CN103736395A - Lithium isotope separation method and single-stage separation factor measurement method thereof - Google Patents
Lithium isotope separation method and single-stage separation factor measurement method thereof Download PDFInfo
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- CN103736395A CN103736395A CN201310700494.XA CN201310700494A CN103736395A CN 103736395 A CN103736395 A CN 103736395A CN 201310700494 A CN201310700494 A CN 201310700494A CN 103736395 A CN103736395 A CN 103736395A
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Abstract
The invention belongs to the technical field of isotope separation, and in particular to a lithium isotope separation method and a single-stage separation factor measurement method thereof. According to the method, lithium isotope separation is realized by utilizing a graphite-organic electrolyte system; the method comprises three steps of oxidation-reduction reaction, isotope exchange reaction and lithium isotope separation. By the method, lithium isotope separation in a non-mercury system is realized; the pollution to an environment and the harm to human health caused by metallic mercury are avoided; the method is easy to operate; moreover, the single-stage separation factor reaches over 1.02, the separation efficiency is high, and the requirement on a single-stage separation factor of lithium isotope separation in industry can be met.
Description
Technical field
The invention belongs to isotope separation technique field, be specifically related to a kind of lithium isotope separation method and single-stage separation factor assay method thereof.
Background technology
Along with growth and the rapid development of economy of world population, people are also rapidly expanded to the demand of the energy.At present, use in the world 85% of the energy to derive from non-renewable oil, natural gas and coal.Global Oil crisis is increasingly serious, and reserves only can maintain the mankind to be continued to use approximately 40 years.In addition, the fossil feedstock such as oil, natural gas and coal is also the direct raw material of numerous industrial products simultaneously, is not only the significant wastage to resource using them as fuel, and severe contamination mankind's environment of depending on for existence.The potential collision hazard of the energy and the deterioration of ecological environment make the new and renewable sources of energy of countries in the world active development including nuclear energy.The nuclear power plant of commercialized running is now the controlled fission reactor based on uranium isotope.Because global uranium resource is extremely limited, only enough use decades, and the product of uranium fission reaction is long-life radiation fragment, once reveal or deal with improperly and will bring great disaster to the mankind.Therefore, developing controlled fusion reactor replaces fission-type reactor to be day by day subject to the extensive concern of countries in the world.Fusion reaction be utilize deuterium (D) and tritium (T) aggregate into helium (
4the huge nuclear energy of He) emitting during core: D+T →
4he (3.52MeV)+n (14.06MeV).There is tritium in occurring in nature, must rely on neutron bombardment hardly
6li produces and constantly breeds:
6li+n → T+
4he.The obtainable energy of fusion reactor is subject to the restriction of lithium isotope resource, and therefore lithium has become the final strategic resource of human future.
Lithium (Li) is the metal that nature is the lightest, and elemental lithium comprises
6two kinds of isotopes of Li and 7Li, its natural abundance is respectively 7.5%, 92.5%.
6li and
7but the similar nulcear properties of the chemical property of Li differs greatly, wherein
7the thermal neutron absorption cross section of Li is only 0.037b, and
6the thermal neutron absorption cross section of Li is 940b, therefore
6li generates tritium and helium after by neutron bombardment, makes tritium continuous propagation in reactor.Therefore
6li is important product tritium raw material and requisite fusion reactor fuel.In addition,
6solid compounds that Li and deuterium form (
6liD) be the important charging of nuclear weapon.Visible, lithium isotope particularly
6li is very close with the relation of military and the energy, in core field, occupies very consequence.Therefore, lithium isotope isolation technics is subject to extensive concern always, countries in the world all nervous, carry out correlative study in confidence.
In industrial production, first good lithium isotope separation method will meet the condition that single-stage separation factor value is greater than 1.02.Therefore, single-stage separation factor α is the important technology index of weighing a separation method industrial value.
Up to now, the unique method of countries in the world industrial production lithium isotope is lithium amalgam method.
Realizing in process of the present invention, inventor finds that in prior art, at least there are the following problems: the method is used a large amount of mercury in Isotope production process, has brought great harm to the mankind and environment.Therefore, be badly in need of finding a kind ofly can substitute lithium amalgam method, to environment and the nontoxic system of the mankind and method simple to operate.
Summary of the invention
The invention provides a kind of lithium isotope separation method, its separative efficiency is high, process simple, it is thorough to separate, and has avoided the use of mercury.The present invention also provides a kind of single-stage separation factor assay method that is applicable to this lithium isotope separation method, can comparatively fast measure the single-stage separation factor of separated oxidate for lithium.
On the one hand, the embodiment of the present invention provides a kind of lithium isotope separation method, described method adopts three electrolysis systems, working electrode, auxiliary electrode and reference electrode are set in electrolytic cell, wherein working electrode is graphite flake, lithium acetate-dimethyl sulphoxide solution that electrolyte solution is, comprises the following steps:
(1) redox reaction: under constant temperature, argon shield condition, first carry out constant-current electrolysis, when the voltage drop of described working electrode is during to steady voltage, be converted to potentiostatic deposition, stop while reaching predetermined electrolysis amount, constantly stir during reaction;
(2) isotope exchange reaction: continue to keep constant temperature, by described working electrode power-off, restart after standing to stir, until isotope exchange reaction
reach balance;
(3) lithium isotope separates: from described electrolytic cell, shift out described working electrode, with the cleaning of dehydration hexane, after the thorough volatilization of hexane to be drained off, by described working electrode heating, obtain the oxide of graphite-phase lithium.
Further, the thickness of described graphite flake is less than or equal to 0.5 millimeter.
Further, the concentration of described lithium acetate-dimethyl sulphoxide solution is 0.025～0.5mol/L.
Further, the predetermined electrolysis amount in its step (1) is 7～30 coulombs, and this predetermined electrolysis amount can and need to be adjusted at any time according to the actual conditions of electrolysis.
Further, the constant current size of current in its step (1) is-0.8～-1.1 milliampere.
Further, the thermostat temperature in its step (1) is 20～40 degrees Celsius.
Further, the time of repose in its step (2) is 4～10 minutes.
Further, the mixing time that restarts to stir in its step (2) is 1～5 minute, and for making isotope fully carry out exchange reaction, this time is preferably 5 minutes, to guarantee that exchange reaction is abundant.
Further, working electrode heating-up temperature in its step (3) is for being more than or equal to 700 degrees Celsius, and preferably, working electrode heating-up temperature is 800 degree, as long as said temperature is not less than 700 degrees Celsius, can meet the condition that described working electrode is converted into graphite-phase oxidate for lithium.
Further, described auxiliary electrode is Pt sheet, and described reference electrode is saturated calomel electrode.
On the other hand, the embodiment of the present invention provides a kind of and it is characterized in that for measuring the method for single-stage separation factor of the separated product that above-mentioned any one lithium isotope separation method obtains, and comprises the following steps:
(4) in the oxide of the graphite-phase lithium obtaining to step (3), add 2mol/L HNO
3, make it to be converted into graphite-phase LiNO
3solution;
(5) electrolyte solution in described electrolytic cell is taken out, the amount that this electrolyte solution takes out can freely be determined, generally can take out 1ml, because the object of taking out this electrolyte solution is just for measuring
6li with
7the ratio of Li, so the amount of taking out is measured needs as long as meet.In the electrolyte solution taking out, add the 2mol/L HNO of same volume
3form mixed solution, mixed solution is evaporated on electric furnace dry to the greatest extent, then be placed in 800 degrees Celsius of Muffle furnaces and heat 10 hours, obtain the oxide of solution phase lithium.In the oxide of described solution phase lithium, add 2mol/L HNO
3, make it to be converted into solution phase LiNO
3solution;
(6) use 3%HNO
3by described graphite-phase LiNO
3solution and solution phase LiNO
3solution dilution is to ppm(10
-6) level, with 3%HNO
3do blank, with 3%HNO
3lithium acetate-the dimethyl sulphoxide solution of dilution natural abundance is to ppm(10
-6) level be standard, utilize inorganic mass spectrometer to carry out isotope ratio measurement, by calculating single-stage separation factor.
Technique scheme has following beneficial effect: because adopted the electrolysis system of graphite flake working electrode and lithium acetate-dimethyl sulfoxide (DMSO) electrolyte, having realized lithium isotope in non-mercury system separates, avoided the pollution to environment and the mankind, and single-stage separation factor has reached more than 1.02, can reach industrial lithium isotope and separate the requirement to single-stage separation factor, the method is the exchange reaction between different valence state lithium isotope, very favourable to obtaining higher single-stage separation factor.In addition, the method is owing to there is no complicated chemical reaction, and solid-liquid two contacts and carry out isotope exchange, and single-stage only need shift out electrolytic cell by graphite electrode after separating and finishing, therefore its also have separation process simple, separate feature thoroughly.This single-stage separation factor assay method adopts nitric acid dissolve oxidate for lithium, can comparatively fast measure the single-stage separation factor of separating Li oxide.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the flow chart of lithium isotope separation method in the embodiment of the present invention.
Fig. 2 is the flow chart of single-stage separation factor assay method in the embodiment of the present invention.
The specific embodiment
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
In the embodiment of the present invention, the concrete principle of redox and isotope exchange reaction is:
First, the Li in electrolyte solution is natural lithium, wherein
7li
+after obtaining an electronics, intercalation forms in graphite linings
7li atom, then solution phase
6li
+with graphite linings
7li atom generation isotope exchange reaction,
6li
+enter graphite-phase,
7li
+enter solution phase, reaction equation is:
Wherein sol represents solution phase, and GICs represents graphite-phase.Its essence is Neutral Lithium Atoms Li and Li
+between isotope exchange reaction.
Adopt three electrolysis systems, working electrode, auxiliary electrode and reference electrode are set in electrolytic cell, wherein working electrode is graphite flake, and lithium acetate-dimethyl sulphoxide solution that electrolyte solution is 0.075mol/L, comprises the following steps:
(1) redox reaction
The graphite flake that employing thickness is 0.2mm is as working electrode (WE), Pt plate electrode is auxiliary electrode (CE), saturated calomel electrode is the three-electrode system of reference electrode (RE), and electrolyte solution is that concentration is lithium acetate-dimethyl sulfoxide (DMSO) (LiCH of 0.05mol/L
3cOO-DMSO) solution.Electrolytic condition is: first under the constant current mode of size of current-0.8mA, carry out electrolysis, when working electrode is to the voltage drop to of reference electrode steady voltage time-3.0V, electrolysis mode is converted to potentiostatic deposition pattern, constant potential is set as lower than steady voltage 0.01V～0.02V, while reaching predetermined electrolysis amount, electrolysis stops, this electrolysis electricity is 7～30 coulombs, and can adjust according to actual conditions; In whole electrolytic process, will stir electrolyte solution, and electrolytic cell is in the condition of 25 ℃ of constant temperature and high-purity argon gas protection;
(2) isotope exchange reaction
By electrode power-off, stirring is stopped simultaneously, after standing 5min, start again to stir 5min, carry out isotope exchange reaction, the temperature in the temperature of this process electrolytic cell and step (1) is consistent;
(3) separation of lithium isotope
Graphite electrode is shifted out from electrolytic cell and use dehydration hexane to clean, hexane to be drained off is thoroughly after volatilization, and graphite electrode is heated in temperature is the Muffle furnace of 800 ℃, obtains the oxide of graphite-phase lithium.
In order to verify isotopic separation effect, after completing lithium isotope separation, utilize inorganic mass spectrometer to measure isotope abundance, and then obtain the single-stage separation factor that lithium isotope separates.The specific embodiment is: in the oxide of the graphite-phase lithium obtaining to above-mentioned steps (3), add 2mol/L HNO
3make it to be converted into graphite-phase LiNO
3solution; Solution part in electrolytic cell is taken out and to the 2mol/L HNO that adds same volume in solution
3, utilize strong acid weak acid principle processed that most of lithium salts is converted into solution phase LiNO
3, then solution is evaporated on electric furnace dryly to the greatest extent, then be placed in 800 degrees Celsius of Muffle furnaces and heat 10 hours, make it chemical species and be converted into the oxide of solution phase lithium, then by the oxide 2mol/LHNO of solution phase lithium
3make it to be converted into solution phase LiNO
3solution; Two kinds of solution of the graphite-phase obtaining and solution phase are used respectively to 3% HNO
3be diluted to ppm(10
-6) level, with 3%HNO
3do blank, do not carry out the LiCH of the natural abundance of isotopic separation
3cOO-3%HNO
3solution does standard, utilizes inorganic mass spectrum to carry out isotope ratio measurement.Obtain being calculated as follows out after the isotopic abundance ratio of two-phase single-stage separation factor:
Wherein (
6li/
7li)
gICsrepresent the abundance ratio of graphite-phase 6Li and 7Li, (
6li/
7li)
solrepresent solution phase
6li with
7the abundance ratio of Li.
The single-stage separation factor α obtaining according to above formula can reach 1.023, meets industrial lithium isotope and separates the requirement to single-stage separation factor.
Embodiment 2
Identical with principle and method in embodiment 1, parameter that different is changes, and embodiment mono-following parameters in embodiment 1 still realizes after implementing, as following table:
In above-described embodiment, adopted the electrolysis system of graphite flake working electrode and lithium acetate-dimethyl sulfoxide (DMSO) electrolyte, having realized lithium isotope in non-mercury system separates, and single-stage separation factor has reached more than 1.02, can reach industrial lithium isotope and separate the requirement to single-stage separation factor.And the reaction in embodiment is the exchange reaction between different valence state lithium isotope, very favourable to obtaining higher single-stage separation factor.In addition, in embodiment, owing to there is no complicated chemical reaction, and reaction contacts and carries out isotope exchange for solid-liquid two, and single-stage only need shift out graphite electrode electrolytic cell after separating and finishing, therefore its also have separation process simply, separate feature thoroughly.Single-stage separation factor assay method in embodiment adopts nitric acid dissolve oxidate for lithium, can comparatively fast measure the single-stage separation factor of separating Li oxide.
The above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only the specific embodiment of the present invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a lithium isotope separation method, is characterized in that, described method adopts three electrolysis systems, working electrode, auxiliary electrode and reference electrode are set in electrolytic cell, wherein working electrode is graphite flake, and lithium acetate-dimethyl sulphoxide solution that electrolyte solution is, comprises the following steps:
(1) redox reaction: under constant temperature, argon shield condition, first carry out constant-current electrolysis, when the voltage drop of described working electrode is during to steady voltage, be converted to potentiostatic deposition, stop while reaching predetermined electrolysis amount, constantly stir during reaction;
(2) isotope exchange reaction: continue to keep constant temperature, by described working electrode power-off, restart after standing to stir;
(3) lithium isotope separates: from described electrolytic cell, shift out described working electrode, with the cleaning of dehydration hexane, after the thorough volatilization of hexane to be drained off, by described working electrode heating, obtain the oxide of graphite-phase lithium.
2. lithium isotope separation method as claimed in claim 1, is characterized in that, the thickness of described graphite flake is less than or equal to 0.5 millimeter.
3. lithium isotope separation method as claimed in claim 1, is characterized in that, the concentration of described lithium acetate-dimethyl sulphoxide solution is 0.025～0.5mol/L.
4. lithium isotope separation method as claimed in claim 1, is characterized in that, the predetermined electrolysis amount in its step (1) is 7～30 coulombs.
5. lithium isotope separation method as claimed in claim 1, is characterized in that, the constant current size of current in its step (1) is-0.8～-1.1 milliampere.
6. lithium isotope separation method as claimed in claim 1, is characterized in that, the thermostat temperature in its step (1) is 20～40 degrees Celsius.
7. lithium isotope separation method as claimed in claim 1, is characterized in that, the time of repose in its step (2) is 4～10 minutes.
8. lithium isotope separation method as claimed in claim 1, is characterized in that, the mixing time that restarts to stir in its step (2) is 1～5 minute.
9. lithium isotope separation method as claimed in claim 1, is characterized in that, the working electrode heating-up temperature in its step (3) is for being more than or equal to 700 degrees Celsius.
10. for measuring the method for single-stage separation factor for the separated product that any one lithium isotope separation method of claim 1～9 obtains, it is characterized in that, comprise the following steps:
(4) in the oxide of the graphite-phase lithium obtaining to step (3), add 2mol/L HNO
3, make it to be converted into graphite-phase LiNO
3solution;
(5) electrolyte solution in described electrolytic cell is taken out, to the 2mol/LHNO that adds same volume in the electrolyte solution taking out
3form mixed solution, mixed solution is evaporated on electric furnace dry to the greatest extent, then be placed in 800 degrees Celsius of Muffle furnaces and heat 10 hours, obtain the oxide of solution phase lithium, in the oxide of described solution phase lithium, add 2mol/L HNO
3, make it to be converted into solution phase LiNO
3solution;
(6) use 3%HNO
3by described graphite-phase LiNO
3solution and solution phase LiNO
3solution dilution is to ppm level, with 3%HNO
3do blank, with 3%HNO
3natural abundance lithium acetate solution to the ppm level of dilution is standard, utilizes inorganic mass spectrometer to carry out isotope ratio measurement, calculates single-stage separation factor.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104730173A (en) * | 2015-03-02 | 2015-06-24 | 中国地质科学院矿产资源研究所 | Method for indicating contribution ratio of ore-forming fluid in formation of porphyry deposit by magma fluid and Tibet geothermal water |
| CN108931417A (en) * | 2018-08-01 | 2018-12-04 | 中国地质科学院矿产资源研究所 | Old stratum carbonate rock lithium isotope analysis method |
| CN114832625A (en) * | 2022-05-24 | 2022-08-02 | 中南大学 | Lithium isotope separation method and device |
| CN115845609A (en) * | 2023-02-20 | 2023-03-28 | 北京核力同创科技有限公司 | Method and device for separating lithium isotopes, electronic equipment and storage medium |
| CN115999363A (en) * | 2023-01-06 | 2023-04-25 | 中南大学 | Lithium isotope multistage electrochemical separation method and device |
| WO2023190771A1 (en) * | 2022-03-31 | 2023-10-05 | 国立大学法人弘前大学 | Lithium isotope concentration device, multi-stage lithium isotope concentration device, and lithium isotope concentration method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104730173A (en) * | 2015-03-02 | 2015-06-24 | 中国地质科学院矿产资源研究所 | Method for indicating contribution ratio of ore-forming fluid in formation of porphyry deposit by magma fluid and Tibet geothermal water |
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| CN115999363A (en) * | 2023-01-06 | 2023-04-25 | 中南大学 | Lithium isotope multistage electrochemical separation method and device |
| CN115845609A (en) * | 2023-02-20 | 2023-03-28 | 北京核力同创科技有限公司 | Method and device for separating lithium isotopes, electronic equipment and storage medium |
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