Shape selectivity in linear paraffins hydroconversion in 10-membered-ring pore zeolites

Pd/zeolite-catalyzed hydroconversion of n-hexadecane (n-C₁₆) and n-heptane (n-C₇) was studied for 10MR (ZSM-5, ZSM-22), 12MR (ZSM-12), and EMM-23 (21MR × 10MR) zeolites. The catalytic activity depended on the Brønsted acidity and the crystalline domain size. n-C₁₆ hydroconversion benefited from short diffusion lengths in ZSM-5 nanosheets compared to bulk ZSM-5. In general, over-cracking is dominant in ZSM-5 with a cracked product distribution skewed to C₄ products, to be explained by a snug fit of particular dibranched isomers at zeolite intersections. This effect is less pronounced for the 1D 10MR pores in ZSM-22, which lacks intersections. Although large pores in ZSM-12 offer relatively high activity, those in EMM-23 do not. Based on selectivity patterns, EMM-23 behaves like ZSM-5, probably because of the trilobe shape of its 21MR pores acting as 10MR pores. Only ZSM-12 offers operation in the ideal hydrocracking regime, in the sense of impediments neither by hydrogenation nor by diffusion. Faster intrazeolite diffusion of n-C₇ in comparison to n-C₁₆ leads to a higher yield of isomers for the nanostructured zeolites. Overall, the hydroconversion of the smaller alkane is more substantially impacted by variations in the crystalline zeolite domain size.