Kinetic Study on Disproportionations of C1 Aldehydes in Supercritical Water: Methanol from Formaldehyde and Formic Acid

Abstract

The reaction pathways and kinetics of C1 aldehydes, formaldehyde (HCHO) and formic acid (HCOOHHOCHO), are studied at 400 °C in neat condition and in supercritical water over a wide range of water density, 0.1−0.6 g/cm³. Formaldehyde exhibits four reactions: (i) the self-disproportionation of formaldehyde generating methanol and formic acid, (ii) the cross-disproportionation between formaldehyde and formic acid generating methanol and carbon dioxide, (iii) the water-independent self-disproportionation of formaldehyde generating methanol and carbon monoxide, and (iv) the decarbonylation of formaldehyde generating hydrogen and carbon monoxide. The self- and cross-disproportionations overwhelm the water-independent self-disproportionation and the formaldehyde decarbonylation. The rate constants of the self- and cross-disproportionations are determined in the water density range of 0.1−0.6 g/cm³. The rate constant of the cross-disproportionation is 2−3 orders of magnitude larger than that of the self-disproportionation, which indicates that formic acid is a stronger reductant than formaldehyde. Combining the kinetic results with our former computational study on the equilibrium constants of the self- and cross-disproportionations, the reaction mechanisms of these disproportionations are discussed within the framework of transition-state theory. The reaction path for methanol production can be controlled by tuning the water density and reactant concentrations. The methanol yield of ∼80% is achieved by mixing formaldehyde with formic acid in the ratio of 1:2 at the water density of 0.4 g/cm³.