NiMoS on alumina-USY zeolite for hydrotreating lignin dimers: Effect of support acidity and cleavage of C-C bond
NiMoS on alumina, USY and mixed alumina-USY supports were studied in a batch reactor to assess the effect of support acidity in valorizing lignin dimers by hydrodeoxygenation (HDO). The reactivity of α-O-4 (benzyl phenyl ether), β-O-4 (2-phenethyl phenyl ether) and 5-5’ (2, 2’ Dihydroxybiphenyl) linkages were investigated in dodecane at 593 K and 5 MPa of H2 pressure. A relatively fast rate of hydrogenolysis of the sp3 hybridized etheric bonds were observed for the catalyst supported on the mixed support. With the α-O-4 linkage, the USY supported catalyst selectively yielded deoxygenated aromatics including BTX products with less residual C-C dimers. For the β-O-4 linkage, analogous trends have been observed but with more aromatics. Interestingly, with 5-5’ linkages the catalyst on USY and mixed support can break the C-C linkages without producing other intermediate C-C dimer byproducts. The results show high hydrocracking and isomerization activities of the catalyst supported on USY and mixed supports. This is consistent with the XRD, Raman, XPS and TEM measurements, where enhanced dispersion of the active phase was observed. However, hydrogenation activity on the USY support is reduced to a significant degree which results in large amount of benzene compared to NiMoS-Al2O3 that produces mostly cyclohexane. In addition, elemental analysis revealed that carbon deposition is higher on the USY-based catalyst compared to the alumina-based catalyst owing to its higher acidity. However, the potential for superior C-C bond cleavage on NiMoS-USY opens the possibility to valorize technical lignin in biorefinery processes.