Abstract
The selective conversion of high-molecular-weight paraffins (C20–C40) into linear alpha-olefins is often hindered by severe diffusion limitations and secondary over-cracking. This study addresses these challenges by transforming low-value natural minerals into sophisticated catalytic systems. We present a “top-down” engineering strategy for designing hierarchical catalysts based on natural Kazakhstani clinoptilolite. The multi-stage modification involves synergistic demineralization and precision chelation (EDTA, sulfosalicylic acid) to generate a tailored mesoporous architecture. This framework serves as a host for the sub-nanometric immobilization of Keggin-type heteropolyacids (PW12, PMo12), ensuring optimal active-phase dispersion. The innovative dual-step modification successfully bypassed the “micropore barrier”, creating a high-surface-area hierarchical network that facilitates the transport of bulky paraffinic molecules. Precise localization of heteropolyacid clusters within the created mesopores resulted in the formation of superstrong Lewis acid sites, as confirmed via temperature-programmed ammonia desorption. These sites triggered a highly efficient monomolecular beta-scission mechanism, suppressing undesirable hydrogen transfer reactions. The resulting catalysts achieved a breakthrough in technical paraffin cracking, delivering a 70% liquid product yield with an unprecedented >50% selectivity toward the C7–C14 α-olefin fraction. This work demonstrates a sustainable pathway for upgrading natural zeolites into high-performance, green catalysts that rival expensive analogs in precision and efficiency.