Production of Branched Alkanes by Upcycling of Waste Polyethylene over Controlled Acid Sites of SO4/ZrO2-Al2O3 Catalyst

Wanying Han; Longfei Lin; Ziyu Cen; Yubin Ke; Qian Xu; Junfa Zhu; Xuelei Mei; Zhanghui Xia; Xinrui Zheng; Yaqin Wang; Yani Liu; Mingyuan He; Haihong Wu; Buxing Han

doi:10.1002/anie.202417923

Production of Branched Alkanes by Upcycling of Waste Polyethylene over Controlled Acid Sites of SO₄/ZrO₂-Al₂O₃ Catalyst

Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202417923. doi: 10.1002/anie.202417923. Epub 2024 Nov 22.

Authors

Wanying Han^{1

2}, Longfei Lin^{3

4}, Ziyu Cen^{3

4}, Yubin Ke⁵, Qian Xu⁶, Junfa Zhu⁶, Xuelei Mei^{1

2}, Zhanghui Xia^{1

2}, Xinrui Zheng^{1

2}, Yaqin Wang^{1

2}, Yani Liu^{1

2}, Mingyuan He^{1

2}, Haihong Wu^{1

2}, Buxing Han^{1

2

3

4}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
² Institute of Eco-Chongming, 20 Cuiniao Road, Chenjia Town, Chongming District, Shanghai, 202162, China.
³ Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
⁴ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
⁵ China Spallation Neutron Source, Institute of High Energy Physics, Chinese Academy of Science, Dongguan, 523000, China.
⁶ National Synchrotron Radiation Laboratory, Department of Chemical Physics and Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei, 230029, China.

PMID: 39537576
DOI: 10.1002/anie.202417923

Abstract

Branched alkanes, which enhance the octane number of gasoline, can be produced from waste polyethylene. However, achieving highly selective production of branched alkanes presents a significant challenge in the upcycling of waste polyethylene. Here, we report a one-pot process to convert polyethylene into gasoline-range hydrocarbons (C₄-C₁₃) with yield of 73.3 % over SO₄/ZrO₂-Al₂O₃ catalyst at 280 °C. The proportion of branched alkanes reaches 90.1 % within the C₄-C₁₃ fraction. Incorporation of sulfate group endows the catalyst with strong Lewis acid sites and weak and moderate Brønsted acid sites. In situ X-ray absorption, in situ infrared spectroscopy, in situ small angle neutron scattering, and DFT calculations reveal that polyethylene activation occurs through the synergy between sulfate groups and strong Lewis acid sites (Zr sites). The weak and moderate Brønsted acid sites preferentially catalyze the isomerization and type A β-scission processes, which favors the formation of branched alkanes, while suppressing competing reactions that produce straight-chain alkanes.

Abstract

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