Mildly Acidic Aluminosilicate Catalysts for Stable Performance in Ethanol Dehydration

Ethanol dehydration is effectively catalyzed by strongly acidic zeolite catalysts which are known, however, to exhibit poor time on stream stability. Alumina and silica-alumina on the other hand are relatively stable but reach only low activity levels. Here, a series of aluminosilicate catalysts (Si:Al ratio = 16) was prepared by non-hydrolytic sol-gel (NHSG) and are shown to feature an intermediate level of activity, between the HZSM-5 zeolite and a commercial silica-alumina. Importantly, the best samples, were very stable with time on stream. Unlike HZSM-5, which also catalyzes ethylene oligomerization due to its strong acid sites and is therefore prone to coking, NHSG prepared catalysts did not produce any traces of ethylene oligomers and did not show any trace of coke formation. Characterization (ICP-OES, N₂ physisorption, TEM, XPS, IR coupled with pyridine adsorption, Raman spectroscopy, solid state NMR spectroscopy) reveal that the unconventional synthetic method presented here allowed to prepare mesoporous aluminosilicate materials with a remarkable degree of homogeneity. It is this thorough dispersion of Al in the amorphous silicate matrix which is responsible for the formation of acid sites which are intermediate (in terms of strength and nature) between those of commercial silica-alumina and HZSM-5 zeolite. The texture of the best NHSG catalyst – mainly mesoporous with a high specific surface area (800 m² g⁻¹) and pore volume (0.5 cm³ g⁻¹) – was also unaffected after reaction. To overcome deactivation issues in ethanol dehydration, this study suggests to target amorphous aluminosilicate catalysts with open mesoporosity and with an intimate mixing of Al and Si.