Benzene co-reaction with methanol and dimethyl ether over zeolite and zeotype catalysts: Evidence of parallel reaction paths to toluene and diphenylmethane

• Published in: Journal of catalysis Vol. 349; pp. 136 - 148
• Main Authors: Martinez-Espin, Juan S., De Wispelaere, Kristof, Westgård Erichsen, Marius, Svelle, Stian, Janssens, Ton V.W., Van Speybroeck, Veronique, Beato, Pablo, Olsbye, Unni
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.05.2017
• Subjects: Benzene; Dimethyl ether; Diphenylmethane; Formaldehyde; Methanol; Methanol-to-hydrocarbons; Methylation; Zeolites; Diphenylmethane; Dimethyl ether; Benzene; Methylation; Zeolites; Formaldehyde; Methanol; Methanol-to-hydrocarbons
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2017.03.007

[Display omitted] •Different reactivity of methanol and DME toward benzene is observed.•DME promotes (successive) methylation of arenes and dealkylation products.•Methanol, in addition to methylated arenes and dealkylation products, gives significant amounts of diphenylmethanes.•The mechanism of diphenylmethane formation involves methanol dehydrogenation to formaldehyde on Brønsted acid sites. The reactivity of methanol (MeOH) and dimethyl ether (DME) toward benzene was studied over zeolitic materials with different topology and acid strength (H-ZSM-5, H-SSZ-24, and H-SAPO-5) at 250–350°C. Higher rates of methylation, and subsequent de-alkylation reactions, were observed with DME compared to MeOH. In addition, significant differences in product distribution based on the choice of methylating agent were observed. For reactions between MeOH and benzene a fraction of diphenylmethanes (DPMs) was formed, while this product group was nearly absent during reactions between DME and benzene. A range of co-feed and isotopic labeling experiments was performed, mainly over H-ZSM-5, in order to elucidate mechanistic information on the pathway from methanol and benzene to DPMs. Overall, these studies revealed that DPM formation involves the dehydrogenation of methanol to formaldehyde on the Brønsted acid site, followed by subsequent reaction with two benzene molecules. Theoretical calculations confirmed the higher reactivity of DME compared to MeOH toward benzene methylation and suggested a plausible route from formaldehyde and benzene to DPM.