Catalytic bio‐oil upgrading to produce renewable fuels has attracted increasing attention in response to the decreasing oil reserves and the increased fuel demand worldwide. Herein, the catalytic hydrodeoxygenation (HDO) of guaiacol with carbon‐supported non‐sulfided metal catalysts was investigated. Catalytic tests were performed at 4.0 MPa and temperatures ranging from 623 to 673 K. Both Ru/C and Mo/C catalysts showed promising catalytic performance in HDO. The selectivity to benzene was 69.5 and 83.5 % at 653 K over Ru/C and 10Mo/C catalysts, respectively. Phenol, with a selectivity as high as 76.5 %, was observed mainly on 1Mo/C. However, the reaction pathway over both catalysts is different. Over the Ru/C catalyst, the OCH3 bond was cleaved to form the primary intermediate catechol, whereas only traces of catechol were detected over Mo/C catalysts. In addition, two types of active sites were detected over Mo samples after reduction in H2 at 973 K. Catalytic studies showed that the demethoxylation of guaiacol is performed over residual MoOx sites with high selectivity to phenol whereas the consecutive HDO of phenol is performed over molybdenum carbide species, which is widely available only on the 10Mo/C sample. Different deactivation patterns were also observed over Ru/C and Mo/C catalysts.
Catalytic conversion of glycerol to gasoline-range alkyl-aromatics has been investigated on a series of zeolites (HZSM-5, HY, Mordenite, and HZSM-22) at 300-400 °C and atmospheric pressure or 2 MPa. Although propenal (acrolein) is the major primary glycerol dehydration product over all zeolites, the pore structure of the zeolite plays a significant role on the final product distribution.The major products over one-dimensional zeolites Mordenite and HZSM-22 are oxygenates (propenal, acetol, and heavy oxygenates) without aromatic formation. HZSM-22 is suitable for the production of acrolein with 86% yield at 100% glycerol conversion. However, it is found that glycerol can be converted to high yields of alkyl-aromatics, mainly C 8 -C 10 over three-dimensional HY and HZSM-5. A longer contact time, higher temperatures, and higher pressures favor the formation of aromatics, with a maximum yield of 60% over HZSM-5. A two-bed configuration with a deoxygenation/hydrogenation catalyst (Pd/ZnO) as the first bed and HZSM-5 as the second bed can further increase the alkyl-aromatic yield. The mono-functional oxygenates produced by the first bed were oligomerized and aromatized into gasoline-range alkyl-aromatics over the second bed.
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