On the deactivation of Zr-loading P-containing mesoporous carbon catalyst during methanol dehydration

Abstract

Dimethyl ether (DME) has received much attention in the last few years due to its potential use as a diesel substitute and it can be obtained from dehydration of biomass-based methanol. γ-Alumina, ZSM-5 and HPAs were tested as catalysts. A carbon-supported zirconium phosphate catalyst was synthesized and tested for methanol dehydration reaction in a high temperature range. Carbon matrix was produced by olive stone waste activated with phosphoric acid (mass acid to olive stone ratio of 2:1) at 800ºC for 2 h. Then, after washing with distilled water and sieving between 100-300μm, the obtained carbon was impregnated with ZrO(NO3)2 and thermal treated at 250ºC for 2 h. Reaction was performed in a fixed-bed reactor at a space time of 75 gcat·s/mmolCH3OH, a partial pressure of 0.04 atm of methanol and temperatures between 450-600ºC. Deactivated samples were exposed to air at 350ºC for 100 min to study the catalyst regeneration. The catalyst showed a high selectivity to DME (≥95%) and an acceptable conversion at Tª lower than 400ºC without noticeable deactivation. At T>400 ºC, deactivation was detected, due to coke deposition, whose rate increases with operating temperature. However, a high selectivity to DME was observed (above 65%) even at very long times on stream (tos). N2 adsorption results pointed out that deposition of coke took place mainly on the surface of the narrow micropores of the catalyst, blocking much of this narrow porosity at long tos. According to XPS analysis, superficial concentration of phosphorus and zirconium were also diminished with coke deposition, although zirconium was decreased to a larger extend. A kinetic model was developed for the catalyst deactivation during methanol dehydration under different reaction conditions, based on coke deposition.