多活性位点季鏻盐型功能化离子液体的二氧化碳捕集行为

采用两步法合成了三种季鏻盐型功能化离子液体[a P4443][AA]([AA]=[Triz]、[2-Op]、[2-Np]),考察了温度、CO_2浓度和烟气组分(水分、氧气)对离子液体吸收CO_2性能的影响。结果表明,在30℃、常压条件下,三种离子液体都具有较高的CO_2捕集能力,[a P4443][Triz]、[a P4443][2-Op]和[a P4443][2-Np]对纯CO_2的吸收量分别为1. 32,1. 57,1. 88 mol CO_2/mol ILs。温度升高和CO_2浓度降低均不利于CO_2吸收;烟气其他组分影响离子液体对CO_2的吸收性能,9%H2O/CO_2,5%O2/CO_2和9%H2O/5%O2/CO_2时,CO_2的饱和吸收量比纯CO_2分别降低了10. 2%,2. 5%和16. 7%。     

[aP4443][Gly]-H2O两元体系物性测定及CO2吸收性能

采用两步法合成了双氨基功能化季鏻类离子液体3-丙胺基-三丁基鏻甘氨酸盐([aP4443][Gly])、3-丙氨基-三丁基鏻丙氨酸盐([aP4443][Ala])和3-丙氨基-三丁基鏻缬氨酸盐([aP4443][Val]),研究了[aP4443][Gly]与水构成的两元体系的粘度和电导率的变化. 结果表明,在298.15~343.15 K温度范围内,随阴离子烷基链增长离子液体粘度增大、电导率减小;随温度升高、含水量增加,[aP4443][Gly]-H2O两元体系的粘度减小、电导率增大. CO2吸收实验表明,添加水后离子液体[aP4443][Gly]对CO2的吸收速率均提高;当水摩尔分数小于0.50时,饱和吸收量增大;当水摩尔分数从0.50增大到0.75时,饱和吸收量减小,说明添加适量水可大幅改善[aP4443][Gly]吸收CO2的行为.     

功能化离子液体的合成及对CO2的吸收

以1-氨丙基-3-甲基咪唑溴盐和甘氨酸为原料,采用两步法合成了一种新型功能性离子液体1-氨丙基-3-甲基咪唑甘氨酸盐([APMim][Gly]),考察对CO_2的吸收性能。采用傅里叶变换红外光谱(FTIR)、热重分析(TG)等进行表征,分析其结构及热稳定性。与N-甲基二乙醇胺(MDEA)溶液对比,研究了压力为1 MPa,不同质量分数的[APMim][Gly]在不同温度下对CO_2的吸收能力,并进行多次循环再生,探讨该离子液体[IL]的循环稳定性。结果表明:在30℃时,质量分数为20%的[APMim][Gly]溶液具有最佳的吸收能力,对CO_2的吸收量可达1.32 mol/mol,远高于MDEA溶液。该离子液体具有良好的再生能力,经过6次循环其吸收率仍高达92.4%。     

分子筛SBA-15负载离子液体[P_(66614)][Triz]脱除氢烷气中CO_2

以高效吸收CO_2的离子液体(IL)[P_(66614)][Triz]作为吸收剂,通过浸渍法负载到两种不同孔径的介孔分子筛SBA-15上,用于脱除生物氢烷气中CO_2,并利用N2吸附仪、扫描电子显微镜(SEM)和高倍透射电子显微镜(HRTEM)对负载材料进行了表征分析。混合吸收剂SBA-15(4.3 nm)-50%[Triz]的吸收容量和吸收速率比SBA-15(6.6 nm)-50%[Triz]的分别提高了12.4%和95.1%,这是由于SBA-15(4.3 nm)的孔道长度更短,避免了填充在孔道内的[P_(66614)][Triz]在反应过程中接触不到CO_2,从而比SBA-15(6.6 nm)-50%[Triz]有更多IL反应活性点参与反应。还研究了不同氢烷气速率下SBA-15(4.3 nm)-50%[Triz]对CO_2的吸收并与2种吸附动力学模型相拟合,结果表明SBA-15(4.3nm)-50%[Triz]对CO_2的吸收更符合准二级吸附动力学模型,表明吸附过程受化学吸附机理的控制,验证了[P_(66614)][Triz]是通过化学反应脱除CO_2。     

胆碱脯氨酸/RTILs支撑液膜的CO_2/N_2分离性能

选用不同种类的室温型离子液体(RTILs)与胆碱脯氨酸离子液体进行混合分别制得[Choline][Pro]/[EMIm][N(CN)_2]、[Choline][Pro]/[bmim][PF_6]以及[Choline][Pro]/[HMIm][NTf_2]混合离子液体,并将其应用于离子液体支撑液膜(SILMs)。考察操作温度、操作压差、RTILs种类和含量对SILMs分离CO_2/N_2性能的影响。结果表明胆碱脯氨酸/RTILs系列SILMs的CO_2通量在343.3~1936.9 barrer之间变化并且CO_2/N_2选择性为10.3~34.8。对CO_2膜过程内在机制探索表明随着[HMIm][NTf2]离子液体在混合离子液体中比例的增加,总阻力1/Kμ会呈现先降低后升高的趋势。与实验现象中随着[HMIm][NTf2]离子液体在混合离子液体中比例的增加CO_2先升高后降低相符。     

分子筛SBA-15负载离子液体[P66614][Triz]脱除氢烷气中CO2

以高效吸收CO₂的离子液体（IL）[P₆₆₆₁₄][Triz]作为吸收剂,通过浸渍法负载到两种不同孔径的介孔分子筛SBA-15上,用于脱除生物氢烷气中CO₂,并利用N₂吸附仪、扫描电子显微镜（SEM）和高倍透射电子显微镜（HRTEM）对负载材料进行了表征分析。混合吸收剂SBA-15（4.3 nm）-50%[Triz]的吸收容量和吸收速率比SBA-15（6.6 nm）-50%[Triz]的分别提高了12.4%和95.1%,这是由于SBA-15（4.3 nm）的孔道长度更短,避免了填充在孔道内的[P₆₆₆₁₄][Triz]在反应过程中接触不到CO₂,从而比SBA-15（6.6 nm）-50%[Triz]有更多IL反应活性点参与反应。还研究了不同氢烷气速率下SBA-15（4.3 nm）-50%[Triz]对CO₂的吸收并与2种吸附动力学模型相拟合,结果表明SBA-15（4.3 nm）-50%[Triz]对CO₂的吸收更符合准二级吸附动力学模型,表明吸附过程受化学吸附机理的控制,验证了[P₆₆₆₁₄][Triz]是通过化学反应脱除CO₂。     

含醚阴离子功能化离子液体高效捕集SO2

发展高效、经济、绿色的SO₂吸收剂不但具有较强的学术价值，而且有良好的应用前景。设计并制备了一系列含醚的阴离子功能化离子液体，系统地研究了阴离子上引入醚基团对离子液体SO₂吸收容量的影响。结果表明，在阴离子的苯环上引入甲氧基，对离子液体的吸收容量有明显提升。当阳离子为摩尔质量更小的三丁基乙基磷[P₄₄₄₂]时，所得离子液体的吸收容量没有明显下降，20℃、10⁵ Pa SO₂下，[P₄₄₄₂][2-CH₃OPhCOO]有效吸收量为每摩尔离子液体吸收3.32 mol SO₂，有效质量吸收量是每克离子液体吸收0.56 g SO₂。六次吸收解吸循环，表明[P₄₄₄₂][2-CH₃OPhCOO]可以高效可逆地捕集SO₂。基于含醚阴离子功能化离子液体的加强效应进行气体捕集的方法，可进一步应用于分离、催化等领域。     

EOS+γ法预测CO_2-[emim] [Tf_2N]超额吉布斯自由能及超额焓

为改善CO_2-离子液体(ILs)制冷吸收体系热力学性质参数报道数据较少的缺陷,选择使用Soave(SRK)方程,Wong-Sandler(WS)混合法则和通用化学活度系数(UNIQUAC)模型对新型制冷吸收工质对CO_2结合1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐(CO_2-[emim][Tf_2N])体系的相平衡数据进行关联,可得CO_2-[emim][Tf_2N]制冷吸收剂体系的超额吉布斯自由能(G~E)、超额焓(H~E)等热力学性质。结果表明:CO_2-[emim][Tf_2N]制冷吸收剂体系的G~E和H~E均受温度、压力和CO_2液相摩尔分数的影响,G~E的变化范围为-878.774—-260.195 J/mol,H~E的变化范围为-296.532—-26.494 5 J/mol,由G~E,H~E均为负值可知混合过程放热,符合热力学变化规律,由此可知CO_2-[emim][Tf_2N]制冷吸收剂体系具有成为吸收制冷循环新工质的基本特征,为CO_2-[emim][Tf_2N]用于吸收式制冷体系提供了依据。     

CO_2-[emim][Tf_2N]的汽液相平衡实验研究

针对氨系、水系等传统吸收式制冷工质对存在腐蚀性强、制冷量小的缺点,自行设计搭建用于测量CO_2-[emim][Tf_2N]汽液相平衡的实验台,在温度范围263. 15～358. 15 K、压力范围0. 17～2. 45 MPa条件下,测定了CO_2在离子液体[emim][Tf_2N]中的相平衡数据。结果表明,CO_2在离子液体[emim][Tf_2N]中的溶解度可达到0. 535,为CO_2-[emim][Tf_2N]在吸收式制冷系统中的应用奠定了基础数据。     

CO_2-[emim][Tf_2N]的汽液相平衡实验研究

针对氨系、水系等传统吸收式制冷工质对存在腐蚀性强、制冷量小的缺点,自行设计搭建用于测量CO_2-[emim][Tf_2N]汽液相平衡的实验台,在温度范围263. 15～358. 15 K、压力范围0. 17～2. 45 MPa条件下,测定了CO_2在离子液体[emim][Tf_2N]中的相平衡数据。结果表明,CO_2在离子液体[emim][Tf_2N]中的溶解度可达到0. 535,为CO_2-[emim][Tf_2N]在吸收式制冷系统中的应用奠定了基础数据。     

Sugar-derived ionic liquids

Ionic liquids (ILs) are special molten salts with melting points below 100 degrees C that are typically constituted of organic cations (imidazolium, pyridinium, sulfonium, phosphonium, etc.) and inorganic anions. Due to their ionic nature, they are endowed with high chemical and thermal stability, good solvent properties, and non-measurable vapor pressure. Although the recycling of ILs partly compensate their rather high cost, it is important to develop new synthetic approaches to less expensive and environmentally sustainable ILs based on renewable raw materials. In fact, most of these alternative solvents are still prepared starting from fossil feedstocks. Until now, only a limited number of ionic liquids have been prepared from renewable sources (e.g., hydroxy acids, amino acids, terpenes), and even less from naturally occurring carbohydrates. This short review describes the synthesis and applications of chiral and achiral ILs obtained from inexpensive sugars.     

Amino acid ionic liquids

The preparation of ionic liquids derived from amino acids, and their properties, are outlined. Since amino acids have both a carboxylic acid residue and an amino group in a single molecule, they can be used as either anions or cations. These groups are also useful in their ability to introduce functional group(s). Twenty different natural amino acids were used as anions, to couple with the 1-ethyl-3-methylimidazolium cation. The salts obtained were all liquid at room temperature. The properties of the resulting ionic liquids (AAILs) depend on the side groups of the amino acids involved. These AAILs, composed of an amino acid with some functional groups such as a hydrogen bonding group, a charged group, or an aromatic ring, had an increased glass transition (or melting) temperature and/or higher viscosity as a result of additional interactions among the ions. Viscosity is reduced and the decomposition temperature of imidazolium-type salts is improved by using the tetrabutylphosphonium cation. The chirality of AAILs was maintained even upon heating to 150 degrees C after acetylation of the free amino group. The amino group was also modified to introduce a strong acid group so as to form hydrophobic and chiral ionic liquids. Unique phase behavior of the resulting hydrophobic ionic liquids and water mixture is found; the mixture is clearly phase separated at room temperature, but the solubility of water in this IL increases upon cooling, to give a homogeneous solution. This phase change is reversible, and separation occurs again by raising the temperature a few degrees. It is extraordinary for an IL/water mixture to display such behavior with a lower critical solution temperature. Some likely applications are proposed for these amino acid derived ionic liquids.     

室温离子液体室

介绍了主要由烷基咪唑盐阳离子及氟阴离子组成的室温离子液体的制备、物理性质、化学性质及其在常温条件下的应用.     

Air-drying with ionic liquids

Ionic liquids (ILs) are employed for air-drying for the first time. The experimental gas–liquid equilibrium (EQ) of N₂/O₂ + [EMIM][BF₄] and N₂/O₂ + [EMIM][BF₄] + H₂O systems under a broad temperature range are measured. The new modified UNIFAC-Lei model is successfully extended to predict the N₂/O₂-IL-H₂O system based on extensive phase EQ data. The air-drying experiment using [EMIM][BF₄] as an absorbent is conducted, confirming that this new technology is effective and efficient. © 2018 American Institute of Chemical Engineers AIChE J, 65: 479–482, 2019     

Electronic conductivity in ionic liquids

The mobility of electrons in the salt-rich regions of Na-NaCl and K-KCl melts has been semi-empirically calculated in terms of electron hopping coupled with a tunneling mechanism. The magnitude, as also the temperature and concentration dependence of the calculated mobility, are consistent with existing literature data.     

“绿色”溶剂离子液的研究进展

近年来，离子液由于其独特的优点, 在生物催化及化学合成领域越来越受到青睐。由于缺乏蒸气压，离子液作为绿色溶剂有很大潜能。此外，离子液不像极性有机溶剂那样会使酶失活，因而简化了类似含有糖类这样极性底物的反应。在离子液中，生物催化反应表现出较高的选择性、较快的反应速率和较高的酶稳定性。但这些溶剂还存在着离子液的纯化、控制水活性和pH、高粘度以及产品分离等问题。     

Gas drying with ionic liquids

The gas drying technology with ionic liquids (ILs) was systematically studied ranging from the molecular level to industrial scale. The COSMO‐RS model was first used to screen the suitable IL and provide theoretical insights at the molecular level. Toward CO₂ gas dehydration, we measured the CO₂ solubility in single [EMIM][Tf₂N] and in the [EMIM][Tf₂N] + H₂O mixture, as well as the vapor‐liquid equilibrium (VLE) of [EMIM][Tf₂N] + H₂O system, to justify the applicability of UNIFAC model. Based on the thermodynamic study, the rigorous equilibrium (EQ) stage mathematical model was established for process simulation. The gas drying experiment with IL was also performed and the water content in gas product can be reduced to 375 ppm. It was confirmed that a less flow rate of absorbent, a higher CO₂ recovery ratio and a much lower energy consumption can be achieved with IL than with the conventional triethylene glycol (TEG). © 2017 American Institute of Chemical Engineers AIChE J, 64: 606–619, 2018     

离子液体的应用进展

离子液体由于具有独特的物理化学性质而成为一种新型的绿色介质,近年来成为国际上研究的前沿和热点。它为开发新型绿色工艺,实现将传统重污染、高能耗工业过程的升级换代提供了新机遇。对离子液体应用的研究进展进行了综述,详细介绍了离子液体在催化科学、电化学、材料科学、环境科学和分离技术等领域的应用,并对其发展方向进行了展望。