Solvent-tuned hydrophobicity for faujasite-catalyzed cycloaddition of biomass-derived dimethylfuran for renewable p-xylene

Ruichang Xiong, Stanley I. Sandler, Dionisios G. Vlachos, Paul J. Dauenhauer

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

Phase equilibria of the high temperature/high pressure heterogeneous catalytic reaction of 2,5-dimethylfuran (DMF), a biomass-derived furan, with ethylene to produce p-xylene was studied as a function of DMF conversion in a constant-pressure reactor. Adsorption of reactants and products onto a zeolite catalyst was computed using a configurational-bias Grand Canonical Monte Carlo (CB-GCMC) simulation, and the vapor-liquid behavior was computed using ASPEN Plus with an appropriate equation of state. It was found that the amount of water adsorbed in H-Y (Si/Al = 2.6) increases significantly as DMF is consumed, but is small in the presence of an aliphatic solvent, here n-heptane, even at high DMF conversion. The presence of the solvent reduces side reactions with water, such as hydrolysis followed by oxyalkylation, and increases p-xylene selectivity, in agreement with experiment. The decrease in the amount of water adsorbed is due to the increased hydrophobic environment in the zeolite as a result of the addition of n-heptane. The increase of ethylene inside the cage by the addition of n-heptane results in a slight increase of p-xylene alkylation. This work presents the first use of molecular simulation to understand mechanistic effects of solvents on the catalytic production of p-xylene in an H-Y zeolite.

Original languageEnglish (US)
Pages (from-to)4086-4091
Number of pages6
JournalGreen Chemistry
Volume16
Issue number9
DOIs
StatePublished - Sep 2014

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Cycloaddition
hydrophobicity
xylene
Xylene
Hydrophobicity
Zeolites
Biomass
Heptane
zeolite
biomass
ethylene
Water
Ethylene
furan
Alkylation
phase equilibrium
Equations of state
equation of state
Phase equilibria
water

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Solvent-tuned hydrophobicity for faujasite-catalyzed cycloaddition of biomass-derived dimethylfuran for renewable p-xylene. / Xiong, Ruichang; Sandler, Stanley I.; Vlachos, Dionisios G.; Dauenhauer, Paul J.

In: Green Chemistry, Vol. 16, No. 9, 09.2014, p. 4086-4091.

Research output: Contribution to journalArticle

Xiong, Ruichang ; Sandler, Stanley I. ; Vlachos, Dionisios G. ; Dauenhauer, Paul J. / Solvent-tuned hydrophobicity for faujasite-catalyzed cycloaddition of biomass-derived dimethylfuran for renewable p-xylene. In: Green Chemistry. 2014 ; Vol. 16, No. 9. pp. 4086-4091.
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