Experiments were performed on the products of glucose decomposition at short residence times to elucidate the reaction pathways and evaluate kinetics of glucose and fructose decomposition in sub- and supercritical water. The conditions were a temperature of 300−400 °C and pressure of 25−40 MPa for extremely short residence times between 0.02 and 2 s. The products of glucose decomposition were fructose, a product of isomerization, 1,6-anhydroglucose, a product of dehydration, and erythrose and glyceraldehyde, products of C−C bond cleavage. Fructose underwent reactions similar to glucose except that it did not form 1,6-anhydroglucose and isomerization to glucose is negligible. The mechanism for the products formed from C−C bond cleavage could be explained by reverse aldol condensation and the double-bond rule of the respective enediols formed during the Lobry de Bruyn Alberda van Ekenstein transformation. The differential equations resulting from the proposed pathways were fit to experimental results to obtain the kinetic rate constants.

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Glucose decomposition kinetics in subcritical and supercritical water were studied for the temperatures 573, 623, and 673 K, pressures between 25 and 40 MPa, and residence times between 0.02 and 2 s. Glucose decomposition products were fructose, saccharinic acids, erythrose, glyceraldehyde, 1,6-anhydroglucose, dihydroxyacetone, pyruvaldehyde, and small amounts of 5-hydroxymethylfurfural. Fructose was also studied and found to decompose to products similar to those of glucose, except that its epimerization to glucose was negligibly low and no formation of 1,6-anhydroglucose was detected. We concluded that only the forward epimerization of glucose to fructose was important. The glucose decomposition pathway could be described in terms of a forward epimerization rate, r gf , a fructose to decomposition products rate, r f , and a glucose to decomposition products rate, r g . A kinetic model based on this pathway gave good correlation of the experimental data. In the subcritical region, r g , r f , and r gf showed only small changes with pressure at a given temperature. In the supercritical region, the rate of glucose decomposition decreased with pressure at a given temperature. The reason for this decrease was mainly due to the decrease in r gf . The pressure effect in the supercritical region shows that there is a shift among the kinetic rates, which can lead to higher selectivity for glucose when decomposing cellulosic materials.

Cellobiose decomposition kinetics and products in sub- and supercritical water were studied with a flow apparatus at temperatures from 300 to 400 °C at pressures from 25 to 40 MPa, and at short residence times (0.04−2 s). Cellobiose was found to decompose via hydrolysis of the glycosidic bond and via pyrolysis of the reducing end. Pyrolysis products were glycosylerythrose (GE) and glycosylglycolaldehyde (GG) which were confirmed by FAB-MS. Hydrolysis products were glucose, erythrose, and glycolaldehyde from cellobiose, GE, and GG, respectively, as well as glucose decomposition products. The kinetics from glucose decomposition were used to fit the experimental results and evaluate rate constants of hydrolysis (k H) and pyrolysis rate constants (k 1 and k 2). The activation energy for the hydrolysis of cellobiose and pyrolysis products GG and GE was found to be 108.6, 110.5, and 106.1 kJ/mol, respectively. In the supercritical region, there was a decrease in the pyrolysis rates k 1 and k 2 and a corresponding increase in hydrolysis selectivity from 85% to 95% as the pressure increased from 30 to 40 MPa.

The degradation kinetics of dihydroxyacetone and glyceraldehyde were studied at temperature ranges of 573−673 K, pressures of 25−40 MPa, and residence times from 0.06 to 1.7 s. The reactions of glyceraldehyde gave both dihydroxyacetone and pyruvaldehyde, and yields of dihydroxyacetone were always higher than those of pyruvaldehyde. The reactions of dihydroxyacetone gave glyceraldehyde and pyruvaldehyde, while the yields of pyruvaldehyde were always higher than those of dihydroxyacetone. This pathway involves the reversible isomerization between glyceraldehyde and dihydroxyacetone and their subsequent dehydration to pyruvaldehyde. A model was formulated on the basis of this pathway, and the kinetic rate constants involved were calculated using the experimental results. As the conditions change from subcritical to supercritical, the Arrhenius relationship becomes discontinuous near the critical point of water. At a constant temperature of 673 K, the kinetics constants showed a general increase with an increase in pressure.