Ionic Liquids in the Pretreatment of Lignocellulosic Biomass

Abstract

This thesis is concerned with the thermal treatment of lignocellulosic biomass using ionic liquids for the purpose of comminution via dissolution, for fractionating the biological composite and for obtaining aqueous solutions of carbohydrate monomers from the pulp via enzymatic hydrolysis. A major focus was the relationship between the choice of the anion and the effectiveness of the treatment. The synthesis of a range of 1-butyl-3-methylimidazolium ionic liquids with strongly hydrogen-bond basic anions was accomplished. Selected, process-relevant physicochemical properties were measured, such as the Kamlet-Taft solvent polarity, hygroscopicity and thermal stability. It was shown that 1-butyl-3-methylimidazolium acetate is not stable at 120°C, while other ionic liquids e.g. 1-butyl-3-methylimidazolium hydrogen sulfate exhibit very good long-term thermal stability. It was shown that hydrogen-bond basic 1-butyl-3-methylimidazolium ionic liquids attract more than stoichiometric quantities of water when exposed to air, suggesting that ionic liquid pretreatment under anhydrous conditions is difficult to achieve. Dissolution of air-dried wood chips in 1-butyl-3-methylimidazolium ionic liquids was attempted. It was shown that the large particle size and the moisture contained in the biomass hamper complete dissolution. The hydrogen-bond basicity of the ionic liquid, described by the Kamlet-Taft parameter ß, was correlated with the ability to expand as well as partially and anisotropically dissolve wood chips. Pretreatment of lignocellulosic biomass with 1-butyl-3- methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium hydrogen sulfate and 1-butyl-3-methylimidazolium methanesulfonate was explored and high saccharification yields were reported. It was found that successful application of methyl sulfate and hydrogen sulfate ionic liquids requires addition of water and that comparatively high water contents are tolerated. Fractionation of lignocellulose into an insoluble cellulose fraction, a solubilised hemicellulose fraction and a lignin containing precipitate was achieved. The influence of water content, pretreatment time and biomass type on the enzymatic saccharification yield and the extent of hemicellulose solubilisation, hydrolysis and dehydration were examined.