Acid Mesoporous Carbon Monoliths from Lignocellulosic Biomass Waste for Methanol Dehydration

Activated carbon monoliths (ACMs), with 25 cells/cm², were prepared from the direct extrusion of Alcell, Kraft lignin and olives stones particles that were impregnated with phosphoric acid, followed by activation at 700 °C. These ACMs were used as catalysts for methanol dehydration reaction under air atmosphere. ACM that was prepared from olive stone and at impregnation ratio of 2, OS2, showed the highest catalytic activity, with a methanol conversion of 75%, a selectivity to dimethyl ether (DME) higher than 90%, and a great stability under the operating conditions studied. The results suggest that the monolithic conformation, with a density channel of 25 cells/cm² avoid the blockage of active sites by coke deposition to a large extent. Methanol conversion for OS2 was reduced to 29% in the presence of 8%v water, at 350 °C, although the selectivity to DME remained higher than 86%. A kinetic model of methanol dehydration in the presence of air was developed, while taking into account the competitive adsorption of water. A Langmuir-Hinshelwood mechanism, whose rate-limiting step was the surface reaction between two adsorbed methanol molecules, represented the experimental data under the conditions studied very well. An activation energy value of 92 kJ/mol for methanol dehydration reaction and adsorption enthalpies for methanol and water of -12 and -35 kJ/mol, respectively, were obtained.