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 language | English (US) |
|---|---|
| Pages (from-to) | 4086-4091 |
| Number of pages | 6 |
| Journal | Green Chemistry |
| Volume | 16 |
| Issue number | 9 |
| DOIs | |
| State | Published - Sep 2014 |
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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 journal › Article
}
TY - JOUR
T1 - Solvent-tuned hydrophobicity for faujasite-catalyzed cycloaddition of biomass-derived dimethylfuran for renewable p-xylene
AU - Xiong, Ruichang
AU - Sandler, Stanley I.
AU - Vlachos, Dionisios G.
AU - Dauenhauer, Paul J.
PY - 2014/9
Y1 - 2014/9
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84906242503&partnerID=8YFLogxK
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U2 - 10.1039/c4gc00727a
DO - 10.1039/c4gc00727a
M3 - Article
AN - SCOPUS:84906242503
VL - 16
SP - 4086
EP - 4091
JO - Green Chemistry
JF - Green Chemistry
SN - 1463-9262
IS - 9
ER -