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Abstract: The effect of hydrogen partial pressure on the hydrogenation of limonene in high-pressure carbon dioxide, catalysed by carbon-supported palladium, was studied. Experiments were performed at various hydrogen pressures in the range from 2.5 up to 4.4MPa at a fixed total pressure of 12.5MPa, where the reaction mixture remains biphasic—liquid+gas. In these conditions, the liquid phase volume is expanded in relation to the initial volume of limonene in a fashion that is strongly dependent on the hydrogen to carbon dioxide pressure ratios. Surprisingly, the main factor in the kinetics of hydrogenation turns out to be the concentration (moldm−3) of limonene, which decreases due to the volumetric expansion of the liquid phase when the CO2 pressure increases. [Copyright &y& Elsevier]

Abstract: Vapour–liquid equilibrium measurements for binary and ternary (carbon dioxide+β-myrcene and carbon dioxide+β-myrcene+hydrogen) systems have been carried out at 323.15K and pressures in the range from 7MPa to the critical pressure of the binary mixture and at pressures from 10 to 14MPa for the investigated ternary systems. Samples from the coexisting phases were taken, and compositions were determined experimentally. Results were correlated using the Peng–Robinson and the Soave–Redlich–Kwong equations of state with the Mathias–Klotz–Prausnitz mixing rule. The set of interaction parameters for the employed equations of state and applied mixing rule for the system of CO2 +β-myrcene and of CO2 +β-myrcene+H2 were obtained. Additionally, the volume expansion of the liquid phase for the binary mixtures (carbon dioxide+β-myrcene and carbon dioxide+limonene) were measured at 323.15K and at pressures from 4MPa up to very close to the critical pressure of the mixture. The ratio of liquid phase total volumes at the given pressure and at 4MPa was calculated. [Copyright &y& Elsevier]

Lignocellulosic materials, such as forest, agriculture, and agroindustrial residues, are among the most important resources for biorefineries to provide fuels, chemicals, and materials in such a way to substitute for, at least in part, the role of petrochemistry in modern society. Most of these sustainable biorefinery products can be produced from plant polysaccharides (glucans, hemicelluloses, starch, and pectic materials) and lignin. In this scenario, cellulosic ethanol has been considered for decades as one of the most promising alternatives to mitigate fossil fuel dependence and carbon dioxide accumulation in the atmosphere. However, a pretreatment method is required to overcome the physical and chemical barriers that exist in the lignin-carbohydrate composite and to render most, if not all, of the plant cell wall components easily available for conversion into valuable products, including the fuel ethanol. Hence, pretreatment is a key step for an economically viable biorefinery. Successful pretreatment method must lead to partial or total separation of the lignocellulosic components, increasing the accessibility of holocellulose to enzymatic hydrolysis with the least inhibitory compounds being released for subsequent steps of enzymatic hydrolysis and fermentation. Each pretreatment technology has a different specificity against both carbohydrates and lignin and may or may not be efficient for different types of biomasses. Furthermore, it is also desirable to develop pretreatment methods with chemicals that are greener and effluent streams that have a lower impact on the environment. This paper provides an overview of the most important pretreatment methods available, including those that are based on the use of green solvents (supercritical fluids and ionic liquids)., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The use of ionic liquids (ILs) for biomass processing has attracted considerable attention recently as it provides distinct features for pre-treated biomass and fractionated materials in comparison to conventional processes. Process intensification through integration of dissolution, fractionation, hydrolysis and/or conversion in one pot should be accomplished to maximise economic and technological feasibility. The possibility of using alternative ILs capable not only of dissolving and deconstructing selectively biomass but also of catalysing reactions simultaneously are a potential solution of this problem. In this Review a critical overview of the state of the art and perspectives of the hydrolysis and conversion of cellulose and lignocellulosic biomass using acidic ILs using no additional catalyst are provided. The efficiency of the process is mainly considered with regard to the hydrolysis and conversion yields obtained and the selectivity of each reaction. The process conditions can be easily tuned to obtain sugars and/or platform chemicals, such as furans and organic acids. On the other hand, product recovery from the IL and its purity are the main challenges for the acceptance of this technology as a feasible alternative to conventional processes., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Pretreatment of lignocellulosic biomass with ionic liquids (ILs) is a promising and challenging process for an alternative method of biomass processing. The present work emphasizes the examination of wheat straw pretreatment using ILs, namely, 1-butyl-3-methylimidazolium hydrogensulfate ([bmim][HSO4]), 1-butyl-3-methylimidazolium thiocyanate ([bmim][SCN]), and 1-butyl-3-methylimidazolium dicyanamide ([bmim][N(CN)2]). Only [bmim][HSO4] was found to achieve a macroscopic complete dissolution of wheat straw during pretreatment. The fractionation process demonstrated to be dependent on the IL used. Using [bmim][SCN], a high-purity lignin-rich material was obtained. In contrast, [bmim][N(CN)2] was a good solvent to produce high-purity carbohydrate-rich fractions. When [bmim][HSO4] was used, a different behavior was observed, exhibiting similarities to an acid hydrolysis pretreatment, and no hemicellulose-rich material was recovered during fractionation. A capillary electrophoresis (CE) technique allowed for a better understanding of this phenomenon. Hydrolysis of carbohydrates was confirmed, although an extended degradation of monosaccharides to furfural and hydroxymethylfurfural (HMF) was observed.

This work is devoted to study pre-treatment methodologies of wheat straw with 1-ethyl-3-methylimidazolium acetate ([emim][CH3COO]) and subsequent fractionation to cellulose, hemicellulose and lignin. The method developed and described here allows the separation into high purity carbohydrate and lignin fractions and permits an efficient IL recovery. A versatility of the established method was confirmed by the IL reuse. The fractionation of completely dissolved biomass led to cellulose-rich and hemicellulose-rich fractions. A high purity lignin was also achieved. To verify the potential further applicability of the obtained carbohydrate-rich fractions, and to evaluate the pre-treatment efficiency, the cellulose fraction resulting from the treatment with [emim][CH3COO] was subjected to enzymatic hydrolysis. Results showed a very high digestibility of the cellulose samples and confirmed a high glucose yield for the optimized pre-treatment methodology., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Fundamental data on 1,4-dioxaspiro[4.5]decane-2-methanol are scarce. This work presents the foremost systematic data on the solubility of 1,4-dioxaspiro[4.5]decane-2-methanol in sustainable solvents such as water and ionic liquids accompanied by the interpretation of interactions occurring in such binary systems. 1,4-Dioxaspiro[4.5]decane-2-methanol, here called protected glycerol, has been synthesized in order to protect the two hydroxyl groups of glycerol, thus avoiding the formation of side products in a specific process. A series of imidazolium salts accompanied by pyridinium, phosphonium, and ammonium ones with various types of counterions were used in this study. The liquid-liquid and solid-liquid equilibrium measurements in binary systems were carried out by using a dynamic method at atmospheric pressure over the temperature range from 273.00 to 378.30 K or below the boiling point of the solvent. Among all tested sustainable solvents, protected glycerol exhibited limited solubility, with only a few of them in the temperature range studied. The majority of the examined ionic liquids, either hydrophilic or hydrophobic, showed complete miscibility with this monohydroxyol. The Fourier-transform infrared (FTIR) spectroscopy studies of solute and solvents showing a miscibility gap and of their mixtures were performed to obtain insight into major inter- and intramolecular interactions in the investigated systems. Furthermore, the differential scanning calorimetry was used for the first time to determine the melting point, the enthalpy of melting, and the temperature and enthalpy of the solid-solid phase transition of 1-allyl-3-methylimidazolium chloride [Amim][Cl]. The results for the solubility of protected glycerol in sustainable solvents can be used to design future alternative reactions, such as telomerization with protected glycerol in ionic liquids for more specific building blocks and extraction/or separation that involves these mixtures., (© 2012 American Chemical Society)

This work presents a systematic investigation into liquid-liquid phase equilibria for systems containing three various ionic liquids and four dienes as they have not been reported yet. The systems employed in this study containing dicyanamide based ionic liquids and dienes reveal the phase envelopes that have a similar shape to binodal curves with the upper critical solution temperature. Generally, 1-methyl-3-octylimidazolium dicyanamide ([C(8)mim][DCA]) was found to be a better solvent for nonpolar dienes. The 1-butyl-3-methylimidazolium dicyanamide ([C(4)mim][DCA]) ionic liquid is a much worse solvent for 1,5-cyclooctadiene, 1,3-cyclooctadiene, 1,5-hexadiene, and 1,7-octadiene compared to other ionic liquids studied. The miscibility gaps shrink for a less polar [C(8)mim][DCA] or even more for 1-dodecyl-3-methylimidazolium dicyanamide ([C(12)mim][DCA]). In the range of the studied temperatures, the solubility of dienes is significantly higher compared to the solubility of the ionic liquids containing the shorter alkyl chain in the cation. The solubility of the presented dienes in ([C(4)mim][DCA]) ionic liquid is also relatively high and may reach up to 0.19 mol fraction of the diene. The attained results demonstrate that nonpolar compounds can be dissolved to some extent in highly charged and polar solvents such as ionic liquids.

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.