Constructing the Al deficiency in Si-O(H)-Al units based on Pt/ZSM-5 for enhanced hydrocracking of polyethylene into high-quality liquid fuel
Xia Zhong, Jie Liu, Li Gao, Junnan Chen, Xiyang Wang, Ying Zhang, Yimin A. Wu, Mozaffar Shakeri, Xia Zhang, Bingsen Zhang
Abstract
Hydrocracking catalysis is a controllable route to plastic waste upgrading. However, the mismatched acid site-driven C-C cleavage and C=C hydrogenation process on metal restrict the efficiency and selectivity in conventional metal/acid bi-functional catalyst. Herein, we introduce Al deficiency in Si-O(H)-Al structural units of Pt/zeolite socony mobil-5 (Pt/ZSM-5) through discharge driven reduction (DR) process to precisely control the ratio of metal to acid, achieving hydrocracking of low-density polyethylene (LDPE) waste at 270 °C with 87.7% conversion and liquid fuel (C5-C21) selectivity of 77.8%. Pair distribution function (PDF) and nuclear magnetic resonance (NMR) spectroscopy demonstrate the partial absent Al sites further resulting short-range local disorder Si-O(H)-Al. Upon pyridine infrared spectroscopy (Py-IR) and CO diffuse reflectance Fourier-transform infrared (CO DRIFT) analysis, the extraction of Al modulates Brønsted acid density of Pt/ZSM-5 with DR process (Pt/Z5DR), improves the interaction between Pt and ZSM-5 support, enhances the cationic of Pt. The metal-acid balance and electron-deficient Pt favor the matching speed of light olefins hydrogenation and the cracking of macromolecule intermediates. Moreover, density functional theory (DFT) calculations identify the thermodynamic stability of Pt/Z5DR and moderate adsorption capability towards light olefins. This work confirms the great potential of precisely controlled molar of metal to acid in metal/zeolite catalysts for LDPE upcycling, providing a viable path for dealing with PE plastic wastes.