离子液体内耦合液膜分离研究
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摘要
传统化学反应及相关化学工业是当今世界严重污染的主要来源,污染的很大部分来自于反应过程中使用的大量易挥发性有机溶剂(VOC)。针对有机溶剂产生的污染,寻找绿色替代溶剂显得尤为重要。离子液体(ILs)是指在室温或接近室温下呈现液态的、完全由阴阳离子所组成的盐,它们具有一些独特的优点,如无毒、不易燃、高热稳定性、宽的液相温度(-100℃～200℃)、易循环利用等。由于这些优点,离子液体被当作绿色溶剂,越来越受到人们的关注。
本文在微波辅助下,合成了中间体溴化1-丁基-3-甲基咪唑([BMIM]Br)、亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF_4)和疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF_6),考察了原料配比、温度、反应时间等因素对生成率的影响,并对合成的产物进行了红外表征及一些物性测定。实验的第二部分是将合成的[BMIM]PF_6用于内耦合液膜体系中,分别研究了苯酚、对硝基酚以及水杨酸的迁移规律,考察了料液相酸度、初始浓度、反萃相NaOH浓度等因素对迁移率的影响,得出了苯酚、对硝基酚以及水杨酸的最佳迁移条件。实验得到以下结论:
(1)[BMIM]Br的最佳合成条件:原料摩尔比1.1:1(溴代正丁烷:N-甲基咪唑),T=85℃,t=4 min;[BMIM]BF_4的最佳合成条件:原料摩尔比1.2:1(NaBF_4:中间体),T=60℃,t=6 min;[BMIM]PF_6的最佳合成条件:原料摩尔比1.1:1(NH_4PF_6:中间体),T=80℃,t=9 min。
(2)两种离子液体的黏度都是随着温度的升高而降低,电导率随着温度的升高而升高;[BMIM]BF_4有一定的吸水性,而[BMIM]PF_6吸水性较弱;溶解性实验表明,离子液体的溶解性与阴离子的类型有很大的关系。
(3)苯酚最佳迁移条件为:温度300 K,搅拌速度350 r/min,料液相pH 3.65,反萃相NaOH浓度0.8 mol/L;对硝基酚最佳迁移条件为:料液相pH 3.21,反萃相NaOH浓度0.1mol/L,离子强度0.4;苯酚和对硝基酚在料液相pH 9.18时可以很好地分离;水杨酸最佳迁移条件为:料液相pH 1.0,反萃相NaOH浓度0.3 mol/L,离子强度0.5。
(4)该内耦合液膜体系迁移上述3种物质,都有一定的滞留现象;液膜迁移后经过处理,能重复利用。
Traditional chemical reactions and correlated chemical industry are the main source of pollution and most of the wastes are volatile organic compounds(VOC).Therefore,it is very essential to find green solvents to replace the organic solvents.Ionic liquids are liquid salts at or close to room temperature,which entirely consist of cations and anions.They have the unique advantages of no-toxicity,no-volatility,no-flammability,high thermal stability,wide liquid range(-100℃～200℃)and facility in recycling etc..Ionic liquids have attracted more and more attention as green solvent because of these advantages.
Synthesises of intermediate 1-butyl-3-methylimidazolium bromide([BMIM]Br),hydrophilic ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM]BF_4)and hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF_6)under microwave irradiation have been studied in this paper.Effects of raw material ratio,temperature, reaction time on the yield have been discussed.Subsequently,structures of the products have been identified by IR and physical properties also have been analyzed.[BMIM]PF_6 synthesized has been applied in the system of inner-coupled liquid membrane to transport phenol, p-nitrophenol and salicylic acid in the second part of the experiment.Effects of pH of the feed solution phase,initial solute concentration in the feed solution phase,sodium hydroxide concentration in the strip solution phase on transport of phenol,p-nitrophenol and salicylic acid have been studied.The optimum transport conditions have been obtained.The conclusions are as follows:
(1)Optimum synthesis condition of 1-butyl-3-methylimidazolium bromide are:raw material ratio 1.1:1(n-bromobutane:n-methylimidazole),T=85℃,t=4 min;Optimum synthesis condition of 1-butyl-3-methylimidazolium tetrafluoroborate are:raw material ratio 1.2:1(NaBF_4: [BMIM]Br),T=60℃,t=6 min;Optimum synthesis condition of 1-butyl-3-methylimidazolium hexafluorophosphate are:raw material ratio 1.1:1(NH_4PF_6:[BMIM]Br,T=80℃,t=9 min.
(2)Viscosities of both ionic liquids decrease as temperature increases,while conductivities are on the contrary;there is certain hydrophilicity in[BMIM]BF_4,while hydrophilicity is very weak in[BMIM]PF_6;solubilities of ionic liquids have great relationship with types of anions.
(3)The optimum transport conditions of phenol:temperature 300 K,stirring speed 350 r/min,pH in the feed solution phase 3.65,sodium hydroxide concentration in the strip solution phase 0.8 mol/L;The optimum transport conditions of p-nitrophenol:pH in the feed solution phase 3.21,sodium hydroxide concentration in the strip solution phase 0.1 mol/L,ionic strength 0.4;The optimum transport conditions of salicylic acid:pH in the feed solution phase 1.0, sodium hydroxide concentration in the strip solution phase 0.3 mol/L,ionic strength 0.5.
(4)There are retention phenomena in the system of inner-coupled liquid membrane;ionic liquids can be reused after treatment.
本文在微波辅助下,合成了中间体溴化1-丁基-3-甲基咪唑([BMIM]Br)、亲水性离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMIM]BF_4)和疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF_6),考察了原料配比、温度、反应时间等因素对生成率的影响,并对合成的产物进行了红外表征及一些物性测定。实验的第二部分是将合成的[BMIM]PF_6用于内耦合液膜体系中,分别研究了苯酚、对硝基酚以及水杨酸的迁移规律,考察了料液相酸度、初始浓度、反萃相NaOH浓度等因素对迁移率的影响,得出了苯酚、对硝基酚以及水杨酸的最佳迁移条件。实验得到以下结论:
(1)[BMIM]Br的最佳合成条件:原料摩尔比1.1:1(溴代正丁烷:N-甲基咪唑),T=85℃,t=4 min;[BMIM]BF_4的最佳合成条件:原料摩尔比1.2:1(NaBF_4:中间体),T=60℃,t=6 min;[BMIM]PF_6的最佳合成条件:原料摩尔比1.1:1(NH_4PF_6:中间体),T=80℃,t=9 min。
(2)两种离子液体的黏度都是随着温度的升高而降低,电导率随着温度的升高而升高;[BMIM]BF_4有一定的吸水性,而[BMIM]PF_6吸水性较弱;溶解性实验表明,离子液体的溶解性与阴离子的类型有很大的关系。
(3)苯酚最佳迁移条件为:温度300 K,搅拌速度350 r/min,料液相pH 3.65,反萃相NaOH浓度0.8 mol/L;对硝基酚最佳迁移条件为:料液相pH 3.21,反萃相NaOH浓度0.1mol/L,离子强度0.4;苯酚和对硝基酚在料液相pH 9.18时可以很好地分离;水杨酸最佳迁移条件为:料液相pH 1.0,反萃相NaOH浓度0.3 mol/L,离子强度0.5。
(4)该内耦合液膜体系迁移上述3种物质,都有一定的滞留现象;液膜迁移后经过处理,能重复利用。
Traditional chemical reactions and correlated chemical industry are the main source of pollution and most of the wastes are volatile organic compounds(VOC).Therefore,it is very essential to find green solvents to replace the organic solvents.Ionic liquids are liquid salts at or close to room temperature,which entirely consist of cations and anions.They have the unique advantages of no-toxicity,no-volatility,no-flammability,high thermal stability,wide liquid range(-100℃～200℃)and facility in recycling etc..Ionic liquids have attracted more and more attention as green solvent because of these advantages.
Synthesises of intermediate 1-butyl-3-methylimidazolium bromide([BMIM]Br),hydrophilic ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM]BF_4)and hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF_6)under microwave irradiation have been studied in this paper.Effects of raw material ratio,temperature, reaction time on the yield have been discussed.Subsequently,structures of the products have been identified by IR and physical properties also have been analyzed.[BMIM]PF_6 synthesized has been applied in the system of inner-coupled liquid membrane to transport phenol, p-nitrophenol and salicylic acid in the second part of the experiment.Effects of pH of the feed solution phase,initial solute concentration in the feed solution phase,sodium hydroxide concentration in the strip solution phase on transport of phenol,p-nitrophenol and salicylic acid have been studied.The optimum transport conditions have been obtained.The conclusions are as follows:
(1)Optimum synthesis condition of 1-butyl-3-methylimidazolium bromide are:raw material ratio 1.1:1(n-bromobutane:n-methylimidazole),T=85℃,t=4 min;Optimum synthesis condition of 1-butyl-3-methylimidazolium tetrafluoroborate are:raw material ratio 1.2:1(NaBF_4: [BMIM]Br),T=60℃,t=6 min;Optimum synthesis condition of 1-butyl-3-methylimidazolium hexafluorophosphate are:raw material ratio 1.1:1(NH_4PF_6:[BMIM]Br,T=80℃,t=9 min.
(2)Viscosities of both ionic liquids decrease as temperature increases,while conductivities are on the contrary;there is certain hydrophilicity in[BMIM]BF_4,while hydrophilicity is very weak in[BMIM]PF_6;solubilities of ionic liquids have great relationship with types of anions.
(3)The optimum transport conditions of phenol:temperature 300 K,stirring speed 350 r/min,pH in the feed solution phase 3.65,sodium hydroxide concentration in the strip solution phase 0.8 mol/L;The optimum transport conditions of p-nitrophenol:pH in the feed solution phase 3.21,sodium hydroxide concentration in the strip solution phase 0.1 mol/L,ionic strength 0.4;The optimum transport conditions of salicylic acid:pH in the feed solution phase 1.0, sodium hydroxide concentration in the strip solution phase 0.3 mol/L,ionic strength 0.5.
(4)There are retention phenomena in the system of inner-coupled liquid membrane;ionic liquids can be reused after treatment.
引文
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