ATR-FTIR Measurement of Biomass Components in Phosphonium Ionic Liquids

Abstract

Qualitative and quantitative measurements of biomass components dissolved in the phosphonium ionic liquids (ILs), trihexyltetradecylphosphonium chloride ([P66614]Cl) and tributylmethylphosphonium methylsulphate ([P4441]MeSO₄), are obtained using attenuated total reflectance-FTIR. Absorption bands related to cellulose, hemicelluloses, and lignin dissolution monitored in situ in biomass-IL mixtures indicate lignin dissolution in both ILs and some holocellulose dissolution in the hydrophilic [P4441]MeSO₄. The kinetics of lignin dissolution reported here indicate that while dissolution in the hydrophobic IL [P66614]Cl appears to follow an accepted mechanism of acid catalyzed β-aryl ether cleavage, dissolution in the hydrophilic IL [P4441]MeSO₄ does not appear to follow this mechanism and may not be followed by condensation reactions (initiated by reactive ketones). The measurement of lignin dissolution in phosphonium ILs based on absorbance at 1510 cm^?1 has demonstrated utility. When coupled with the gravimetric Klason lignin method, ATR-FTIR study of reaction mixtures can lead to a better understanding of the delignification process.     

离子液体在生物催化中的应用

近年来,离子液体(ILs)以其独特的优势成为生物催化反应研究的热点,尤其是作为生物催化反应的溶剂或共溶剂的研究更是备受关注.许多酶能在ILs或其形成的两相体系或单相体系中保持催化活性.如目前研究最多的脂肪酶,有多种能在ILs中表现出活性稳定、反应选择性提高、产率提高等优良特性;某些蛋白酶在ILs中稳定性提高,具有酯酶的活性;β-半乳糖苷酶在ILs中的催化产率提高;全细胞在ILs中的催化反应效果也较好;但是也有某些酶,如纤维素酶、某些过氧化物酶等在ILs中活性会降低或丧失.因此有关这一方面的研究还有待进一步深入.     

Applications and Mechanisms of Ionic Liquids in Whole-Cell Biotransformation

Ionic liquids (ILs), entirely composed of cations and anions, are liquid solvents at room temperature. They are interesting due to their low vapor pressure, high polarity and thermostability, and also for the possibility to fine-tune their physicochemical properties through modification of the chemical structures of their cations or anions. In recent years, ILs have been widely used in biotechnological fields involving whole-cell biotransformations of biodiesel or biomass, and organic compound synthesis with cells. Research studies in these fields have increased from the past decades and compared to the typical solvents, ILs are the most promising alternative solvents for cell biotransformations. However, there are increasing limitations and new challenges in whole-cell biotransformations with ILs. There is little understanding of the mechanisms of ILs’ interactions with cells, and much remains to be clarified. Further investigations are required to overcome the drawbacks of their applications and to broaden their application spectrum. This work mainly reviews the applications of ILs in whole-cell biotransformations, and the possible mechanisms of ILs in microbial cell biotransformation are proposed and discussed.     

Ionic liquids as entrainer in extractive distillation for effectively separating 1-propanol–water azeotropic mixture

Economically separating 1-propanol(NPA) from water is an emergent issue for producing pharmaceutical intermediates such as n-propyl acetate, n-propylamine and so on. In this work, fourionic liquids(ILs) 1-ethyl-3-methylimidazolium thiocyanate([EMIM][SCN]), 1-butyl-3-methylimidazolium tetrafluoroborate([BMIM][BF₄]), 1,3-dimethylimidazolium methylsulfate([MMIM][MS]), 1,3-dimethylimidazolium dimethylphosphate([MMIM][DMP]) were introduced as potential entrainers for separating NPA–water a...     

Structural Reorganization of Imidazolium Ionic Liquids Induced by Pressure-Enhanced Ionic Liquid—Polyethylene Oxide Interactions

Mixtures of polyethylene oxide (PEO, M.W.~900,000) and imidazolium ionic liquids (ILs) are studied using high-pressure Fourier-transform infrared spectroscopy. At ambient pressure, the spectral features in the C–H stretching region reveal that PEO can disturb the local structures of the imidazolium rings of [BMIM]⁺ and [HMIM]⁺. The pressure-induced phase transition of pure 1-butyl-3-methylimidazolium bromide ([BMIM]Br) is observed at a pressure of 0.4 GPa. Pressure-enhanced [BMIM]Br-PEO interactions may assist PEO in dividing [BMIM]Br clusters to hinder the aggregation of [BMIM]Br under high pressures. The C–H absorptions of pure 1-hexyl-3-methylimidazolium bromide [HMIM]Br do not show band narrowing under high pressures, as observed for pure [BMIM]Br. The band narrowing of C–H peaks is observed at 1.5 GPa for the [HMIM]Br-PEO mixture containing 80 wt% of [HMIM]Br. The presence of PEO may reorganize [HMIM]Br clusters into a semi-crystalline network under high pressures. The differences in aggregation states for ambient-pressure phase and high-pressure phase may suggest the potential of [HMIM]Br-PEO (M.W.~900,000) for serving as optical or electronic switches.     

壳聚糖季鏻盐共混膜的制备及性能研究

用溶液共混法成功地制备了壳聚糖与季鏻盐共混膜,并利用红外光谱、透光率、力学性能、吸水率及抑菌性能测试对其进行了表征。结果表明,共混膜中壳聚糖分子与季鏻盐分子间存在一定相互作用及良好的相容性,季鏻盐含量的增加减小了共混膜的吸水率,增加了其抑菌性能,在季鏻盐含量为20%时,共混膜的综合性能最佳,其中,抗张强度达到60.8 MPa,透光率为85%。     

Removal of carbon dioxide from flue gases in packed column using ionic liquids

The study of CO₂ absorption in ionic liquids (ILs): [Emim] [Ac], [Bmim] [Ac] in a packed column is presented. The influence of mass transfer resistances, initial CO₂ concentration, absorption temperature and 2, 5, 10% wt. water addition on CO₂ removal efficiency was investigated. The resistance in series model and estimated values of enhancement factor were used to predict with good accuracy mass fluxes of absorbed carbon dioxide for both ILs. The CO₂ absorption efficiency in packed column depends on temperature and initial CO₂ concentration. The addition of small amounts of water to [Emim][Ac] is of minor effect on CO₂ absorption.     

离子液体催化苯与苄氯的烷基化合成二苯甲烷

考察了离子液体催化Friedel-Crafts苄基化制备二苯甲烷,同时考察了AlCl3的摩尔分数、离子液体用量及不同离子液体等因素对苯与苄氯烷基化反应的影响。实验结果表明,离子液体的催化活性与其酸强度密切相关,酸性条件下离子液体才显示催化活性。AlCl3摩尔分数为66.7%,催化剂(离子液体)用量3.3g、反应温度80℃及常压反应条件下,1-丁基-3-甲基氯咪唑,N-丁基氯吡啶与AlCl3形成的离子液体具有较高的二苯甲烷选择性,分别为97.4%和92.1%。离子液体催化剂重复使用4次后,活性基本没有降低。     

Electrochemistry of TiF4 in 1-butyl-2,3-dimethylimidazolium tetrafluoroborate

Electrochemical behaviour of Ti(IV) species in the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMImBF₄) was studied by means of chronopotentiometry (CP) and cyclic voltammetry (CV) in melts with different concentrations of TiF₄ (2-35 mol%) within a temperature range of 65-180 °C. The electrochemical reduction of Ti(IV) was suggested to proceed via the sequence of one-electron steps with the formation of poorly soluble low valence intermediates (LVI). LVIs undergo further solid-state electrochemical reduction to Ti metal. Thin Ti coatings on a Pt substrate were thus obtained and characterized by ESEM method. FTIR spectroscopy was used for identification of the electrochemical active species of Ti(IV). The reaction 2BF₄⁻ + TiF₄ ⇔ TiF₆²⁻ + 2BF₃↑ takes place in the concentrated solutions of TiF₄ at elevated temperatures.     

混合澄清槽内离子液体体系的三相流体动力学模拟

离子液体是近年来被广泛研究的新兴绿色溶剂,其在乏燃料后处理技术中具有潜在的工业应用前景。但由于缺乏对萃取反应器中离子液体流动特性的研究,制约了离子液体萃取体系的实际应用。本文以萃取工艺中广泛应用的混合澄清槽为对象,以去离子水及1-丁基-3-甲基咪唑双(三氟甲磺酰)亚胺盐（[C₄mim][NTf₂]）分别作为水相及有机相,考虑上层空气对流动行为的影响,对其混合室进行计算流体力学（computational fluid dynamics, CFD）模拟,考察不同转速、流比及温度下的有机相分布、压力场、湍动程度等。结果表明,模拟结果较好地符合实验结果,且最大误差小于6.3%;转速能直观地提升混合性能,但当超过500r/min后,继续提高转速将显著增大出口气量,从而可能对澄清室的分相性能提出更高要求;增大流比、升温均能提升350r/min转速下的有机、水相混合能力,升温还有效减小了桨力矩,但当温度超过303K时,继续升温对于桨力矩、有机相速度的改变不明显。因此,实际工艺条件建议结合升温与转速调节,在实现较好混合性能的同时,减少对澄清室分相性能的要求。本文在建立离子液体三相体系数值模拟方法的同时,为混合澄清槽的工况优化提供合理建议,并为离子液体萃取体系的深入研究提供了参考。     

Quaternary ammonium salts ionic liquids for immobilization of chiral Ru-BINAP complexes in asymmetric hydrogenation of β-ketoesters

Chiral catalytic complex (R)—[RuCl(binap)(p-cymene)]Cl was used in asymmetric hydrogenation of methyl acetoacetate to methyl-3-hydroxybutyrate in the mixed methanol-ionic liquid phase. Quaternary ammonium salts ionic liquids, namely n-alkyl-triethylammonium bis(trifluoromethane sulfonyl) imides (N_R222Tf₂N, R = 6, 7, 8, 10, 12, 14), were prepared and employed in this transformation. Enough evidence was provided that only a small amount of this type of IL in a conventional solvent was necessary to accommodate the catalytic complex and that the reaction could be carried out with very high enantioselectivity. Similarly it was proved that under optimized conditions the catalytic complex immobilized in this manner could be used repeatedly. A part of the work was focused on the role of the alkyl chain length in the N_R222Tf₂N ionic liquid which was found as very essential. Role of the reaction impurities with origin in the synthesis of the employed ILs was also investigated.     

Rigorous correlations for predicting the solubility of H2S in methylimidazolium-based ionic liquids

Two general and simple models, a group contribution correlation (model I) and an empirical relation (model II), were proposed to predict the solubility of H₂S in methylimidazolium based ionic liquids (ILs) over wide range of temperatures (303.15-363.15 K) and pressures (60.8-2016.8 kPa). The constants of the suggested functionality relations were found via the Nelder-Mead simplex algorithm. Both correlations were trained with 407 data points of H₂S solubility in 9 methylimidazolium based ILs and tested through 121 H₂S solubility data points of 3 different methylimidazolium based ILs to ensure generality. A comprehensive statistical evaluation showed that both suggested correlations are vigorous and have satisfactory error trends. The dataset was subjected to a statistical outlier diagnostic test and the validity of the database was confirmed. In addition, the sensitivity analysis revealed that the experimental data and both models have the same responses toward pressure and temperature, which indicates the reliability of the proposed correlations.     

Efficient Halogenation of Aromatic Systems Using N‐Halosuccinimides in Ionic Liquids

A simple, rapid and highly regioselective green protocol has been developed for the halogenation of aromatic systems with N‐halosuccinimides using room temperature ionic liquids (ILs) as novel and recyclable reaction media to produce the corresponding halogenated aromatic compounds in high to quantitative yields. N‐Halosuccinimides show enhanced reactivity in ionic liquids thereby reducing the reaction times dramatically and improving the yields substantially.     

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exch...     

Physical and electrochemical properties of room-temperature dicyanamide ionic liquids based on quaternary phosphonium cations

The physicochemical and electrochemical properties of room temperature ionic liquids based on quaternary phosphonium cations together with a dicyanamide anion are presented in this report. The most dicyanamide-based phosphonium ionic liquids prepared were hydrophilic, except ionic liquids containing a long alkyl chain in the phosohonium cation. It was found that asymmetric phosphonium cations gave low-melting salts in combination with a dicyanamide anion. The dicyanamide-based phosphonium ionic liquids exhibited relatively low viscosities and high conductivities when compared to those of the corresponding ammonium ionic liquids. Particularly, the ionic liquids containing a methoxy group in the phosphonium cations indicated very low viscosities. Comparatively good electrochemical stability of the dicyanamide-based phosphonium ionic liquids was confirmed by voltammetric measurements. The thermogravimetric analysis suggested that the dicyanamide-based phosphonium ionic liquids showed higher thermal stability than those of the corresponding ammonium ionic liquids, indicating an improving effect of the phosphonium cations on the thermal stability.     

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