Energy & Fuels, Vol.27, No.2, 975-984, 2013
Hydrodeoxygenation of Guaiacol, A Surrogate of Lignin Pyrolysis Vapors, Over Iron Based Catalysts: Kinetics and Modeling of the Lignin to Aromatics Integrated Process
Biosourced aromatics (BTX (benzene, toluene, xylene) and phenols) could be produced by lignin pyrolysis coupled with catalytic hydrodeoxygenation (HDO) of uncondensed pyrolysis vapors. Guaiacol is used as a model compound to study the catalytic HDO over Fe/SiO2 catalyst. Experiments were conducted in a fixed bed reactor operated at 673 K (1 atm) with a gas mixture (guaiacol, H-upsilon, H2O, CO, CO2) that mimics the real gas composition from lignin pyrolysis. Fe/SiO2 catalyst was shown to be selective for guaiacol HDO into benzene and phenols because it does not catalyze the aromatic ring hydrogenation. Major and minor products are modeled by a semidetailed kinetic mechanism. A deactivation law is also determined. The kinetic model is then included in an Aspen Plus model of lignin to BTX process. Aspen Plus model handles (1) pyrolysis of lignin, including char, oligomers, gases and aromatic yields, (2) catalytic conversion of aromatics by the kinetic model, (3) heat exchangers, and (4) BTX vapors recovery by scrubbing with 1-methyl-naphthalene. Mass and carbon balances, heat demand, and selectivity in desired products are given for the overall process. The effect of gas dilution from pyrolysis reactor on BTX losses, heat demand, and scrubbing solvent flow rate is highlighted. High carrier gas flow rates (as required for biomass pyrolysis in fluidized bed) lead to the entrainment of fines and oligomers, dilute the products, and impact considerably the process intensification.