CN104357677A - Method for extracting lithium from salt lake brine - Google Patents

Method for extracting lithium from salt lake brine Download PDF

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Publication number
CN104357677A
CN104357677A CN201410693097.9A CN201410693097A CN104357677A CN 104357677 A CN104357677 A CN 104357677A CN 201410693097 A CN201410693097 A CN 201410693097A CN 104357677 A CN104357677 A CN 104357677A
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Prior art keywords
lithium
salt lake
extract
lake brine
extracted
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CN201410693097.9A
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Inventor
姬连敏
李丽娟
时东
李晋峰
宋雪雪
聂锋
宋富根
曾忠民
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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    • 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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  • Extraction Or Liquid Replacement (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for extracting lithium from salt lake brine. The method comprises the following steps: adding HCl and FeCl3.6H2O to an extract water phase (an LiCl-MgCl2-H2O system), and controlling the ratio of amount of substances of iron and lithium to be 1.3 to 1; standing after fully mixing the extract water phase with an extract organic phase in a volume ratio of 1 to 2, and separating a liquid phase. By adopting the method, the problems that the corrosivity of high-concentration tributyl phosphate towards extraction equipment is stronger and the dissolution loss of an extracting agent in water is serious in long-term operation are solved, and the lithium extraction efficiency of the prior art is achieved. The extraction method is simple and reliable to operate.

Description

The method of lithium is extracted in a kind of salt lake brine
Technical field
The invention belongs to extraction chemistry, chemical technology field, particularly relate to a kind of method utilizing composite extractant to extract lithium from salt lake brine.
Background technology
Salt lake brine is rich in several mineral materials, is also wherein 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, how therefrom separation and Extraction lithium is the important topic of current research.
Lithium not only has important application in national defense industry, and the 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.
Solvent extraction technology is the effective technology of the various metal of separation and Extraction from solution, it has that separation efficiency is high, technology and equipment is simple, operation serialization, be easy to realize the advantages such as control automatically, is considered to one of the most promising method of extraction and isolation lithium from high Mg/Li ratio bittern.At present, the most frequently used extraction system is with tributyl phosphate (TBP) for extraction agent, and iron trichloride is coextraction agent, and sulfonated kerosene is thinner; Wherein Li and Fe is with LiFeCl 4form coextraction enter organic phase, with MgCl a large amount of in aqueous phase 2and other metals realize being separated.But need the tributyl phosphate using high density in this system, stronger to the corrodibility of extraction equipment, and in long-term operation extraction agent not only in water molten damage serious, and in acidic medium, tributyl phosphate is easily degraded, and particularly it limits the application of its industrial-scale to the serious swelling action of the material for making extraction equipment.
Summary of the invention
Being to provide for overcoming above not enough the object of the invention a kind of method extracting lithium in salt lake brine, comprising the following steps:
1) extracted organic phase is prepared: extracted organic phase comprises composite extractant and thinner, wherein composite extractant is by tributyl phosphate and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide by volume per-cent is that 30 ~ 80%:20% ~ 70% mixes, and thinner is sulfonated kerosene;
2) aqueous phase extracted: be LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is that 1:2 fully mixes rear leaving standstill and liquid phase separation.
Wherein, the volume ratio of composite extractant and thinner is: 1:1.
Wherein, step 4) the sufficient condition of mixing for concussion 6min.
Preferably, step 3) in lithium concentration be 1.9604g/L.
Preferably, tributyl phosphate and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide volume percent are 50%:50%.
The invention provides extracted organic phase and extracting process that Lithium from Salt Lake Brine is extracted, reduce extraction agent tributyl phosphate concentration of the prior art, the further corrodibility of tributyl phosphate to extraction equipment improving high density is stronger, and in long-term operation the extraction agent problem that not only molten damage is serious in water, and reach prior art extraction lithium efficiency.Operation is simple and reliable for extracting process.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described.
Embodiment 1
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 300mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 700mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Embodiment 2
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 400mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 600mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Embodiment 3
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 500mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 500mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Embodiment 4
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 600mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 400mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Embodiment 5
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 700mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 300mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Embodiment 6
Extract the method for lithium in this salt lake brine that the present embodiment provides, comprising:
1) extracted organic phase is prepared: get tributyl phosphate 800mL and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide 200mL is mixed into composite extractant, and getting 1000mL sulfonated kerosene is that thinner adds in composite extractant;
2) aqueous phase extracted: the salt lake brine getting saturated magnesium chloride solution is LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the ratio of the amount of substance of control iron, lithium is 1.3:1, and at this moment lithium concentration is 1.9604g/L, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is leave standstill and liquid phase separation after 1:2 fully mixes concussion 6min.Detect Separation of Li and Mg data.In table 1.
Table 1
Separation of Li and Mg data are detected after above six embodiments extraction, analytical table 1 can draw, although tributyl phosphate (TBP) content is higher, lithium percentage extraction relatively also can be higher, but suitably mix N, N-bis-(2-ethylhexyl)-3-butanone ethanamide (ND2EHBTA), still can keep higher lithium separation efficiency, see that the result lithium percentage extraction of several embodiment is between 65.11% ~ 89.24%, completely can be suitable with existing tributyl phosphate (TBP) extraction efficiency, and Separation of Li and Mg factor also reaches nearly 200 even more than 500.Separating effect is obvious.
To sum up, the method extracting lithium in the extracted organic phase of this extraction lithium provided by the invention and salt lake brine can lithium effectively in separated salt lake bittern water, overcome the defect that the corrodibility of existing high-concentration phosphoric acid tri-n-butyl to extraction equipment is stronger, and extraction agent molten damage problem in water is controlled in long-term operation.

Claims (5)

1. extract a method for lithium in salt lake brine, it is characterized in that, comprise the following steps:
1) extracted organic phase is prepared: extracted organic phase comprises composite extractant and thinner, wherein composite extractant is by tributyl phosphate and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide by volume per-cent is that 30 ~ 80%:20% ~ 70% mixes, and thinner is sulfonated kerosene;
2) aqueous phase extracted: be LiCl-MgCl 2-H 2o system;
3) in aqueous phase extracted, HCl, FeCl is added 36H 2o, wherein, the amount of substance ratio of control iron, lithium is 1.3:1, and acid concentration is 0.05mol/L;
4) by step 3) aqueous phase extracted and the step 1 that obtain) the extracted organic phase volume ratio that obtains is that 1:2 fully mixes rear leaving standstill and liquid phase separation.
2. extract the method for lithium in salt lake brine according to claim 1, it is characterized in that, the volume ratio of described composite extractant and thinner is: 1:1.
3. extract the method for lithium in salt lake brine according to claim 1, it is characterized in that, described step 4) mixing condition for concussion 6min.
4. extract the method for lithium in salt lake brine according to claim 1, it is characterized in that, described lithium concentration is 1.9604g/L.
5. extract the method for lithium in magnesium chloride solution according to claim 1, it is characterized in that, described tributyl phosphate and N, N-bis-(2-ethylhexyl)-3-butanone ethanamide volume percent are 50%:50%.
CN201410693097.9A 2014-11-26 2014-11-26 Method for extracting lithium from salt lake brine Pending CN104357677A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105177288A (en) * 2015-10-28 2015-12-23 中国科学院青海盐湖研究所 Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio
CN106191445A (en) * 2016-06-30 2016-12-07 南昌航空大学 The separation method of lithium ion in a kind of lithium ion battery leachate
CN107447118A (en) * 2016-06-01 2017-12-08 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system, extracting process and back extraction method
CN107447109A (en) * 2016-06-01 2017-12-08 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system, extracting process and back extraction method
CN107619926A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 The application of amides compound, containing its extracts composition and extraction system
CN107619934A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system and its application
CN107619930A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 The application of amides compound, containing its extracts composition and extraction system
CN109264835A (en) * 2018-10-09 2019-01-25 天津科技大学 Continuous electrochemical element extraction system
WO2019114816A1 (en) * 2017-12-16 2019-06-20 虔东稀土集团股份有限公司 Extraction method for lithium element
CN115874050A (en) * 2022-10-31 2023-03-31 广东松泉环保设备有限公司 Neutral extractant and preparation process 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
CN102602965A (en) * 2011-01-20 2012-07-25 凯米涛弗特公司 Production of high purity lithium compounds directly from lithium containing brines
CN103523804A (en) * 2012-11-16 2014-01-22 中国科学院上海有机化学研究所 Method for extracting lithium salt from lithium-contained brine by using extraction process
CN103572071A (en) * 2013-11-15 2014-02-12 中国科学院青海盐湖研究所 Method for refining lithium from salt lake brine with high magnesium-lithium ratio
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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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
CN102602965A (en) * 2011-01-20 2012-07-25 凯米涛弗特公司 Production of high purity lithium compounds directly from lithium containing brines
CN103523804A (en) * 2012-11-16 2014-01-22 中国科学院上海有机化学研究所 Method for extracting lithium salt from lithium-contained brine by using extraction process
CN103572071A (en) * 2013-11-15 2014-02-12 中国科学院青海盐湖研究所 Method for refining lithium from salt lake brine with high magnesium-lithium ratio
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Cited By (18)

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CN105177288B (en) * 2015-10-28 2018-04-03 中国科学院青海盐湖研究所 A kind of method that lithium hydroxide is prepared using salt lake brine with high magnesium-lithium ratio
CN105177288A (en) * 2015-10-28 2015-12-23 中国科学院青海盐湖研究所 Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio
CN107447118A (en) * 2016-06-01 2017-12-08 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system, extracting process and back extraction method
CN107447109A (en) * 2016-06-01 2017-12-08 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system, extracting process and back extraction method
CN107447118B (en) * 2016-06-01 2020-12-29 中国科学院上海有机化学研究所 Extraction composition, extraction system, extraction method and back extraction method
CN107447109B (en) * 2016-06-01 2020-08-07 中国科学院上海有机化学研究所 Extraction composition, extraction system, extraction method and back extraction method
CN106191445A (en) * 2016-06-30 2016-12-07 南昌航空大学 The separation method of lithium ion in a kind of lithium ion battery leachate
CN107619934B (en) * 2016-07-15 2020-08-07 中国科学院上海有机化学研究所 Extraction composition, extraction system and application thereof
CN107619930B (en) * 2016-07-15 2020-08-07 中国科学院上海有机化学研究所 Application of amide compounds, extraction composition containing amide compounds and extraction system
CN107619926B (en) * 2016-07-15 2020-08-07 中国科学院上海有机化学研究所 Application of amide compounds, extraction composition containing amide compounds and extraction system
CN107619930A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 The application of amides compound, containing its extracts composition and extraction system
CN107619934A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 A kind of extracts composition, extraction system and its application
CN107619926A (en) * 2016-07-15 2018-01-23 中国科学院上海有机化学研究所 The application of amides compound, containing its extracts composition and extraction system
WO2019114816A1 (en) * 2017-12-16 2019-06-20 虔东稀土集团股份有限公司 Extraction method for lithium element
CN109264835A (en) * 2018-10-09 2019-01-25 天津科技大学 Continuous electrochemical element extraction system
CN109264835B (en) * 2018-10-09 2021-08-06 天津科技大学 Continuous electrochemical element extraction system
CN115874050A (en) * 2022-10-31 2023-03-31 广东松泉环保设备有限公司 Neutral extractant and preparation process thereof
CN115874050B (en) * 2022-10-31 2023-09-19 广东松泉环保设备有限公司 Neutral extractant and its preparing process

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