Developing Advanced Catalysts for the Conversion of Polyolefinic Waste Plastics into Fuels and Chemicals

TLDR

Polyolefin cracking with conventional solid acids is limited by steric and diffusional hindrances, underscoring the need for catalysts with accessible acid sites such as mesoporous, extra‑large pore, delaminated, or pillared zeolites. This review explores catalytic cracking of polyolefins over solid acids, focusing on catalyst roles in fuel and chemical synthesis and on current reaction systems. The authors examine mesoporous and nanozeolite catalysts that enhance activity, and propose two‑step processes combining thermal treatment with catalytic conversion and reforming to maintain activity. Hierarchical zeolites with bimodal micropore–mesopore distributions emerge as the most active catalysts, representing a breakthrough that is expected to drive further advances in polyolefin cracking.

Abstract

The present review is aimed at exploring the field of the catalytic cracking of polyolefins over solid acids, focusing on the role played by the catalysts toward the synthesis of fuels and chemicals as well as on the reaction systems currently used. Initially, conventional solid acids, such as micrometer sized crystal zeolites and silica–alumina, were used to establish the relationship among their activity, selectivity, and deactivation in the polyolefin cracking and the inherent properties of the catalysts (acidity, pore structure); however, the occurrence of steric and diffusional hindrances for entering the zeolite micropores posed by the bulky nature of the polyolefins highlighted the importance of having easily accessible acid sites, either through mesopores or by a high external surface area. This fact led toward the investigation of mesoporous materials (Al-MCM-41, Al-SBA-15) and nanozeolites, which allowed increasing the catalytic activities, especially for the case of polypropylene. Further advances have come by the application of hierarchical zeolites whose bimodal micropore–mesopore size distribution has turned them into the most active catalysts for polymer cracking. In this regard, hierarchical zeolites may be regarded as a clear breakthrough, and it is expected that future research on them will bring new achievements in the field of catalytic cracking of polyolefins. In addition, other materials with high accessibility toward the active sites, such as extra-large pore zeolites, delaminated zeolites, or pillared zeolite nanosheets, can also be considered potentially promising catalysts. From a commercial point of view, two-step processes seem to be the most feasible option, including a combination of thermal treatments with subsequent catalytic conversion and reforming, which allows the catalytic activity to be preserved against different types of deactivation.