extraction phase is used for reacting with the lithium salt solution phase to obtain a first enriched organic phase;
the tube filled with the low concentration acidic aqueous solution is used for eluting the first enriched organic phase, and comprises: dropwise injecting the first enriched organic phase into the pipe body filled with the low-concentration acidic aqueous solution, wherein the first enriched organic phase is concentrated at the bottom of the pipe body to form a second enriched organic phase;
the back extraction liquid is used for back extraction of the first solution to obtain enriched liquid 6 A solution of Li.
Preferably, the organic extraction phase comprises an extractant and a diluent mixed with each other; wherein,
the extractant is selected from any one of the compounds shown in the following formulas 1 to 3,
in the compounds shown in the formulas 1 to 3, R is selected from alkyl, alkoxy, amino, nitro or phenyl with 0 to 20 carbon atoms, X is N or O, and N is 0, 1 or 2;
the diluent is selected from one or more of iodobenzene, dichloromethane, carbon tetrachloride, chloroform, 1, 2-dichloroethane, nitrobenzene or 1, 2-trichloroethane.
Preferably, the concentration of the extractant in the organic extraction phase is 0.4mol/L to 0.8mol/L.
Preferably, the lithium salt in the lithium salt solution phase is selected from LiCl, liBr, liI, liOH, liNO 3 、LiClO 4 、LiSCN、CH 3 COOLi、CF 3 COOLi、CHF 2 COOLi、CH 2 FCOOLi and Li [ NTf 2 ]The concentration of lithium salt in the lithium salt solution is 1mol/L to 4mol/L.
Preferably, the organic extract phase and the lithium salt solution phase are mixed according to the volume ratio of 1 (1-10) to carry out oscillation extraction reaction, so as to obtain the first enriched organic phase.
Preferably, the strip liquor is selected from HCl, HBr, HI, naCl, KCl, H 2 SO 4 、HNO 3 And HClO 4 The concentration of the back extraction liquid is 1mol/L to 5mol/L.
Preferably, the low concentration acidic aqueous solution is HCl, HBr, HI, H 2 SO 4 、HNO 3 And HClO 4 The concentration of the solute in the low-concentration acidic aqueous solution is 0.1mol/L to 1mol/L.
Preferably, the concentration of the solute in the low-concentration acidic aqueous solution is 0.2mol/L to 0.8mol/L.
Preferably, the second enriched organic phase is withdrawn from the tube and the aqueous solution thereof is removed by centrifugation.
Preferably, the height of the pipe body filled with the low-concentration acidic aqueous solution is 0.5-2 m.
According to the lithium isotope separation and enrichment system provided by the embodiment of the invention, the first enriched organic phase is eluted by arranging the pipe body filled with the low-concentration acidic aqueous solution, and the organic phase is eluted 7 Li is eluted more into the aqueous solution, 6 the proportion of Li retained in the organic phase is greater, and the improvement 6 The separation and enrichment abundance of Li; in addition, the organic extraction phase is made into organic droplets to be contacted with the low-concentration acidic aqueous solution, so that the contact area is increased, and the reaction time is saved.
Drawings
FIG. 1 is a schematic view showing the structure of a pipe body filled with a low-concentration acidic aqueous solution in an embodiment of the present invention;
fig. 2 is a process flow diagram of a method for separation and enrichment of lithium isotopes in an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are merely exemplary and the invention is not limited to these embodiments.
It should be noted here that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, while other details not greatly related to the present invention are omitted.
The abundance of a lithium isotope refers to the ratio of the content of one isotope of lithium in the total lithium elements, and the increased abundance of a lithium isotope refers to the percentage of one isotope of lithium that is increased after isotope separation and enrichment, compared to before enrichment, and 6 abundance of Li 6 Li%) and the increased abundance (. DELTA.h #) 6 Li%)) can be expressed as: Δh% 6 Li％)＝h 2 ( 6 Li％)-h 1 ( 6 Li%; wherein, deltah is% 6 Li%) refers to increased lithium isotope abundance, h 1 ( 6 Li%) refers to the abundance of lithium isotopes before separation and enrichment, h 2 ( 6 Li%) refers to the abundance of the lithium isotope after separation and enrichment.
The abundance before and after separation is calculated and obtained after testing the thousandth deviation of the lithium isotope by using an inductively coupled plasma mass spectrometer, and the calculation formula is as follows:in the formula: 7 Li/ 6 Li SVEC = 12.177, standard lithium for test unit 7 Li and Li 6 Abundance ratio of Li; delta 7/6 Li (mill) is the relative deviation of one thousandth and is directly given by the test instrument. Thus, two out of the three quantities in the above equation are known [ ] 7 Li/ 6 Li SVEC And delta 7/6 Li (mill)) numberValues, thereby calculating the experimental sample 7 Li/ 6 Li Sample of Is a numerical value of (2).
Since the total content of two isotopes of lithium is 100%, it is set 6 The abundance of Li is x, then 7 The abundance of Li is 1-x, then: 7 Li/ 6 Li sample of = (1-x)/x, thereby obtaining 6 Specific values of Li abundance x.
The embodiment of the invention provides a separation and enrichment system of lithium isotopes, which comprises an organic extraction phase, a lithium salt solution phase, a back extraction solution and a pipe body filled with low-concentration acidic aqueous solution; wherein the organic extraction phase is used for reacting with the lithium salt solution phase to obtain a first enriched organic phase; the tube filled with the low concentration acidic aqueous solution is used for eluting the first enriched organic phase, and comprises: dropwise injecting the first enriched organic phase into the pipe body filled with the low-concentration acidic aqueous solution, wherein the first enriched organic phase is concentrated at the bottom of the pipe body to form a second enriched organic phase; the back extraction liquid is used for back extraction of the first solution to obtain enriched liquid 6 A solution of Li.
Wherein the organic extraction phase comprises an extractant and a diluent mixed with each other.
Specifically, the extractant is selected from any one of the compounds represented by the following formulas 1 to 3,
in the compounds shown in the formulas 1 to 3, R is selected from alkyl, alkoxy, amino, nitro or phenyl with the carbon number of 0 to 20, X is N or O, and N is 0, 1 or 2.
Specifically, the diluent is selected from one or more of iodobenzene, dichloromethane, carbon tetrachloride, chloroform, 1, 2-dichloroethane, nitrobenzene or 1, 2-trichloroethane.
In a preferred embodiment, the extractant concentration in the organic extract phase is from 0.4mol/L to 0.8mol/L.
Wherein the lithium salt in the lithium salt solution phase is selected from LiCl, liBr, liI, liOH, liNO 3 、LiClO 4 、LiSCN、CH 3 COOLi、CF 3 COOLi、CHF 2 COOLi、CH 2 FCOOLi and Li [ NTf 2 ]One or two or more of them.
In a preferred embodiment, the concentration of lithium salt in the lithium salt solution is 1mol/L to 4mol/L.
Referring to fig. 1, the pipe body 1 filled with the low-concentration acidic aqueous solution is, for example, a glass pipe, and includes a liquid inlet 11 at the top, a water stop valve 12 at the bottom, and a liquid outlet 13, after the low-concentration acidic aqueous solution 2 is filled into the pipe body 1, the first enriched organic phase is injected into the pipe body 1 filled with the low-concentration acidic aqueous solution 2 drop by drop through the injector 3, and the organic phase drops 4 sink in the low-concentration acidic aqueous solution 2 under the action of self gravity and are accumulated at the bottom of the pipe body, thereby obtaining the second enriched organic phase 5. After the aggregation is completed, the water stop valve 12 can be opened to take out the second enriched organic phase 5.
The height of the tube 1 (i.e., the height of the first concentrated organic phase droplets freely falling in the low-concentration acidic aqueous solution) is preferably 0.5 meter or more, preferably 0.5 meter to 2 meters, and more preferably 0.5 meter to 1 meter.
Wherein the low-concentration acidic aqueous solution is HCl, HBr, HI, H 2 SO 4 、HNO 3 And HClO 4 An aqueous solution of one or more of the substances. Further preferably, the concentration of the solute in the low-concentration acidic aqueous solution is 0.1mol/L to 1mol/L. In a more preferred embodiment, the concentration of the solute in the low concentration acidic aqueous solution is 0.2mol/L to 0.8mol/L.
Wherein the back extraction liquid is selected from HCl, HBr, HI, naCl, KCl, H 2 SO 4 、HNO 3 And HClO 4 One or two or more of them. In a preferred embodiment, the concentration of the stripping solution is 1mol/L to 5mol/L.
With the above concept of the separation and enrichment system of lithium isotopes, referring to fig. 2, the process applied to separation and enrichment of lithium isotopes includes the following steps:
and S1, dissolving an extractant in a diluent to prepare an organic extract phase.
As described above, the concentration of the extractant in the organic extract phase is preferably 0.4mol/L to 0.8mol/L.
And S2, dissolving lithium salt in water to prepare a lithium salt solution phase.
As described above, the concentration of the lithium salt in the lithium salt solution is preferably 1mol/L to 4mol/L.
And S3, mixing the organic extraction phase and the lithium salt solution phase, performing oscillation extraction, and centrifugally separating and removing unreacted lithium salt solution phase after the extraction is finished to obtain a first enriched organic phase.
Specifically, the organic extraction phase and the lithium salt solution phase are mixed and then placed in a centrifuge tube, and then the centrifuge tube is placed in oscillation equipment for oscillation extraction, wherein the time of oscillation extraction can be 1-30 min.
In a preferred scheme, the organic extraction phase and the lithium salt solution phase are mixed according to the volume ratio of 1 (1-5) for extraction reaction.
And S4, dropwise injecting the first enriched organic phase into a pipe body filled with the low-concentration acidic aqueous solution, wherein the first enriched organic phase is concentrated at the bottom of the pipe body to form a second enriched organic phase.
In a preferred embodiment, in step S4, the second enriched organic phase is removed from the tube and the aqueous solution thereof is removed by centrifugation.
In a more preferred scheme, the concentrated organic phase obtained by gathering the step S4 at the bottom of the pipe body is repeatedly operated for a plurality of times according to the step S4, so as to obtain the second concentrated organic phase. Specifically, the first enriched organic phase is dropwise injected into a pipe filled with low-concentration acidic aqueous solution, so that the first enriched organic phase is gathered at the bottom of the pipe, the gathered enriched organic phase is taken out and then injected into the pipe filled with the low-concentration acidic aqueous solution, and after repeated for a plurality of times, the enriched organic phase obtained by the last gathering is the second enriched organic phase.
In the step S4, the first enriched organic phase extracted in the step S3 contains 6 Li and Li 7 Li, the lithium ion extracted in the organic phase falls in the acidic aqueous solution, due to the crown ether (extractant) pair 6 Li and Li 7 Difference in Li selectivity of 6 Li and Li 7 Li is eluted by an acidic aqueous solution in unequal proportions, wherein 7 The proportion of Li diffused into the acidic aqueous solution 7 The ratio of Li in the organic phase is more 6 The proportion of Li retained in the organic phase is greater, thus allowing the resulting second enriched organic phase to be 6 The abundance of Li is increased. In addition, due to extraction in the organic phase 6 Li and Li 7 Li is eluted from the acidic aqueous solution, inevitably resulting in lithium loss, but since lithium isotopes are much more expensive than lithium salts, it is also important to sacrifice a small portion of the lithium resources and to increase the abundance of lithium isotopes. Therefore, the acidic aqueous solution in the invention adopts low-concentration acidic aqueous solution, the preferable concentration is 0.1mol/L to 1mol/L, the more preferable concentration is 0.2mol/L to 0.8mol/L, and the target lithium isotope is improved 6 Li) while minimizing the amount of lithium resource lost.
S5, back-extracting the second enriched organic phase by using back-extracting solution to obtain enriched organic phase 6 A solution of Li.
As described above, the concentration of the stripping solution is preferably 1mol/L to 5mol/L.
Example 1
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant 12-crown-4 (structural formula 3) is dissolved in chloroform to prepare an organic extract phase with the concentration of the extractant of 0.8mol/L.
(2) LiClO is added 4 Is dissolved in water for configurationForming a 3mol/L lithium salt solution in which 6 The abundance of Li was 7.57%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 5, placing the mixture into a centrifuge tube, oscillating and extracting for 30min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 0.2mol/L HCl aqueous solution into a glass tube with the height of 0.5m, pumping the reacted organic extraction phase from the top of the glass tube into the HCl aqueous solution in the form of liquid drops, opening a water stop valve to collect the organic extraction phase after the organic extraction phase completely and freely falls to an organic extraction phase collecting area at the bottom of the glass tube, pumping the collected organic extraction phase from the top of the glass tube by using a syringe, and injecting the organic extraction phase into fresh aqueous solution in the form of liquid drops, and repeating the steps for 5 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 4 times volume of 1mol/L HCl solution for 3 times to obtain concentrated extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.40%, which is improved by 0.83% compared with the initial abundance.
Example 2
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) Dissolving extractant 15-crown-5 (structural formula 1) in 1, 2-trichloroethane to obtain organic extract phase with concentration of extractant of 0.6 mol/L.
(2) Li [ NTf ] 2 ]A lithium salt solution dissolved in water to prepare 4mol/L, wherein 6 The abundance of Li was 7.50%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 1, placing the mixture into a centrifuge tube, oscillating and extracting for 1min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 1mol/L of aqueous HCl solution into a glass tube with the height of 0.5m, pumping the reacted organic extract phase into the aqueous HCl solution in the form of liquid drops from the top of the glass tube by using a syringe, opening a water stop valve after the organic extract phase completely and freely falls to an organic extract phase gathering area at the bottom of the glass tube, pumping the gathered organic extract phase out by using the syringe, and injecting the concentrated organic extract phase into fresh aqueous solution in the form of liquid drops from the top of the glass tube, and repeating the steps for 5 times.
(5) After removal of the aqueous solution in the organic extract phase by centrifugation, the aqueous solution was purified by 2 volumes of 1mol/L H 2 SO 4 Back-extracting the solution for 3 times to obtain enriched solution 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.34%, which is improved by 0.84% compared with the initial abundance.
Example 3
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant dibenzo 15-crown-5 (structural formula 2) is dissolved in chloroform to prepare an organic extract phase with the concentration of the extractant of 0.5 mol/L.
(2) Li [ NTf ] 2 ]1mol/L of lithium salt solution dissolved in water, wherein 6 The abundance of Li was 7.50%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 10, placing the mixture into a centrifuge tube, oscillating and extracting for 5min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 0.6mol/L HCl aqueous solution into a glass tube with the height of 0.5m, pumping the reacted organic extraction phase from the top of the glass tube into the HCl aqueous solution in the form of liquid drops, opening a water stop valve to collect the organic extraction phase after the organic extraction phase completely and freely falls to an organic extraction phase collecting area at the bottom of the glass tube, pumping the collected organic extraction phase from the top of the glass tube by using a syringe, and injecting the organic extraction phase into fresh aqueous solution in the form of liquid drops, and repeating the steps for 8 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 2 times volume of 5mol/L HBr solution for 3 times to obtain enriched extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.78%, which is improved by 1.28% compared with the initial abundance.
Example 4
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant 4-nitrobenzo 15-crown-5 (structural formula 1) is dissolved in carbon tetrachloride to prepare an organic extract phase with the concentration of the extractant of 0.6 mol/L.
(2) Dissolving LiI in water to prepare a lithium salt solution with the concentration of 4mol/L, wherein 6 The abundance of Li was 7.61%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 4, placing the mixture into a centrifuge tube, oscillating and extracting for 20min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 0.2mol/L of aqueous HCl solution into a glass tube with the height of 1 meter, pumping the reacted organic extraction phase from the top of the glass tube in the form of liquid drops, injecting the organic extraction phase into the aqueous HCl solution, opening a water stop valve after the organic extraction phase completely and freely falls to an organic extraction phase aggregation area at the bottom of the glass tube, pumping the aggregated organic extraction phase from the top of the glass tube by using a syringe, injecting the organic extraction phase into fresh aqueous solution in the form of liquid drops, and repeating the operation for 5 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 3 times volume of 2mol/L HCl solution for 3 times to obtain concentrated extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.73%, which is improved by 1.12% compared with the initial abundance.
Example 5
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant benzo 15-crown-5 (structural formula 1) is dissolved in 1, 2-dichloroethane to prepare an organic extract phase with the concentration of the extractant of 0.8mol/L.
(2) LiNO is to 3 A lithium salt solution in water in an amount of 3mol/L 6 The abundance of Li was 7.57%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 5, placing the mixture into a centrifuge tube, oscillating and extracting for 30min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 0.1mol/L HCl aqueous solution into a glass tube with the height of 1 meter, pumping the reacted organic extract phase into the HCl aqueous solution in the form of liquid drops from the top of the glass tube by using a syringe, opening a water stop valve after the organic extract phase completely and freely falls to an organic extract phase gathering area at the bottom of the glass tube, pumping the gathered organic extract phase out by using the syringe, pumping the gathered organic extract phase into fresh aqueous solution in the form of liquid drops from the top of the glass tube, and repeating the steps for 3 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 1 times volume of 1mol/L HCl solution for 3 times to obtain concentrated extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.38%, which is improved by 0.81% compared with the initial abundance.
Example 6
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant dibenzo 15-crown-5 (structural formula 2) is dissolved in methylene dichloride to prepare an organic extract phase with the concentration of the extractant of 0.6 mol/L.
(2) Li [ NTf ] 2 ]A lithium salt solution dissolved in water to prepare 2mol/L, wherein 6 The abundance of Li was 7.50%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 5, placing the mixture into a centrifuge tube, oscillating and extracting for 2min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling a glass tube with the height of 0.8m with 0.8mol/L of HBr aqueous solution, pumping the reacted organic extract phase from the top of the glass tube in the form of liquid drops, injecting the organic extract phase into the HBr aqueous solution, opening a water stop valve after the organic extract phase completely and freely falls to an organic extract phase aggregation area at the bottom of the glass tube, pumping the aggregated organic extract phase from the top of the glass tube by using a syringe, injecting the organic extract phase into the fresh aqueous solution in the form of liquid drops, and repeating the steps for 5 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 4 times volume of 1mol/L HCl solution for 3 times to obtain concentrated extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.49%, which is improved by 0.99% compared with the initial abundance.
Example 7
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) The extractant 4 aminobenzo 15-crown-5 (structural formula 1) was dissolved in chloroform to prepare an organic extract phase having an extractant concentration of 0.4 mol/L.
(2) Li [ NTf ] 2 ]1mol/L of lithium salt solution dissolved in water, wherein 6 The abundance of Li was 7.50%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1: and 5, placing the mixture into a centrifuge tube, oscillating and extracting for 10min, and centrifuging to remove the reacted lithium salt solution.
(4) Filling 0.4mol/L HCl aqueous solution into a glass tube with the height of 1 meter, pumping the reacted organic extract phase into the HCl aqueous solution in the form of liquid drops from the top of the glass tube by using a syringe, opening a water stop valve after the organic extract phase completely and freely falls to an organic extract phase gathering area at the bottom of the glass tube, pumping the gathered organic extract phase out by using the syringe, and injecting the gathered organic extract phase into fresh aqueous solution in the form of liquid drops from the top of the glass tube, and repeating the steps for 4 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and usingBack-extracting with 4 times volume of 1mol/L HCl solution for 3 times to obtain enriched solution 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.47%, which is improved by 0.97% compared with the initial abundance.
Example 8
The separation and enrichment system of lithium isotopes and the technical process for separating and enriching lithium isotopes provided by the embodiment are as follows:
(1) Dissolving extractant benzo 15-crown-5 (structural formula 1) in 1, 2-trichloroethane to obtain organic extract phase with concentration of 0.8mol/L extractant.
(2) Li [ NTf ] 2 ]A lithium salt solution in water in an amount of 3mol/L 6 The abundance of Li was 7.50%.
(3) Mixing the organic extraction phase and the lithium salt solution phase according to the volume ratio of 1:8, placing the mixture into a centrifuge tube, oscillating and extracting for 5min, and centrifuging to remove the reacted lithium salt solution.
(4) H to be 0.1mol/L 2 SO 4 Filling the glass tube with a height of 1 meter with aqueous solution, pumping the reacted organic extract phase by a syringe, and injecting the organic extract phase into the H from the top of the glass tube in the form of liquid drops 2 SO 4 In the aqueous solution, after the organic extraction phase completely and freely falls to an aggregation area of the organic extraction phase at the bottom of the glass tube, a water stop valve is opened to collect the organic extraction phase, the aggregated organic extraction phase is pumped out by a syringe and is injected into the fresh aqueous solution in the form of liquid drops from the top of the glass tube, and the process is repeated for 7 times.
(5) Centrifuging to remove aqueous solution in organic extract phase, and back-extracting with 4 times volume of 1mol/L HCl solution for 3 times to obtain concentrated extract 6 Li solution back extraction liquid.
(6) And measuring the abundance of the lithium isotope in the strip liquor, and calculating the abundance improved by the lithium isotope. Results of the measurement: 6 the abundance of Li is 8.87%, which is improved by 1.37% compared with the initial abundance.
In summary, the embodiment of the invention provides the lithium isotope separationEluting the first enriched organic phase from the enrichment system by providing a tube filled with a low concentration acidic aqueous solution, the organic phase 7 Li is eluted more into the aqueous solution, 6 the proportion of Li retained in the organic phase is greater, and the improvement 6 The separation and enrichment abundance of Li; in addition, the organic extraction phase is made into organic droplets to be contacted with the low-concentration acidic aqueous solution, so that the contact area is increased, and the reaction time is saved.
The foregoing is merely exemplary of the application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the application and are intended to be comprehended within the scope of the application.
Claims (7)
1. A separation and enrichment system of lithium isotopes, which is characterized by comprising an organic extraction phase, a lithium salt solution phase, a back extraction solution and a pipe body filled with low-concentration acidic aqueous solution; wherein,
the organic extraction phase is used for reacting with the lithium salt solution phase to obtain a first enriched organic phase;
the tube filled with the low concentration acidic aqueous solution is used for eluting the first enriched organic phase, and comprises: dropwise injecting the first enriched organic phase into the pipe body filled with the low-concentration acidic aqueous solution, wherein the first enriched organic phase is concentrated at the bottom of the pipe body to form a second enriched organic phase; wherein the low-concentration acidic aqueous solution is HCl, HBr, HI, H 2 SO 4 、HNO 3 And HClO 4 The concentration of the solute in the low-concentration acidic aqueous solution is 0.2mol/L to 0.8mol/L; the height of the pipe body is 0.5-2 m;
the back extraction liquid is used for back extraction of the first solution to obtain enriched liquid 6 A solution of Li.
2. The lithium isotope separation and enrichment system of claim 1, wherein the organic extraction phase comprises an extractant and a diluent mixed with each other; wherein,
the extractant is selected from any one of the compounds shown in the following formulas 1 to 3,
in the compounds shown in the formulas 1 to 3, R is selected from alkyl, alkoxy, amino, nitro or phenyl with 0 to 20 carbon atoms, X is N or O, and N is 0, 1 or 2;
the diluent is selected from one or more of iodobenzene, dichloromethane, carbon tetrachloride, chloroform, 1, 2-dichloroethane, nitrobenzene or 1, 2-trichloroethane.
3. The lithium isotope separation and enrichment system according to claim 2, wherein the concentration of the extractant in the organic extraction phase is 0.4mol/L to 0.8mol/L.
4. The lithium isotope separation and enrichment system according to claim 1, wherein the lithium salt in the lithium salt solution phase is selected from LiCl, liBr, liI, liOH, liNO 3 、LiClO 4 、LiSCN、CH 3 COOLi、CF 3 COOLi、CHF 2 COOLi、CH 2 FCOOLi and Li [ NTf 2 ]The concentration of lithium salt in the lithium salt solution is 1mol/L to 4mol/L.
5. The lithium isotope separation and enrichment system according to claim 1, wherein the organic extraction phase and the lithium salt solution phase are mixed according to a volume ratio of 1 (1-10) to perform an oscillation extraction reaction, and the first enriched organic phase is obtained.
6. According to claimThe lithium isotope separation and enrichment system according to claim 1, wherein the stripping solution is selected from HCl, HBr, HI, naCl, KCl, H 2 SO 4 、HNO 3 And HClO 4 The concentration of the back extraction liquid is 1mol/L to 5mol/L.
7. The system for precipitation separation of lithium isotopes of claim 1, wherein the second enriched organic phase is withdrawn from the tube and the aqueous solution thereof is removed by centrifugation.
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| US5344623A (en) * | 1993-06-15 | 1994-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for the extraction of strontium from acidic solutions |
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| US5344623A (en) * | 1993-06-15 | 1994-09-06 | The United States Of America As Represented By The United States Department Of Energy | Process for the extraction of strontium from acidic solutions |
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