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The objective of this work is to explore and test a new method to improve the p-/m-xylene selectivity through catalytic hydrodeoxygenation and methylation of lignin-based phenols. The hydrodeoxygenation (HDO) of m-cresol and co-catalytic conversion of m-cresol with methanol at different molar ratio over Pt/HZSM-5 were studied to investigate the effect of methanol on co-feeding process. In order to explain the reason why p-/m-xylene selectivity increases, the co-catalytic conversion of m-cresol with methanol under N2, and conversion of the intermediate were carried out. Additionally, we applied this procedure (co-conversion with methanol) to different catalysts and other two phenols (guaiacol and p-cresol). 2. ResultsandDiscussion In this paper, the HZSM-5 (SiO2/Al2O3 of 25, 57, and 107), desilicated HZSM-5, and HBeta (SiO2/Al2O3 of 25) zeolites were denoted as Z-25, Z-57, Z-107, Z-57D, and B-25, respectively. In this section, the hydrodeoxygenation of m-cresol was firstly carried out over Pt/Z-57. Then catalytic hydrodeoxygenation and methylation of m-cresol at different molar ratio were studied to investigate the methanol effect on the p-/m-xylene selectivity. Immediately following, co-catalytic conversion under N2 and the intermediate conversion were researched to illustrate the methanol effect on p-/m-xylene selectivity. Based on the discussion above, possible reaction routes for catalytic hydrodeoxygenation and methylation of m-cresol over Pt/Z-57 in the presence of H2 were proposed. Thirdly, in order to validate the reaction routes, catalytic hydrodeoxygenation, and methylation of m-cresol were also conducted over a series of catalysts. Fourthly, the co-conversion with methanol was applied to other kinds of lignin-based phenols to verify its effectiveness. 2.1. Catalytic Hydrodeoxygenation of m-Cresol over Pt/Z-57 Figure 1 presents the conversion of m-cresol and product distribution with the reaction temperature over Pt/Z-57 catalyst. With the increasing reaction temperature, all the m-cresol conversion is greater than 95% and slightly changes. However, the product distribution significantly changes. For instance, the toluene selectivity increases from 9.8% at 573 K to 39.8% at 673 K and alters a little at higher temperature, while the selectivity of alkanes (including methylcyclohexane, 1,3-dimethylcyclopentane, and C3–6) sharply declines from 88.2% at 573 K to 4.4% at 723 K. The p-/m-xylene and o-xylene selectivities have similar variation trend as the toluene selectivity, with separately reaching 16.3% and 4.7% at 673 K and changing a little at higher temperature. Selectivities of benzene and polyalkylated benzenes also raise and reach up to 13.8% and 3.3% at 723 K, respectively. The different selectivity tendencies between aromatic compounds and alkanes could be explained by the fact that at low temperature hydrogenation of toluene and benzene 207PDF Image | Zeolite Catalysis
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