[bmim][PF6]-DMF-水三元体系的液液相平衡测定

为得到含N,N-二甲基甲酰胺(DMF)废水中萃取回收DMF工艺所需的基础数据,用液液平衡釜常压下测定了1-丁基-3-甲基咪唑六氟磷酸盐([bmim][PF6)离子液体-DMF-H2O三元体系在283.15～323.15 K下的液液分层曲线和液液相平衡数据.在此基础上,考察了三元体系中DMF和[bmim][PF6]离子液体的含量以及温度对[bmim][PF6]的选择性系数的影响.实验结果表明,液液平衡相图中两相区面积随温度升高而减小;相同温度下,[bmim][PF6]的选择性系数随着三元体系中DMF的含量增加而减小,随着离子液体用量增加而增大;溶液组成一定时,[bmim][PF6]的选择性系数随着温度升高而减小;当DMF的含量大于10％时,温度对选择性系数影响不大;283.15 K,三元体系中DMF的质量分数为2.04％时,选择性系数可达33.62,[bmim][PF6]用于萃取分离水中的DMF可行.     

离子液体-水体系的相平衡

通过对1-丁基-3-甲基咪唑四氟硼酸盐([bmim][PF4])离子液体 水体系相平衡及NaCl、NaBF4和氯化1-丁基-3-甲基咪唑([bmim]Cl)对离子液体 水体系相平衡的影响进行了研究,结果表明: 离子液体[bmim][BF4] H2O二元体系具有典型的最高上临界溶解温度(UCST)行为,其最高上临界温度为5.3℃左右,临界组成为50%(水的质量分数); NaCl和NaBF4降低 [bmim][BF4] H2O体系的混溶性,而[bmim]Cl增加该体系的混溶性.由此得到一种简单定性地判断离子液体[bmim][BF4]中可能存在的杂质种类和水平的方法,并利用此结果可设计纯化该离子液体的绿色工艺.     

离子液体[bmim]BF_4与溶剂DMSO相互作用的研究

在298.1~323.15 K范围内,测定了1-丁基-3-甲基咪唑四氟硼酸盐离子液体([bmim]BF4)与DMSO混合体系的密度和粘度,研究发现:随着DMSO加入量的增加,混合体系的密度和粘度均减小。在此条件下,计算了此离子液体的粘度活化参数,η∞、Ea、性粘度B-系数及过量对数粘度,结果表明:Ea与DMSO的摩尔分数成线性关系,线性方程为:Ea=-0.836xDMSO+2.587(r=0.98),粘度B-系数随温度的升高而减小,[bmim]BF4-DMSO混合体系的过量对数粘度在全组成范围内均为正值。     

TiCl_4在离子液体[emim]BF_4及[bmim]PF_6中的电化学性能

在[emim]BF4离子液体中Pt片电极上通过恒电位电沉积制备出金属Ti。采用液/液连续萃取方法对亲水性离子液体[emim]BF4进行提纯,高纯水多次洗涤方法对疏水性离子液体[bmim]PF6进行提纯。在[emim]BF4和[bmim]PF6两种离子液体中研究了Ti Cl4的循环伏安,在含有Ti Cl4的[emim]BF4离子液体中,研究了Pt片电极上的恒电位电沉积。结果表明,连续萃取方法提纯[emim]BF4及高纯水多次洗涤[bmim]PF6,可使两种离子液体纯度分别达到实验要求;在离子液体[emim]BF4中,在Pt片电极上,在-1.8 V(vs Pt)下电解2 h,沉积物中的Ti含量达82.8%。     

TiCl_4在离子液体[emim]BF_4及[bmim]PF_6中的电化学性能

在[emim]BF4离子液体中Pt片电极上通过恒电位电沉积制备出金属Ti。采用液/液连续萃取方法对亲水性离子液体[emim]BF4进行提纯,高纯水多次洗涤方法对疏水性离子液体[bmim]PF6进行提纯。在[emim]BF4和[bmim]PF6两种离子液体中研究了Ti Cl4的循环伏安,在含有Ti Cl4的[emim]BF4离子液体中,研究了Pt片电极上的恒电位电沉积。结果表明,连续萃取方法提纯[emim]BF4及高纯水多次洗涤[bmim]PF6,可使两种离子液体纯度分别达到实验要求;在离子液体[emim]BF4中,在Pt片电极上,在-1.8 V(vs Pt)下电解2 h,沉积物中的Ti含量达82.8%。     

阴离子表面活性剂SDS与离子液体[bmim][PF6]的相互作用研究

采用IHNMR、荧光发射光谱以及UV光谱研究了阴离子表面活性荆SDS与离子液体[bmim][PF6]的相互作用.结果表明,SDS胶束对[bmim][PF6]固有近紫外吸收和荧光发射具有显著敏化作用.IHNMR分析结果表明,[bmim][PF6]在SDS胶束中的增溶部位为SDS胶束的栅栏层,[bmim][PF6]渗入SDS胶束栅栏层的最大深度为SDS分子的C3亚甲基附近.     

离子液体[bmim][Tf2N]的分子动力学模拟

建立了离子液体1-正丁基3-甲基咪唑双（三氟甲基磺酰基）酰亚胺（[bmim][Tf₂N]）的全原子模型,并分别在五种不同的温度和五种不同的压力下对其进行了分子动力学模拟。将[bmim][Tf₂N]密度的模拟结果与实验结果进行了比较,两者吻合良好,验证了模型准确性。此外,还对[bmim][Tf₂N]内部的相互作用能随温度和压力的变化规律进行了分析,结果表明：离子液体内部的库仑能、范德华能、长程作用能均随温度的升高而增加,系统达到平衡所需时间随之变短;相对温度而言,压力对离子液体内部相互作用能的影响较小;在各种相互作用能中,范德华能随温度和压力的变化最大;温度和压力对离子液体的构型不会产生影响。     

功能离子液体[NH_2ebim][PF_6]的合成及其吸收CO_2的研究

采用两步法合成了离子液体1-胺乙基丁基咪唑六氟磷酸盐([NH2ebim][PF6]),进行吸收CO2的研究。结果表明,CO2与离子液体[NH2ebim][PF6]的反应摩尔比介于0.5~1.0,模拟[NH2ebim][PF6]的溶解度参数为18.09 MPa0.5,比常规离子液体的溶解度参数更接近CO2的溶解度参数,说明[NH2ebim][PF6]与CO2有更好的互溶性,利于对CO2的吸收。     

离子液体[bmim]BF4与溶剂DMS0相互作用的研究

在298.1～323.15 K范围内,测定了1-丁基-3-甲基咪唑四氟硼酸盐离子液体([bmim]BF4)与DMSO混合体系的密度和粘度,研究发现:随着DMSO加入量的增加,混合体系的密度和粘度均减小.在此条件下,计算了此离子液体的粘度活化参数,η∞、Ea、性粘度B-系数及过量对数粘度,结果表明:Ea与DMSO的摩尔分...     

[bmim][BF4]离子液体中PCl3催化的液相贝克曼重排

在1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF4])与甲苯组成的两相体系中,以三氯化磷(PCl3)为催化剂,实现了由环己酮肟制备己内酰胺的液相贝克曼重排反应,两相体系有利于反应控制和体系取热. 研究了环己酮肟用量、PCl3用量、反应时间和反应温度对重排效果的影响. 优化反应条件为: 2 ml [bmim][BF4], 5 ml甲苯, 0.3 ml PCl3, 5 ml 2 mol/L环己酮肟-甲苯溶液, 90oC, 反应时间10~30 min. 此时,环己酮肟转化率达98.96%,生成己内酰胺的选择性达87.30%,PCl3催化转化数达2.88. 生成的大部分己内酰胺在离子液体相.     

Purification of flue gas by ionic liquids: Carbon monoxide capture in [bmim][Tf2N]

Knowledge of the solubility of carbon monoxide in ionic liquids is important for investigating the potential use of ionic liquids in reactions and gas separations. There is very limited information available on the capacity of ionic liquids to capture CO. The solubility of CO in 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide was investigated experimentally up to temperatures and pressures of 460 K and 10 MPa, respectively. The solubility was shown to be only slightly temperature‐dependent, and the P–T diagram for a constant composition mixture is concave‐downward with a peak in pressure. By comparing the single‐gas solubility results of CO with various other gases in the same ionic liquid, it seems that ionic liquids can potentially be used as gas‐separating media. However, although the single‐gas solubilities vary considerably among some gases, further studies on mixed (multicomponent) gases should be carried out as the presence of other components can influence the solubility of each gas component. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3886–3891, 2013     

High-pressure solubility of carbon dioxide in imidazolium-based ionic liquids with anions [PF6] and [BF4]

The solubility of carbon dioxide in three ionic liquids (ILs) under supercritical fluid condition was measured at pressures up to 32 MPa and at temperatures of 313.15, 323.15, and 333.15 K in a high-pressure view cell. The imidazolium-derivative ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), and 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][BF₄]) were employed in this research. The effects of pressure, temperature, nature of anion and cation as well as the water content on the solubility of CO₂ in the ILs were investigated experimentally. The solubility of CO₂ in the IL was higher for the ILs with longer cationic alkyl group and for the ILs with lower anion polarity. The lower the water content or the lower the temperature as well as the higher the pressure, the higher was the solubility of CO₂.     

胶原在两种离子液体[BMIM]Cl和[BMIM]Ac中的溶解及再生结构比较

采用离子交换法, 以1-丁基-3-甲基氯代咪唑([BMIM]Cl)为原料合成了咪唑醋酸盐型离子液体([BMIM]Ac), 以两者为溶剂研究了胶原纤维在咪唑类离子液体中的溶解行为及再生前后的结构与热稳定性变化。结果表明, 胶原纤维在CH₃COO^-和Cl^-型离子液体中均能溶解, 但具有明显不同的溶解特性。相对[BMIM]Cl的溶解性能而言, [BMIM]Ac能够在较低的温度下获得高浓度和良好流动性的胶原溶液, 而且再生胶原的三股螺旋结构保留度更高。FTIR、UV、XRD、CD、TG分析结果表明, 胶原在咪唑离子液体中溶解前后其化学结构未发生明显变化, 而三股螺旋的保留度和热稳定性略有降低。     

Microwave accelerated preparation of [bmim][HSO4] ionic liquid: an acid catalyst for improved synthesis of coumarins

A efficient and easy method for preparation of (1-butyl-3-methyl-imidazolium hydrogen sulphate) ionic liquid using sodium bisulphate in place of concentrated sulphuric acid by microwave irradiation had been developed by us with manifold reduction in time. Further, this acidic room temperature ionic liquid has been exploited for the synthesis of coumarins under microwave irradiation and solventless conditions in short duration of time with quantitative yields, for the first time.     

负载[APMIm][Br]离子液体吸收CO2的性能

1-氨丙基-3-甲基咪唑溴盐（[APMIm][Br]）离子液体通过化学反应捕集CO₂。采用浸渍-蒸发将[APMIm][Br]离子液体负载在硅胶表面,通过比表面孔隙吸附测定仪、热重分析仪（TGA）对吸收剂的结构与性能进行研究,负载量为10%～50%,温度为303.15～323.15 K,CO₂浓度分别为10%、30%、50%。结果表明：硅胶表面的离子液体薄膜厚度达到86 nm（负载40%）时,具有最快的吸收速率,且受CO₂浓度和温度变化的影响较小,平衡吸收量在50% CO₂体系中达到理论吸收量的80%,随着温度的升高而降低,当负载量为50%时,膜厚增加到230 nm,导致吸收速率和平衡吸收量大幅度下降。值得注意的是：负载离子液体吸收剂在循环使用3次之后,结构与性能均保持不变,表现出一定的工业运用前景。     

A new approach for correlating of H2S solubility in [emim][Lac], [bmim][ac] and [emim][pro] ionic liquids using two-parts combined models

Two bi-part combined models containing reaction equilibrium thermodynamic model and an equation of state (EoS) including cubic plus association (CPA) or modified Soave-Redlich-Kwong (SRK), were employed to correlate H₂S solubility in ionic liquids [emim][Lac], [bmim][Ac] and [emim][Pro]. RETM and CPA/mSRK are responsible for chemical and phase equilibria calculations, respectively. The RETM defines a complex formation reaction between an H₂S and two IL molecules into the liquid phase so that a complex in the form of H₂S(IL)₂ is probable to produce. On the other side, CPA/mSRK EoSs perform phase equilibria computations to find pressure and vapor phase concentrations. In the case of CPA, both of H₂S and the ionic liquids were considered as self-associating components which pursue 4C and 2B schemes, respectively. This model computes the pure IL parameters using experimental density data. In this work, critical properties were estimated through the modified Lydersen-Joback-Reid method, Eotvos and Guggenheim relations. Afterward, the binary systems were investigated by applying RETM. CPA presents average absolute deviations (AADs) equal to 2.41%, 13.42% and 3.52% for [emim][Lac], [bmim][Ac], and [emim][Pro], respectively. Moreover, the AADs obtained by mSRK are 3.75%, 5.07%, and 6.06%, respectively. As it is evident from the results, the combination of RETM with both CPA and mSRK EoSs will result in good correlation accuracy.     

The thermal gravimetric studies for polymer samples of polyvinyl chloride (PVC) and polyvinyl alcohol (PVA) obtained by treatment with ionic liquid [bmim]Br

The development related to the effective degradation or recycling of polymeric material are of high priority in research because of solid waste removal problems in the environment and to establish sustainable conditions. Ionic liquids having low vapour pressure and other useful properties are finding increasing applications in the field of polymer science. In the present report, we describe the studies related to the plasticizing effect of simple 1-butyl-3-methyl-imidazolium bromide (an ionic liquid) on polyvinyl chloride. The admixtures of PVC and IL were subjected to heating (353–453 K) as a function of time (1–7 h). The resulting product stability was studied by TGA. Similar studies were carried out with PVA via glycolysis, i.e. in presence of ethylene glycol and products obtained were studied by TGA. Our results indicate that the addition of ionic liquid stabilizes the polyvinyl chloride and prevents liberation of HCl, while the polyvinyl alcohol gets degraded rapidly. These findings support the hypothesis of solubilization and degradation depending upon structural characteristics of polymeric molecules. The implications of these findings are discussed in terms of electrostatic, ion dipole and H-bonding interactions within polymer molecules influenced by thermal energy effects.     

A more efficient synthetic process of N-arylphthalimides in ionic liquid [bmim][BF4]

Two room temperature ionic liquids were used to catalyze N-alkylation of phthalic anhydride and aromatic amines without requiring any other organic solvent and catalyst. The comparative study shows that [bmim][BF₄] is more suitable to synthesize N-arylphthalimides due to its easy handling. IR, UV, and ¹H NMR spectroscopy for partial products were made.     

[Bmim][PF6]高效吸收二氯甲烷及流程模拟

采用智能重量吸附仪测量了不同温度、压力下二氯甲烷(CH2Cl2)在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF6])中的溶解度,用NRTL方程建立了离子液体?二氯甲烷体系的气液平衡模型,拟合得到二元交互作用参数,计算所得的二氯甲烷溶解度与实验数据吻合良好,平均相对误差为3.16%. 构建了离子液体处理含二氯甲烷尾气及资源回收利用的常压吸收?减压闪蒸解吸工艺和模型,模型适用范围为温度278.15~308.15 K,压力0~0.1 MPa. 对吸收塔进行了模拟和灵敏度分析,获得了常温常压吸收条件下的最佳操作工艺参数.