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.

Lignocellulosic biomass composes a diversity of feedstock raw materials representing an abundant and renewable carbon source. In majority lignocellulose is constituted by carbohydrate macromolecules, namely cellulose and hemicellulose, and by lignin, a polyphenilpropanoid macromolecule. Between these biomacromolecules, there are several covalent and non-covalent interactions defining an intricate, complex and rigid structure of lignocellulose. The deconstruction of the lignocellulosic biomass makes these fractions susceptible for easier transformation to large number of commodities including energy, chemicals and material within the concept of biorefinery. Generally, the biomass pre-treatment depends on the final goal in the biomass processing. The recalcitrance of lignocellulose materials is the main limitation of its processing once the inherent costs are excessively high for the conventional pre-treatments. Furthermore, none of the currently known processes is highly selective and efficient for the satisfactory and versatile use, thus, new methodologies are still studied broadly. The ionic liquid technology on biomass processing is relatively recent and first studies were focused on the lignocellulosic biomass dissolution in different ionic liquids (ILs). The dissolution in IL drives to the structural changes in the regenerated biomass by reduction of cellulose crystallinity and lignin content contrasting to the original biomass. These findings provided ILs as tools to perform biomass pre-treatment and the advantageous use of their specific properties over the conventional pre-treatment processes. This review shows the critical outlook on the study of biomass dissolution and changes occurred in the biomass during this process as well as on the influence of several crucial parameters that govern the dissolution and further pre-treatment process. The review of currently known methods of biomass fractionation in IL and aqueous-IL mixtures is also discussed here and perspectives regarding these topics are given as well.

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.

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Aqueous biphasic systems based on ionic liquids (ILs) have been researched as promising extraction and purification routes for a huge diversity of compounds. The inherent tunability offered by ILs combined with the large variety of salts available underlines the reliable phase equilibrium data. In this vein, this work presents novel aqueous biphasic systems based on the 1-butyl-1-methylpyrrolidinium cation combined with anions derived from organic acids, such as acetate, trifluoroacetate, hexanoate, adipate, and one halogenated anion, bromide, in the presence of a powerful salting out species, the inorganic salt K3PO4. The capacity of these ILs to undergo phase separation is discussed in regard to the chemical structure of the IL anion. The results here obtained were compared with those determined for poly­(ionic liquid) analogues, and it was observed that while in ILs the hydrophobicity of the anion has the major role in phase splitting, in poly­(ionic liquid)­s that role is played by the polymer molecular weight. The effect of temperature on the phase equilibria is addressed.