Synergistic conversion of glucose into 5-hydroxymethylfurfural in ionic liquid-water mixtures.

A method for converting glucose into 5-hydroxymethylfurfural (5-HMF) without using chromium-containing catalysts was developed. The method uses ionic liquid-water mixtures with a ZrO(2) catalyst. Addition of a certain amount of water (10-50 wt.%) into the 1,3-dialkylimidazolium chloride ionic liquid promoted the formation of 5-HMF from glucose compared with that in either pure water or in the pure ionic liquid. A 5-HMF yield of 53% was obtained within 10 min at 200 °C in a 50:50 w/w% 1-hexyl-3-methyl imidazolium chloride-water mixture in the presence of ZrO(2). The 1,3-dialkylimidazolium ionic liquids having Cl(-) or HSO(4)(-) anions were effective for promoting 5-HMF formation. Addition of protic solvents such as methanol and ethanol to the ionic liquid had a similar synergistic effect as water and promoted fructose and 5-HMF formation. The results reported in this work can be extended to other fields, where the ratio of ionic liquid and protic solvent can be adjusted to promote the desired reactions.

Fast transformation of glucose and di-/polysaccharides into 5-hydroxymethylfurfural by microwave heating in an ionic liquid/catalyst system.

An efficient method for converting glucose into 5-hydroxymethylfurfural (5-HMF), in the presence of CrCl3 catalyst, is developed by using the ionic liquid 1-butyl-3-methyl imidazolium chloride as solvent. A 5-HMF yield of 71 % is achieved in 30 s for 96 % glucose conversion with microwave heating at 140 °C. The activation energy of glucose conversion is determined to be 114.6 kJ mol(-1), with a pre-exponential factor of 3.5 x 10(14) min(-1). Fructose, sucrose, cellobiose, and cellulose are studied and 5-HMF yields of 54 % are obtained for cellulose conversion at 150 °C during 10 min of reaction time. Recycling of the ionic liquid and CrCl3 is demonstrated with six cycles of use.

Acrolein synthesis from glycerol in hot-compressed water.

Glycerol conversion was conducted in hot-compressed water (HCW: 573-673 K, 25-34.5 MPa) using a batch and a flow apparatus and the influences of temperature, H(2)SO(4), glycerol concentration, and pressure, were examined. The yield of acrolein was enhanced by higher glycerol and H(2)SO(4) concentration, and higher pressure. Approximately 80% selectivity of acrolein was obtained at 90% of glycerol conversion with an acid catalyst in supercritical condition (673 K and 34.5 MPa). The rate constant of acrolein decomposition was always higher than that of acrolein formation in the absence of acid catalyst but the rate constant of acrolein formation could be overcome that of acrolein decomposition by addition acid in supercritical condition.

Glucose reactions within the heating period and the effect of heating rate on the reactions in hot compressed water.

Glucose reactions were conducted in hot compressed water (473-773 K, 4-40 MPa) by means of a batch-type reactor. The reactions in the heating period (about for 60s) were observed. More than 80% of the glucose was consumed in the heating period above 573 K. Gasification of glucose was promoted with increasing temperature. The effect of heating rate (from 4.2 to 15.8K/s) on glucose conversion was also examined, and gasification of glucose was enhanced with increasing the heating rate.

Glucose reactions with acid and base catalysts in hot compressed water at 473 K.

The effects of the homogeneous catalysts (H(2)SO(4) and NaOH) and heterogeneous catalysts (TiO(2) and ZrO(2)) on glucose reactions were examined in hot compressed water (473 K) by a batch-type reactor. From the homogeneous catalyst studies, we confirmed that the acid catalyst promoted dehydration, while isomerization of glucose to fructose was catalyzed by alkali. Anatase TiO(2) was found to act as an acid catalyst to promote formation of 5-hydroxymethylfuraldehyde (HMF). Zirconia (ZrO(2)) was a base catalyst to promote the isomerization of glucose. The effects of the additives were also confirmed through fructose reactions.