[Bmim][PF_6]-丁酮肟-水-硫酸铵体系液液平衡的研究
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摘要
酮胺法生产丁酮肟过程中会副产含有丁酮肟的硫酸铵水溶液,需采用合适的溶剂来萃取回收其中的丁酮肟。作为可替代传统有机溶剂的"绿色溶剂",离子液体在萃取分离领域显现出良好的应用前景。测定了疏水性离子液体[Bmim][PF_6]-水-硫酸铵、[Bmim][PF6]-丁酮肟-水和[Bmim][PF_6]-丁酮肟-水-硫酸铵体系在303.15 K时的液液平衡数据,使用Bachman方程验证了实验数据的可靠性,同时计算了丁酮肟的分配系数(D)。在此基础上,考察了萃取时间、硫酸铵浓度和丁酮肟浓度对硫酸铵水溶液中丁酮肟的萃取效果的影响。实验结果表明,萃取较快达到平衡且效果较好。硫酸铵能提高萃取效果,且硫酸铵浓度越大,萃取效果越好。最后使用Rajendran改进的Eisen-Joffe方程对所得[Bmim][PF_6]-丁酮肟-水-硫酸铵体系的液液平衡数据进行了关联计算,结果表明计算值与实验值符合较好。研究结果能为工业上利用离子液体[Bmim][PF_6]萃取硫酸铵水溶液中的低浓度丁酮肟提供一定的参考。
Ammonium sulfate aqueous solutions containing butanone oxime are usually produced as a by-product in butanone oxime synthesis, and it is necessary to find appropriate solvents to extract and recycle butanone oxime from the solution. ILs as "green solvents" are considered as the most promising alternatives to conventional organic solvents, which show good prospect in separation applications. Liquid-liquid equilibrium(LLE) data of hydrophobic ionic liquid [Bmim][PF_6]-water-ammonium sulfate, [Bmim][PF_6]-butanone oxime-water and [Bmim][PF_6]-butanone oxime-water-ammonium sulfate systems were determined at 303.15 K, and the Bachman equation was used to examine the consistency of the experimental data, and the distribution coefficient(D) of butanone oxime was calculated. Moreover, the influence of extraction time and the concentrations of ammonium sulfate and butanone oxime in the initial aqueous solutions on extraction were investigated. Experimental results show that extraction equilibrium is reached quickly with good extraction efficiency. Higher concentration of ammonium sulfate would result in better extraction efficiency. Moreover, the experimental LLE data of [Bmim][PF_6]-butanone oxime-water-ammonium sulfate are correlated with a Rajendran adjusted Eisen-Joffe equation, and the calculated values are in good agreement with the experimental values. These results help the industrial application of [Bmim][PF_6] on extracting low concentration butanone oxime from ammonium sulfate aqueous solutions.
Ammonium sulfate aqueous solutions containing butanone oxime are usually produced as a by-product in butanone oxime synthesis, and it is necessary to find appropriate solvents to extract and recycle butanone oxime from the solution. ILs as "green solvents" are considered as the most promising alternatives to conventional organic solvents, which show good prospect in separation applications. Liquid-liquid equilibrium(LLE) data of hydrophobic ionic liquid [Bmim][PF_6]-water-ammonium sulfate, [Bmim][PF_6]-butanone oxime-water and [Bmim][PF_6]-butanone oxime-water-ammonium sulfate systems were determined at 303.15 K, and the Bachman equation was used to examine the consistency of the experimental data, and the distribution coefficient(D) of butanone oxime was calculated. Moreover, the influence of extraction time and the concentrations of ammonium sulfate and butanone oxime in the initial aqueous solutions on extraction were investigated. Experimental results show that extraction equilibrium is reached quickly with good extraction efficiency. Higher concentration of ammonium sulfate would result in better extraction efficiency. Moreover, the experimental LLE data of [Bmim][PF_6]-butanone oxime-water-ammonium sulfate are correlated with a Rajendran adjusted Eisen-Joffe equation, and the calculated values are in good agreement with the experimental values. These results help the industrial application of [Bmim][PF_6] on extracting low concentration butanone oxime from ammonium sulfate aqueous solutions.
引文
[1]LI Meng(李猛),LIU Jun-dong(刘俊东),NA Hong-zhuang(那宏壮).Application and advancement in synthesis of 2-butanone oxime(丁酮肟的应用与合成进展)[J].Chemical Engineer(化学工程师),2006,20(7):42-43.
[2]LIU Ming(刘明),HE Chao-hong(何潮洪),HUANG Zhi-yao(黄志尧),et al.Measurement of thermal conductivity for systems of methyl ethyl ketoxime with methyl ethyl ketone and n-hexane separately(丁酮肟-丁酮、丁酮肟-正己烷体系导热系数的测定)[J].J Chem Eng of Chinese Unive(高校化学工程学报),2011,25(4):547-553.
[3]ZHENG Bo-yu(郑博予),FANG Sheng(房升),HE Chao-hong(何潮洪).Measurement and correlation of densities and viscosities for binary mixtures of methyl ethyl ketoxime with methyl ethyl ketone,cylclohexane,and n-hexane(丁酮肟-丁酮、正己烷、环己烷二元体系密度和黏度的测定及关联)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2010,24(6):911-916.
[4]ZHAO Jun-ming(赵俊明).Simulation and optimization of the reactive extraction process for MEKO production with HPO process(磷酸羟胺法制丁酮肟反应萃取过程的模拟与优化)[D].Shanghai(上海):East China University of Science and Technology(华东理工大学),2013.
[5]Huddleston J G,Willauer H D,Swatloski R P,et al.Room temperature ionic liquids as novel media for‘clean’liquid-liquid extraction[J].Chemical Communications,1998(16):1765-1766.
[6]Seddon K R.Ionic liquids for clean technology[J].Journal of Chemical Technology and Biotechnology,1997,68(4):351-356.
[7]Liu J F,Chi Y G,Jiang G B.Screening the extractability of some typical environmental pollutants by ionic liquids in liquid-phase micro-extraction[J].Journal of Separation Science,2005,28(1):87-91.
[8]Pereiro A B,Araújo J M M,Oliveira F S S,et al.Solubility of inorganic salts in pure ionic liquids[J].The Journal of Chemical Thermodynamics,2012,55(12):29-36.
[9]WU Su-fang(吴素芳),LIU Jian-qing(刘建青),XU You-tian(徐有田),et al.Determination of cyclohexanone oxime in esters by spectrophotometry(分光光度法测定转位酯中环己酮肟)[J].Chinese Journal of Analytical Chemistry(分析化学),2002,30(7):891.
[10]Bachman I.Tie lines in ternary liquid systems[J].Industrial and Engineering Chemistry,Analytical Edition,1940,12(1):38-39.
[11]Xu D M,Wu C X,Zhang Q,et al.Liquid–liquid equilibrium for the ternary systems water+2-methyl-1-propanol+butyl acetate and water+2-methyl-2-propanol+butyl acetate at(298.15 and 323.15)K[J].Fluid Phase Equilibria,2014,381(11):60-66.
[12]Chen Y,Wang Z,Li L B.Liquid–liquid equilibria for ternary systems:methyl butyl ketone+phenol+water and methyl butyl ketone+hydroquinone+water at 298.15 K and 323.15 K[J].J Chem Eng Data,2014,59(9):2750-2755.
[13]ZHUANG Liu-xing(庄六星),BAI Lu(白璐).Measurement of liquid-liquid equilibrium data for the ternary system of water+acetic acid+diisopropyl Ether(水-醋酸-二异丙醚三元体系液液相平衡数据的测定)[J].Shanghai Chemical Industry(上海化工),2011,36(6):10-12.
[14]REN Hong-dong(任洪东),CUI Xian-bao(崔现宝),YANG Zhi-cai(杨志才).The oretical prediction of separation adding salt(盐效分离作用理论预测)[J].Chemical Engineering(China)(化学工程),2004,32(2):6-9.
[15]Quzhou Jinhua Chemical Co.Ltd(衢州锦华化工有限公司),Zhejiang University(浙江大学).Acceptance materials on science and technology projects of Zhejiang Province:development and application of reaction-separation intergration technologies(浙江省科技计划项目验收资料:反应-分离集成技术的开发及其推广应用)[Z].2009.
[16]Hand D B.The distribution of consolute liquid between two immiscible liquid[J].Journal of Physical Chemistry,1930,34(9):1961-2000.
[17]Eisen E O,Joffe J.Salt effects in liquid-liquid equilibria[J].Journal of Chemistry and Engineering Data,1966,11(4):480-484.
[18]Rajendran M,Srinivasan D.Measurement and prediction of liquid-liquid equilibria of ethyl acetate-methanol-water in the presence of dissolved inorganic salts[J].Fluid Phase Equilibria,1988,40(1):53-75.
[19]Rajendran M,Renganarayanan S,Srinivasan D.Salt effect in phase equilibria:effect of dissolved inorganic salts on the liquid-liquid equilibria of benzene-2-propanol-water system and the vapor-liquid equilibria of its constituent binaries[J].Fluid Phase Equilibria,1989,50(1-2):133-164.
[2]LIU Ming(刘明),HE Chao-hong(何潮洪),HUANG Zhi-yao(黄志尧),et al.Measurement of thermal conductivity for systems of methyl ethyl ketoxime with methyl ethyl ketone and n-hexane separately(丁酮肟-丁酮、丁酮肟-正己烷体系导热系数的测定)[J].J Chem Eng of Chinese Unive(高校化学工程学报),2011,25(4):547-553.
[3]ZHENG Bo-yu(郑博予),FANG Sheng(房升),HE Chao-hong(何潮洪).Measurement and correlation of densities and viscosities for binary mixtures of methyl ethyl ketoxime with methyl ethyl ketone,cylclohexane,and n-hexane(丁酮肟-丁酮、正己烷、环己烷二元体系密度和黏度的测定及关联)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2010,24(6):911-916.
[4]ZHAO Jun-ming(赵俊明).Simulation and optimization of the reactive extraction process for MEKO production with HPO process(磷酸羟胺法制丁酮肟反应萃取过程的模拟与优化)[D].Shanghai(上海):East China University of Science and Technology(华东理工大学),2013.
[5]Huddleston J G,Willauer H D,Swatloski R P,et al.Room temperature ionic liquids as novel media for‘clean’liquid-liquid extraction[J].Chemical Communications,1998(16):1765-1766.
[6]Seddon K R.Ionic liquids for clean technology[J].Journal of Chemical Technology and Biotechnology,1997,68(4):351-356.
[7]Liu J F,Chi Y G,Jiang G B.Screening the extractability of some typical environmental pollutants by ionic liquids in liquid-phase micro-extraction[J].Journal of Separation Science,2005,28(1):87-91.
[8]Pereiro A B,Araújo J M M,Oliveira F S S,et al.Solubility of inorganic salts in pure ionic liquids[J].The Journal of Chemical Thermodynamics,2012,55(12):29-36.
[9]WU Su-fang(吴素芳),LIU Jian-qing(刘建青),XU You-tian(徐有田),et al.Determination of cyclohexanone oxime in esters by spectrophotometry(分光光度法测定转位酯中环己酮肟)[J].Chinese Journal of Analytical Chemistry(分析化学),2002,30(7):891.
[10]Bachman I.Tie lines in ternary liquid systems[J].Industrial and Engineering Chemistry,Analytical Edition,1940,12(1):38-39.
[11]Xu D M,Wu C X,Zhang Q,et al.Liquid–liquid equilibrium for the ternary systems water+2-methyl-1-propanol+butyl acetate and water+2-methyl-2-propanol+butyl acetate at(298.15 and 323.15)K[J].Fluid Phase Equilibria,2014,381(11):60-66.
[12]Chen Y,Wang Z,Li L B.Liquid–liquid equilibria for ternary systems:methyl butyl ketone+phenol+water and methyl butyl ketone+hydroquinone+water at 298.15 K and 323.15 K[J].J Chem Eng Data,2014,59(9):2750-2755.
[13]ZHUANG Liu-xing(庄六星),BAI Lu(白璐).Measurement of liquid-liquid equilibrium data for the ternary system of water+acetic acid+diisopropyl Ether(水-醋酸-二异丙醚三元体系液液相平衡数据的测定)[J].Shanghai Chemical Industry(上海化工),2011,36(6):10-12.
[14]REN Hong-dong(任洪东),CUI Xian-bao(崔现宝),YANG Zhi-cai(杨志才).The oretical prediction of separation adding salt(盐效分离作用理论预测)[J].Chemical Engineering(China)(化学工程),2004,32(2):6-9.
[15]Quzhou Jinhua Chemical Co.Ltd(衢州锦华化工有限公司),Zhejiang University(浙江大学).Acceptance materials on science and technology projects of Zhejiang Province:development and application of reaction-separation intergration technologies(浙江省科技计划项目验收资料:反应-分离集成技术的开发及其推广应用)[Z].2009.
[16]Hand D B.The distribution of consolute liquid between two immiscible liquid[J].Journal of Physical Chemistry,1930,34(9):1961-2000.
[17]Eisen E O,Joffe J.Salt effects in liquid-liquid equilibria[J].Journal of Chemistry and Engineering Data,1966,11(4):480-484.
[18]Rajendran M,Srinivasan D.Measurement and prediction of liquid-liquid equilibria of ethyl acetate-methanol-water in the presence of dissolved inorganic salts[J].Fluid Phase Equilibria,1988,40(1):53-75.
[19]Rajendran M,Renganarayanan S,Srinivasan D.Salt effect in phase equilibria:effect of dissolved inorganic salts on the liquid-liquid equilibria of benzene-2-propanol-water system and the vapor-liquid equilibria of its constituent binaries[J].Fluid Phase Equilibria,1989,50(1-2):133-164.