4.5 Article

Study on catalytic pyrolysis mechanism of natural rubber (NR) over Zn-modified ZSM5 catalysts

Journal

JOURNAL OF THE ENERGY INSTITUTE
Volume 94, Issue -, Pages 210-221

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.joei.2020.09.005

Keywords

Natural rubber; D-limonene; Catalytic pyrolysis; Zn-containing ZSM5; Py-GC/MS

Categories

Funding

  1. National Natural Science Foundation of China [51806078]
  2. Foundation of State Key Laboratory of Coal Combustion [FSKLCCB1904]

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The introduction of Zn species into zeolites can enhance the selectivity of aromatic hydrocarbons in NR pyrolysis products, especially BTEX, but excessive Zn loading has a negative effect. Zn/ZSM5 catalyst prepared by ion-exchange method showed higher selectivity towards BTEX due to more Zn species existed in the form of divalent zinc ions.
In this work, NR and D-limonene were pyrolyzed using ZSM5, Zn/ZSM5, ZnO/ZSM5 and ZnS/ZSM5 catalysts on a Py-GCMS system. The effects of Zn loading (1, 3, 5 wt%) and catalyst preparation methods (impregnation method, ion-exchange method) on catalytic pyrolysis experiments were studied. The results indicated the introduction of Zn species into zeolites can form new Lewis acid (L acid) sites at the expense of Bronsted acid (B acid) sites. For Zn/ZSM5 catalysts prepared by impregnation method, Zn species mainly existed in the form of the divalent zinc cation at the exchange sites and ZnO, and the proportion of ZnO increased with the Zn loading increasing. For Zn/ZSM5 catalyst prepared by ion-exchange method, most Zn2+ were tightly interacted with zeolite framework. For ZnO/ZSM5 and ZnS/ZSM5 catalysts, the Zn species primarily existed in the form of ZnO and ZnS, respectively. Py-GC/MS experimental results showed that proper Zn loading helped to improve the selectivity of aromatic hydrocarbons in NR pyrolysis products, especially BTEX (Benzene, Toluene, Ethylbenzene, Xylene), but excessive Zn loading had a negative effect. Compared with impregnation method, Zn/ZSM5 catalyst prepared by ion-exchange method showed higher selectivity towards BTEX due to more Zn species existed in the form of divalent zinc ions. (C) 2020 Energy Institute. Published by Elsevier Ltd. All rights reserved.

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