冠醚离子液体萃取分离水溶液中Rb~+和Cs~+
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摘要
合成了1-丁基-3-乙酰基苯并21冠7双三氟甲磺酰亚胺盐、1-己基-3-乙酰基苯并21冠7双三氟甲磺酰亚胺盐和1-辛基-3-乙酰基苯并21冠7双三氟甲磺酰亚胺盐3种不同烷基链长的冠醚离子液体([C_n(benzo21C7)AIm]NTf_2,n=4,6,8,简称为C_n-CrownIL)。将合成的冠醚离子液体与1-丁基-3-甲基咪唑双三氟甲磺酰亚胺离子液体([C_4MIm]NTf_2)混合,构建了C_n-CrownIL/[C_4MIm]NTf_2复配系统。结果表明,C_n-CrownIL/[C_4MIm]NTf_2对水溶液中的Rb~+和Cs~+具有非常高的萃取能力,即使溶液中Rb~+和Cs~+质量浓度低至10 mg/L,萃取剂对Rb~+和Cs~+仍保持高达97%以上的萃取率。吸附Rb~+和Cs~+的萃取剂可利用稀硝酸洗脱而实现重复利用,5次循环后,萃取剂对Rb~+和Cs~+的萃取率依然可达90%。理论计算表明,C_4-CrownIL/[C_4MIm]NTf_2萃取Rb~+和Cs~+依赖的是冠醚单元中的O原子与Rb~+和Cs~+之间较强的络合作用,冠醚空腔大小与Rb~+和Cs~+的离子半径高度匹配是C_4-CrownIL/[C_4MIm]NTf_2优先萃取Rb~+和Cs~+的重要原因。
The hydrophobic 1-alkyl-3-acetyl-benzo21 crown 7 bis(trifluoromethylsulfonyl)imide ionic liquid [C_n(benzo21 C7)AIm]NTf_2(n=4,6,8) abbreviated by C_n-CrownIL were synthesized. The synthesized crown ether ionic liquids were characterized by IR and NMR. The crown ether ionic liquid was mixed with 1-butyl-3-methyl-imidazole bis(trifluoromethylsulfonyl)imide ionic liquid([C_4MIm]NTf_2) to construct C_n-CrownIL/[C_4MIm]NTf_2 complexes. It was found that the hydrophobicity of C_n-CrownIL/[C_4MIm]NTf_2 ensured the formation of a phase separation system of aqueous solution. The results showed that C_n-CrownIL/[C_4MIm]NTf_(2 )had a high extraction for Rb~+ and Cs~(+ ), the extraction efficiency was almost 100% which was higher than other metal ions, and the order of metal ions extraction efficiency was Cs~+>Rb~+>K~+>Ca~(2+)>Na~+>Mg~(2+)>Li~+. Even though the concentrations of Rb~+ and Cs~(+ )were as low as 10 mg/L, the extraction efficiency remained above 97%. The addition of [C_4MIm]NTf_2 in the extractant greatly improved the extraction efficiency. The extraction rate of C_n-CrownIL/[C_4MIm]NTf_2 was very high and the extraction equilibrium could be achieved after 10 min. By increasing of alkyl chain length, the extraction efficiency of NTf~-_2 crown ether for Rb~(+ )and Cs~(+ )decreased slightly, but still was maintained above 85%. The extraction efficiency of Rb~(+ )and Cs~+ increased with the increase of solution pH. The recycle of C_n-CrownIL/[C_4MIm]NTf_2 can be realized by adding diluted nitric acid to reextract Rb~+ and Cs~+. Results from recycling tests showed that the extraction efficiency of Rb~+ and Cs~(+ )was still above 90% after five recycling tests. Theoretical calculations showed that the extraction of C_4-CrownIL/[C_4MIm]NTf_2 for Rb~+ and Cs~+ depended on the strong complexation of the oxygen atom in the crown ether with Rb~+ and Cs~+, but the primary reason was that the cavity size of crown ether highly matched the ion-radius of Rb~+ and Cs~+.
The hydrophobic 1-alkyl-3-acetyl-benzo21 crown 7 bis(trifluoromethylsulfonyl)imide ionic liquid [C_n(benzo21 C7)AIm]NTf_2(n=4,6,8) abbreviated by C_n-CrownIL were synthesized. The synthesized crown ether ionic liquids were characterized by IR and NMR. The crown ether ionic liquid was mixed with 1-butyl-3-methyl-imidazole bis(trifluoromethylsulfonyl)imide ionic liquid([C_4MIm]NTf_2) to construct C_n-CrownIL/[C_4MIm]NTf_2 complexes. It was found that the hydrophobicity of C_n-CrownIL/[C_4MIm]NTf_2 ensured the formation of a phase separation system of aqueous solution. The results showed that C_n-CrownIL/[C_4MIm]NTf_(2 )had a high extraction for Rb~+ and Cs~(+ ), the extraction efficiency was almost 100% which was higher than other metal ions, and the order of metal ions extraction efficiency was Cs~+>Rb~+>K~+>Ca~(2+)>Na~+>Mg~(2+)>Li~+. Even though the concentrations of Rb~+ and Cs~(+ )were as low as 10 mg/L, the extraction efficiency remained above 97%. The addition of [C_4MIm]NTf_2 in the extractant greatly improved the extraction efficiency. The extraction rate of C_n-CrownIL/[C_4MIm]NTf_2 was very high and the extraction equilibrium could be achieved after 10 min. By increasing of alkyl chain length, the extraction efficiency of NTf~-_2 crown ether for Rb~(+ )and Cs~(+ )decreased slightly, but still was maintained above 85%. The extraction efficiency of Rb~(+ )and Cs~+ increased with the increase of solution pH. The recycle of C_n-CrownIL/[C_4MIm]NTf_2 can be realized by adding diluted nitric acid to reextract Rb~+ and Cs~+. Results from recycling tests showed that the extraction efficiency of Rb~+ and Cs~(+ )was still above 90% after five recycling tests. Theoretical calculations showed that the extraction of C_4-CrownIL/[C_4MIm]NTf_2 for Rb~+ and Cs~+ depended on the strong complexation of the oxygen atom in the crown ether with Rb~+ and Cs~+, but the primary reason was that the cavity size of crown ether highly matched the ion-radius of Rb~+ and Cs~+.
引文
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[11] DAYANAND P, DATTATRAYA C, ABHIJEET M, et al. Novel crown ether functionalized imidazolium-based acidic ionic liquid catalyzed synthesis of pyrazole derivatives under solvent-free conditions[J]. Research on Chemical Intermediate, 2015, 41(9): 6843-6858.
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[13] REY E C, TORREJOS, GRACE M, et al. Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid[J]. Hydrometallurgy, 2016, 164: 362-371.
[14] ZHAO Y, TRUHLAR D G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals[J]. Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), 2008, 120(1): 215-241.
[15] LEININGEER T, NICKLASS A, KüCHLE W, et al. The accuracy of the pseudopotential approximation: Non-frozen-core effects for spectroscopic constants of alkali fluorides XF (X=K, Rb, Cs)[J]. Chemical Physics Letters, 1996, 255(4): 274-280.
[16] WEIGEND F, AHLRICHS R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy[J]. Physical Chemistry Chemical Physics, 2005, 7(18): 3297-3305.
[17] LU T, CHEN F. Multiwfn: A multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
[18] HUMPHREY W, DALKE A, SCHILTEN K. VMD: Visual molecular dynamics[J]. Journal of molecular graphics, 1996, 14(1): 33-38.
[19] LUO H, DAI S, BONNESEN P V, et al. Extraction of cesium ions from aqueous solutions using calix[4]arene-bis(tert-octylbenzo-crown-6) in ionic liquids[J]. Analytical Chemistry, 2004, 76(11): 3078-3083.
[20] SACHLEBEN R A, DENG Y, BAILEY D R, et al. Ringsize and substituent effects in the eolvent extraction of alkali metal nitrates by crown ethers in 1, 2-dichloroethane and 1-octanol[J]. Solvent Extraction and Ion Exchange, 1996, 14(6): 995-1015.
[21] 李长平, 辛宝平, 徐文国, 等.疏水性离子液体为溶剂对Co2+和Cd2+废水的萃取性能[J]. 过程化工学报, 2007, 7(4): 674-678.
[22] CUKROWSKI I, GOVENDER K K, MITORAJ M P, et al. QTAIM and ETS-NOCV analyses of intramolecular CH…HC interactions in metal complexes[J]. The Journal of Physical Chemistry A, 2011, 115(45): 12746-12757.
[2] 刘珊. 粗粒磷钼酸铵及其复合物对铷/铯离子的选择性吸附研究[D].长沙: 湖南大学, 2012.
[3] 安莲英, 赵琳, 黄献奖, 等.磷钨酸铵-海藻酸钙复合吸附剂分离铷、钾工艺研究[J]. 矿物岩石, 2015, 35(3): 1-5.
[4] JANKOWSKI C K, DOZOL J F, ALLAIN F. Use of cesium salts for detection of crownether macrocycles with the electrospray ionization mass spectrometry technique[J]. Polish Journal of Chemistry, 2002, 76(5): 701-711.
[5] WANG J C, ZHANG X W, SONG C L. Extracting performance of cesium by25, 27-bis(2-propyloxy) calix[4]-26, 28-crown-6(iPr-C[4]C-6) in n-octanol[J]. Separation Science and Technology, 2005, 40(16): 3381-3392.
[6] 杨少华, 赖晓晖, 王君, 等.t-BAMBP萃取分离高钾钠卤水中的铷工艺研究[J]. 有色金属科学与工程, 2015, 6(5): 17-21.
[7] VISSER A E, SWATLOSKI R P, REICHERT M W, et al. Traditional extractants in nontraditional solvents: Groups 1 and 2 extraction by crown ethers in room-temperature ionic liquids[J]. Industrial & Engineering Chemistry Research, 2000, 39 (10): 3596-3604.
[8] XU C, YUAN L Y, SHEN X, et al. Efficient removal ofcaesium ions from aqueous solution using a calix crown ether in ionic liquids: Mechanism and radiation effect[J]. Dalton Transactions, 2010, 39(16): 3897-3902.
[9] SANGKI C, SERGEI V, DZYUBA, et al. Influence of structural variation in room-temperature ionic liquids on the selectivity and efficiency of competitive alkali metal salt extraction by a crown ether[J].Analytical Chemistry, 2001, 73(15): 3737-3741.
[10] 车佳宁, 刘飞, 彭昌军, 等.疏水性胍类离子液体萃取水溶液中的重金属离子[J]. 华东理工大学学报(自然科学版), 2016, 42 (6): 782-787.
[11] DAYANAND P, DATTATRAYA C, ABHIJEET M, et al. Novel crown ether functionalized imidazolium-based acidic ionic liquid catalyzed synthesis of pyrazole derivatives under solvent-free conditions[J]. Research on Chemical Intermediate, 2015, 41(9): 6843-6858.
[12] DAI S, JU Y H, BARNES C E. Solvent extraction of strontium nitrate by a crown ether using room-temperature ionic liquids[J].Journal of the Chemical Society, 1999(8): 1201-1202.
[13] REY E C, TORREJOS, GRACE M, et al. Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid[J]. Hydrometallurgy, 2016, 164: 362-371.
[14] ZHAO Y, TRUHLAR D G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals[J]. Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), 2008, 120(1): 215-241.
[15] LEININGEER T, NICKLASS A, KüCHLE W, et al. The accuracy of the pseudopotential approximation: Non-frozen-core effects for spectroscopic constants of alkali fluorides XF (X=K, Rb, Cs)[J]. Chemical Physics Letters, 1996, 255(4): 274-280.
[16] WEIGEND F, AHLRICHS R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy[J]. Physical Chemistry Chemical Physics, 2005, 7(18): 3297-3305.
[17] LU T, CHEN F. Multiwfn: A multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
[18] HUMPHREY W, DALKE A, SCHILTEN K. VMD: Visual molecular dynamics[J]. Journal of molecular graphics, 1996, 14(1): 33-38.
[19] LUO H, DAI S, BONNESEN P V, et al. Extraction of cesium ions from aqueous solutions using calix[4]arene-bis(tert-octylbenzo-crown-6) in ionic liquids[J]. Analytical Chemistry, 2004, 76(11): 3078-3083.
[20] SACHLEBEN R A, DENG Y, BAILEY D R, et al. Ringsize and substituent effects in the eolvent extraction of alkali metal nitrates by crown ethers in 1, 2-dichloroethane and 1-octanol[J]. Solvent Extraction and Ion Exchange, 1996, 14(6): 995-1015.
[21] 李长平, 辛宝平, 徐文国, 等.疏水性离子液体为溶剂对Co2+和Cd2+废水的萃取性能[J]. 过程化工学报, 2007, 7(4): 674-678.
[22] CUKROWSKI I, GOVENDER K K, MITORAJ M P, et al. QTAIM and ETS-NOCV analyses of intramolecular CH…HC interactions in metal complexes[J]. The Journal of Physical Chemistry A, 2011, 115(45): 12746-12757.