CN104263970A - Lithium ion extracting agent - Google Patents
Lithium ion extracting agent Download PDFInfo
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- CN104263970A CN104263970A CN201410477644.XA CN201410477644A CN104263970A CN 104263970 A CN104263970 A CN 104263970A CN 201410477644 A CN201410477644 A CN 201410477644A CN 104263970 A CN104263970 A CN 104263970A
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- lithium ion
- ionic liquid
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Abstract
The invention relates to the technical field of extraction and in particular relates to a lithium ion extracting agent. The lithium ion extracting agent is used for extracting and separating lithium ions from a water phase containing the lithium ions, and comprises tributyl phosphate and ionic liquid, wherein the volume ratio of the ionic liquid to tributyl phosphate is not greater than 1 to 1. The extracting agent is green and environment-friendly; in particular, the extracting agent is prepared from high-hydrophobicity imidazolium ionic liquid and TBP, so that the problem that the environment pollution is caused by volatilization of a large quantity of organic solvents in the extraction operation process in the prior art can be avoided; two phases can be easily separated after extracting; the lithium ion extracting agent has a good popularization prospect.
Description
Technical field
The present invention relates to abstraction technique field, especially to the improvement of its extraction agent of extraction and separation technology of Lithium from Salt Lake Brine ion.
Background technology
Lithium not only has important application in national defense industry, and its importance in national economy also shows, day by day particularly at energy field:
6li and
7li is that important materials used is reacted in the fuel of following fusion reactor and nuclear fission respectively; It is also growing as the demand of battery material.Therefore, lithium has the title of " energy metal of 21 century ".Demand sustainable growth both at home and abroad to lithium, therefore utilizes extremely urgent to the research and development of lithium resource.
Salt lake brine is the important sources of lithium.China has abundant salt lake brine lithium resource, and its standing stock are at the forefront in the world.But containing many kinds of metal ions in salt lake brine, therefore how therefrom separation and Extraction lithium is the important topic needing research.
Current salt lake brine is carried lithium technological method and is mainly contained evaporative crystallization partition method, salting-out process, the semi-transparent embrane method of selectivity, the precipitator method, solvent extration, ion exchange method etc.Wherein, solvent extration is from low grade brine, extract lithium comparatively effective means, and this method can realize the high efficiency selected to object ion, especially puies forward lithium effect to the salt lake brine of high Mg/Li ratio better.Currently used extraction agent mostly is phosphorous organic extractant, amine extractant, diketone, crown ether and mixed extractant, and wherein studying more is phosphorous organic extractant.Common extraction system is with tributyl phosphate (TBP) for extraction agent, and iron trichloride is association's extraction agent, and sulfonated kerosene is thinner.Take tributyl phosphate as its percentage extraction of method high (total yield of lithium is about 90%) of extraction agent extraction lithium, technical process is simple, has very wide application prospect
Ionic liquid (IL) has some peculiar properties: (1) does not almost have vapour pressure, non-volatile, nonflammable, not oxidizable, adjustable viscosity; (2) ionic liquid is many organism, organometallic compound, mineral compound, the even good solvent of macromolecular material, a non-water, two-phase system that polarity is adjustable can be provided, in chemical separation process, can be used as that the non-co-of a water is molten to be used mutually; (3) water and air is stablized, convenient operation process, be easy to reclaim.Ionic liquid environmental protection is pollution-free, can reuse again, can be applied to extracting and separating aspect.
When utilizing solvent extration to extract lithium from Salt-lake brine, the extraction system usually adopted is with tributyl phosphate (TBP) and sulfonated kerosene composition.The shortcoming of existing extraction agent is to use a large amount of volatile organic solvent in extraction process, can bring severe contamination to environment, and the use of volatile solvent also can cause the molten damage of certain system.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of extraction agent of lithium ion, the extraction system of existing TBP, sulfonated kerosene can be replaced, while ensureing extraction efficiency, reduce environmental pollution.
This extraction agent, described extraction agent comprises tributyl phosphate and ionic liquid, and the volume ratio of described ionic liquid and described tributyl phosphate is not higher than 1:1.
Wherein, the volume ratio of described ionic liquid and described tributyl phosphate is not higher than 2:3.
Wherein, the volume ratio of described ionic liquid and described tributyl phosphate is 0.2 ~ 0.5:1.
Wherein, described ionic liquid is imidazole salts.
Wherein, described ionic liquid is imidazole phosphate.
Wherein, described ionic liquid is at least one in 1-butyl-3-Methylimidazole hexafluorophosphate, 1-hexyl-3-Methylimidazole hexafluorophosphate, 1-octyl group-3-Methylimidazole hexafluorophosphate.
Beneficial effect:
The invention provides a kind of extraction agent of environmental protection, especially glyoxaline ion liquid that hydrophobicity is stronger and TBP is utilized to form extraction agent, prior art can be overcome in extracting operation process, have a large amount of organic solvent easily to volatilize cause the problem of Heavy environmental pollution, extraction is easy to realize two-phase laminated flow after occurring, and has good promotion prospect.
Embodiment
Embodiment 1
The invention provides a kind of extraction agent, for carrying out the extracting and separating of lithium ion to the aqueous phase (extraction stoste) containing lithium ion, it comprises tributyl phosphate (TBP) and ionic liquid, and the volume ratio of described ionic liquid and described tributyl phosphate is not higher than 1:1.
In embodiments of the invention, preferably typical imidazoles salt is mixed to form extraction agent as ionic liquid and TBP, carries out the parallel control experiment of several groups of lithium ion extractions, to obtain preferably extraction process parameters.Introduce the process adopting this extraction agent to extract salt lake lithium ion below.
Extraction temperature: room temperature (about 20 DEG C)
Extraction stoste: ginseng is shown in Table 1.
Table 1 salt lake brine (extraction stoste) forms
| Ionic species | Li + | Mg 2+ | Na + | K + | Cl - |
| Ionic concn/gL -1 | 2 | 92 | 3.2 | 1.8 | 284.11 |
The Mg coexisted in salt lake brine
2+to separation Li
+there is direct impact, from salt lake brine, be separated Li
+its essence carries out the separation of magnesium lithium exactly.Therefore from salt lake brine, when separating Li, generally adopt solvent extration first to the Li in salt lake brine
+extract, then obtain the secondary bittern of low Mg/Li ratio through back extraction, be converted into low Mg/Li ratio secondary bittern by salt lake brine with high magnesium-lithium ratio, then obtain lithium product through the step such as demagging, precipitation.
Above-mentioned be that the sodium perchlorate solid of 1:1 is configured to aqueous phase containing adding with lithium ion mol ratio in lithium bittern.Filter because of the solid sodium chloride that salting-out effect produces in described aqueous phase, the aqueous phase after filtration is for subsequent use.
By tributyl phosphate (TBP) and imidazoles salt 1-butyl-3-Methylimidazole hexafluorophosphate ([C
4mim] [PF
6]) to be mixedly configured into some groups of extraction agents in the ratio of table 2 for subsequent use.Extraction agent and aqueous phase compared with O/A be 1:1, the ratio (n (ClO of the amount of substance of perchlorate and lithium ion
4 -): n (Li
+)) be also under the condition of 1:1, at room temperature mixing concussion 10min, leaves standstill 20min, by two-phase laminated flow.To being separated the organic phase that obtains and raffinate, to analyze (see table 2) known, as the volume ratio (V of ionic liquid and TBP
iL: V
tBP) not higher than all (V more than 50% of the extraction efficiency in 2:3,10min
iL: V
tBPbe control experiment when=0), especially at V
iL: V
tBPbe 1 ~ 3:4 ~ 7 scope in extraction efficiency the highest, illustrate that the effect of extracting of this volume ratio is better.
Volume ratio (the V of table 2 different ionic liquid and TBP
iL: V
tBP) the different extraction efficiency % that obtain
| V IL：V TBP | 0 | 1:9 | 2:8 | 3:7 | 4:6 |
| Extraction efficiency/% | 53.02 | 58.22 | 65.49 | 62.24 | 60.04 |
Embodiment 2
Further, the contrast experiment that the present embodiment also provides several imidazole phosphate to mix with TBP as ionic liquid, wherein, the extraction step of the present embodiment, compared with embodiment 1, is be that the sodium perchlorate solid of 2:1 is configured to aqueous phase containing adding with lithium ion mol ratio in lithium bittern unlike the present embodiment; And V
iL: V
tBPthen be defined as 1:4, compare O/A and be defined as 2:1.Several imidazole salts and extraction efficiency as shown in table 2:
Several imidazole salts of table 3 and extraction efficiency thereof
| Ionic liquid | [C 4mim][PF 6] | [C 6mim][PF 6] | [C 8mim][PF 6] |
| Extraction efficiency/% | 87.28 | 83.00 | 80.82 |
As can be seen from Table 3, imidazoles phosphoric acid salt such as 1-butyl-3-Methylimidazole hexafluorophosphate ([C
4mim] [PF
6]), 1-hexyl-3-Methylimidazole hexafluorophosphate ([C
6mim] [PF
6]), 1-octyl group-3-Methylimidazole hexafluorophosphate ([C
8mim] [PF
6]) extraction agent that forms with TBP all can obtain preferably extraction efficiency (reaching 80%).Further, in imidazoles phosphoric acid salt, substituting group carbochain is longer, and the extraction agent extraction efficiency that itself and TBP form is lower.Reason may be that substituting group carbochain is longer, and cationic hydrophobicity is stronger because the extraction mechanisms of ionic liquid in this system is cationic exchange, more difficultly exchanges with lithium ion, so extraction efficiency is lower.
Claims (6)
1. an extraction agent for lithium ion, for carrying out the extracting and separating of lithium ion to containing in the aqueous phase of lithium ion, it is characterized in that, described extraction agent comprises tributyl phosphate and ionic liquid, and the volume ratio of described ionic liquid and described tributyl phosphate is not higher than 1:1.
2. the extraction agent of lithium ion according to claim 1, it is characterized in that, the volume ratio of described ionic liquid and described tributyl phosphate is not higher than 2:3.
3. the extraction agent of lithium ion according to claim 1 or 2, it is characterized in that, the volume ratio of described ionic liquid and described tributyl phosphate is 0.2 ~ 0.5:1.
4. the extraction agent of lithium ion according to claim 1 or 2, it is characterized in that, described ionic liquid is imidazole salts.
5. the extraction agent of lithium ion according to claim 4, it is characterized in that, described ionic liquid is imidazole phosphate.
6. the extraction agent of lithium ion according to claim 5, it is characterized in that, described ionic liquid is at least one in 1-butyl-3-Methylimidazole hexafluorophosphate, 1-hexyl-3-Methylimidazole hexafluorophosphate, 1-octyl group-3-Methylimidazole hexafluorophosphate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498184A (en) * | 2016-12-07 | 2017-03-15 | 青海柴达木兴华锂盐有限公司 | A kind of extraction system of lithium |
| CN108504868A (en) * | 2018-05-15 | 2018-09-07 | 中国科学院过程工程研究所 | A kind of method of lithium metal in recycling waste and old lithium ion battery |
| CN108866352A (en) * | 2017-12-04 | 2018-11-23 | 青海柴达木兴华锂盐有限公司 | The technique that Phosphate Ionic Liquids extract the lithium production lithium carbonate in salt lake bittern |
| CN108892158A (en) * | 2018-07-18 | 2018-11-27 | 北京化工大学 | The method of lithium ion is extracted using non-fluorine non-ferric ionic liquid as co-extraction agent |
| CN110551894A (en) * | 2019-10-17 | 2019-12-10 | 青海民族大学 | Extraction separation system for separating rubidium ions from salt lake brine and use method thereof |
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| CN102312110A (en) * | 2010-07-09 | 2012-01-11 | 何涛 | Method for extracting alkali metal from salt lake brine and seawater through membrane extraction-back extraction |
| CN102992358A (en) * | 2012-02-24 | 2013-03-27 | 中国科学院青海盐湖研究所 | Method for extracting lithium salt from lithium brine |
| CN103031448A (en) * | 2012-12-04 | 2013-04-10 | 中国科学院过程工程研究所 | Method for preenriching and separating lithium and boron from salt lake brine by liquid-liquid-liquid three-phase extraction |
| CN103710549A (en) * | 2013-12-13 | 2014-04-09 | 天津科技大学 | Method for efficiently extracting lithium from salt lake brine |
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| CN101767804A (en) * | 2009-12-25 | 2010-07-07 | 江南大学 | Method for extracting lithium from salt lake brine |
| CN102312110A (en) * | 2010-07-09 | 2012-01-11 | 何涛 | Method for extracting alkali metal from salt lake brine and seawater through membrane extraction-back extraction |
| CN102992358A (en) * | 2012-02-24 | 2013-03-27 | 中国科学院青海盐湖研究所 | Method for extracting lithium salt from lithium brine |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498184A (en) * | 2016-12-07 | 2017-03-15 | 青海柴达木兴华锂盐有限公司 | A kind of extraction system of lithium |
| CN108866352A (en) * | 2017-12-04 | 2018-11-23 | 青海柴达木兴华锂盐有限公司 | The technique that Phosphate Ionic Liquids extract the lithium production lithium carbonate in salt lake bittern |
| CN108504868A (en) * | 2018-05-15 | 2018-09-07 | 中国科学院过程工程研究所 | A kind of method of lithium metal in recycling waste and old lithium ion battery |
| CN108504868B (en) * | 2018-05-15 | 2020-03-10 | 中国科学院过程工程研究所 | Method for recovering metal lithium in waste lithium ion battery |
| CN108892158A (en) * | 2018-07-18 | 2018-11-27 | 北京化工大学 | The method of lithium ion is extracted using non-fluorine non-ferric ionic liquid as co-extraction agent |
| CN110551894A (en) * | 2019-10-17 | 2019-12-10 | 青海民族大学 | Extraction separation system for separating rubidium ions from salt lake brine and use method thereof |
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Application publication date: 20150107 |