1-butyl-3-methylimidazolium-chloride and sulfuric-acid

In this paper, the kinetics of acid-catalyzed cellulose hydrolysis in ionic liquids (ILs) was investigated by using 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as the model IL. General kinetic equations for the formation of glucose as well as cellooligomers were constructed at a molecular level, assuming that cellulose is fully dissolved to form a homogenous solution and that the scission of the glycosidic bond occurs randomly within the cellulose chain. Experimental data were well fitted according to these equations. Variations of kinetic parameters in the presence of different water content indicated that water behaved also as a base to decrease the acidity of the reaction medium. More importantly, it offered a profile of the evolution of cellooligomers. These results provided insights into the detailed mechanisms of cellulose hydrolysis in a non-aqueous, homogenous environment and should be valuable for developing strategies to depolymerize lignocellulosic biomass.

Topics: Catalysis; Cellobiose; Cellulose; Glucose; Hydrolysis; Imidazoles; Kinetics; Sulfuric Acids

A biomass pretreatment process was developed using acidified ionic liquid (IL) solutions containing 10-30% water. Pretreatment of sugarcane bagasse at 130°C for 30 min by aqueous 1-butyl-3-methylimidazolium chloride (BMIMCl) solution containing 1.2% HCl resulted in a glucan digestibility of 94-100% after 72 h of enzymatic hydrolysis. HCl was found to be a more effective catalyst than H(2)SO(4) or FeCl(3). Increasing acid concentration (from 0.4% to 1.2%) and reaction temperature (from 90 to 130°C) increased glucan digestibility. The glucan digestibility of solid residue obtained with the acidified BMIMCl solution that was re-used for three times was >97%. The addition of water to ILs for pretreatment could significantly reduce IL solvent costs and allow for increased biomass loadings, making the pretreatment by ILs a more economic proposition.

Topics: Biotechnology; Catalysis; Cellulose; Glucans; Glucose; Hydrochloric Acid; Hydrolysis; Imidazoles; Ionic Liquids; Kinetics; Saccharum; Solutions; Spectroscopy, Fourier Transform Infrared; Sulfuric Acids; Temperature; Time Factors; Water

Conversion of fructose and glucose into 5-hydroxymethylfurfural (HMF) was investigated in various imidazolium ionic liquids, including 1-butyl-3-methylimidazolium chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride (HmimCl), 1-octyl-3-methylimidazolium chloride (OmimCl), 1-benzyl-3-methylimidazolium chloride (BemimCl), 1-Butyl-2,3-dimethylimidazolium chloride (BdmimCl), and 1-butyl-3-methylimidazolium p-toluenesulfonate (BmimPS). The acidic C-2 hydrogen of imidazolium cations was shown to play a major role in the dehydration of fructose in the absence of a catalyst, such as sulfuric acid or CrCl(3). Both the alkyl groups of imidazolium cations and the type of anions affected the reactivity of the carbohydrates. Although, except BmimCl and BemimCl, other four ionic liquids could only achieve not more than 25% HMF yields without an additional catalyst, 60-80% HMF yields were achieved in HmimCl, BdmimCl, and BmimPS in the presence of sulfuric acid or CrCl(3) in sufficient quantities.

Topics: Borates; Catalysis; Chlorides; Chromium Compounds; Fructose; Furaldehyde; Glucose; Imidazoles; Ionic Liquids; Sulfuric Acids

The reactivity of monosaccharides, furfural, and 5-hydroxymethyl-2-furfural (HMF) in the presence of a Brønsted acid (added as H(2)SO(4)) in the ionic liquid 1-butyl-3-methylimidazolium chloride (BMImCl) is investigated at 120 °C. Fructose is converted much faster than mannose, glucose, and xylose and yields HMF with high selectivity, even in the absence of acid. Conversion of mannose, glucose, and xylose involves more complex reaction networks. Only small amounts of furfural and HMF are converted in the absence of other reactants but both compounds are consumed when monosaccharides and their degradation products are present. Acid-catalyzed degradation reactions also lead to the formation of solid residues (humins).

Topics: Catalysis; Furans; Imidazoles; Monosaccharides; Sulfuric Acids