盐湖卤水萃取提锂及其机理研究
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摘要
我国西部拥有丰富的卤水锂资源,是世界上最具开发价值的盐湖区之一,但绝大部分盐湖卤水中锂离子含量低,同时富含大量的钠、钾、钙、镁离子,因此实现锂离子与其它离子的高效分离,是开发我国盐湖锂资源的关键所在。本文以盐湖卤水体系为研究对象,采用分子模拟和实验相结合的方法研究萃取剂与卤水中各离子之间的相互作用,初步建立了盐湖卤水萃取提锂的作用机理模型和计算方法,为后续萃取剂的改进提供依据。
论文首先通过研究西台及察尔汗卤水蒸发过程中的化学组成变化,盐类析出顺序、种类和物理化学性质的变化,获得锂在卤水蒸发过程中的富集与损失规律,为盐湖提锂工艺的优化提供依据。
选择经过富集的老卤作为水相,TBP-煤油-FeCl3萃取体系作为萃取剂,对锂离子萃取—反萃过程进行系统研究。实验结果表明,TBP-煤油-FeCl3萃取体系对锂离子的选择性较好,萃取效果稳定。获得了萃取的最优工艺条件：萃取相比O/A为1.5,TBP质量分数为75%,[Fe3+]/[Li+]为2,[H+]为0.02 mol/L,萃取时间为20 min,萃取温度为20℃；洗涤的相比为15；反萃取的盐酸浓度为1 mol/L,相比为2.5。锂离子的单级萃取率可达到90%左右,反萃取液中锂离子浓度约为1.670g/L,单级循环锂离子收率约为70%,并通过斜率法确定了萃取反应萃合比为2,萃取平衡常数为5.26 L3.mol-3.
通过红外与核磁分析研究,初步探明是TBP上的P=O双键与LiFeCl4金属络合物的配位水分子产生氢键作用而使得金属络合物与TBP结合。利用分子模拟对萃取机理进行进一步研究,结果证明了LiFeCl4是通过3个配位水分子与TBP结合的。通过比较LiFeCl4、NaFeCl4、KFeCl4与TBP结合后最优结构的结合能,证明TBP-煤油-FeCl3萃取体系对锂离子具有选择性。
There exists a large amount of lithium resource at Qinghai and Tibet in China, the world's most valuable salt lake areas. It is very difficult to separate lithium from salt lake brine, since lithium ion content is low, and others ions, such as sodium, potassium, calcium, magnesium ions contents are high in brine. In this work, the extraction mechanism and extraction process of lithium from salt lake brine were studied theritically and experimentally, the moluculor modeling method was used to study the interaction between extraction agent molecular and metal ions, in order to provide a theoretical basis for the optimal selection and improvement on extraction agent in the future.
To increase the extraction efficency of lithium from salt lake brine, firstly, lithium ion in West taijnar and Quarhan salt lake brine was concentrated from the lower concentration (<30mmol/L) to a higer concentration (>200mmol/L) by natural evaporation under the ambient environmrntal condition. The evaporation condition, the physical and chemical properties of crsystallized salt, and chemical composition in the concentrated brine, were researched, the suitable brine for the lithium extraction experiment was selected.
Then, the lithium ion in the concentrated brine was extracted using a organic phase of tributyl phosphate(TBP)-kerosene-FeCl3. The experimental results showed that the extraction system could recover lithium ion from brine with the higer selectivity, and the extraction process was more efficient and stable. The operating conditions were optimized experimentally by studying the single factors of extraction O/A ratio, extractant composition, molar ratio of Fe3+ to Li+and so on. The optimal condition for the extraction process were: extraction O/A=1.5, TBP%=75%, [Fe3+]/[Li+]=2, [H+]=0.02 mol/L, extraction time=20 min; washing O/A=15; back extraction O/A-20, back extraction [H+]=1 mol/L.
Furthermore, the complex compound of lithium ion and TBP was investigated by IR and NMR. The results showed that the interaction among litium ion, FeCl3, TBP was by hydrogen bond. The mechanism was further studied by the molecular simulation. The results showed that LiFeCl4 complex compound and TBP were associated through three coordinated water molecules, and the TBP-kerosene-FeCl3 extraction system can extracted lithium ion with higher selectivity.
论文首先通过研究西台及察尔汗卤水蒸发过程中的化学组成变化,盐类析出顺序、种类和物理化学性质的变化,获得锂在卤水蒸发过程中的富集与损失规律,为盐湖提锂工艺的优化提供依据。
选择经过富集的老卤作为水相,TBP-煤油-FeCl3萃取体系作为萃取剂,对锂离子萃取—反萃过程进行系统研究。实验结果表明,TBP-煤油-FeCl3萃取体系对锂离子的选择性较好,萃取效果稳定。获得了萃取的最优工艺条件：萃取相比O/A为1.5,TBP质量分数为75%,[Fe3+]/[Li+]为2,[H+]为0.02 mol/L,萃取时间为20 min,萃取温度为20℃；洗涤的相比为15；反萃取的盐酸浓度为1 mol/L,相比为2.5。锂离子的单级萃取率可达到90%左右,反萃取液中锂离子浓度约为1.670g/L,单级循环锂离子收率约为70%,并通过斜率法确定了萃取反应萃合比为2,萃取平衡常数为5.26 L3.mol-3.
通过红外与核磁分析研究,初步探明是TBP上的P=O双键与LiFeCl4金属络合物的配位水分子产生氢键作用而使得金属络合物与TBP结合。利用分子模拟对萃取机理进行进一步研究,结果证明了LiFeCl4是通过3个配位水分子与TBP结合的。通过比较LiFeCl4、NaFeCl4、KFeCl4与TBP结合后最优结构的结合能,证明TBP-煤油-FeCl3萃取体系对锂离子具有选择性。
There exists a large amount of lithium resource at Qinghai and Tibet in China, the world's most valuable salt lake areas. It is very difficult to separate lithium from salt lake brine, since lithium ion content is low, and others ions, such as sodium, potassium, calcium, magnesium ions contents are high in brine. In this work, the extraction mechanism and extraction process of lithium from salt lake brine were studied theritically and experimentally, the moluculor modeling method was used to study the interaction between extraction agent molecular and metal ions, in order to provide a theoretical basis for the optimal selection and improvement on extraction agent in the future.
To increase the extraction efficency of lithium from salt lake brine, firstly, lithium ion in West taijnar and Quarhan salt lake brine was concentrated from the lower concentration (<30mmol/L) to a higer concentration (>200mmol/L) by natural evaporation under the ambient environmrntal condition. The evaporation condition, the physical and chemical properties of crsystallized salt, and chemical composition in the concentrated brine, were researched, the suitable brine for the lithium extraction experiment was selected.
Then, the lithium ion in the concentrated brine was extracted using a organic phase of tributyl phosphate(TBP)-kerosene-FeCl3. The experimental results showed that the extraction system could recover lithium ion from brine with the higer selectivity, and the extraction process was more efficient and stable. The operating conditions were optimized experimentally by studying the single factors of extraction O/A ratio, extractant composition, molar ratio of Fe3+ to Li+and so on. The optimal condition for the extraction process were: extraction O/A=1.5, TBP%=75%, [Fe3+]/[Li+]=2, [H+]=0.02 mol/L, extraction time=20 min; washing O/A=15; back extraction O/A-20, back extraction [H+]=1 mol/L.
Furthermore, the complex compound of lithium ion and TBP was investigated by IR and NMR. The results showed that the interaction among litium ion, FeCl3, TBP was by hydrogen bond. The mechanism was further studied by the molecular simulation. The results showed that LiFeCl4 complex compound and TBP were associated through three coordinated water molecules, and the TBP-kerosene-FeCl3 extraction system can extracted lithium ion with higher selectivity.
引文
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