Renewable Aromatics from Tree-Borne Oils over Zeolite Catalysts Promoted by Transition Metals

ACS Appl Mater Interfaces. 2020 Jun 3;12(22):24756-24766. doi: 10.1021/acsami.0c04149. Epub 2020 May 21.

Abstract

Despite the ever-growing demand for benzene-toluene-xylene (BTX), the alternative route of production from tree-borne oils is rarely investigated and poorly understood. Here, we have synthesized a Zn-loaded Y-zeolite catalyst for the continuous production of bio-BTX from tree-borne oils (nonedible seed oil), e.g., neem oil. Our approach involves low-temperature selective cracking-dehydrogenation-aromatization of neem oil over metal-supported catalysts to xylene-rich aromatics. The physicochemical properties of the prepared catalyst were characterized using powder XRD, N2 physisorption, TEM, NH3-TPD, XPS, Py-FTIR, solid-NMR, and TG analyses. Mesoporous Y-zeolites with a pore diameter of 7.4 Å showed better selectivity toward aromatics and were found to be the most effective catalyst for the aromatization process, especially for BTX. The aromatic yield was found to increase with the addition of Zn, and the highest conversion of 90-94% with an ∼75% BTX yield was achieved with the ZnY catalyst. During aromatization, a sizable number of short alkanes and olefins were also obtained on acidic Y-zeolites. The off-gas composition shows the presence of ∼45% C2-C4 olefins with 8.9% H2. The incorporation of Zn species can promote the dehydrogenation activity, and the subsequent aromatization required a suitable pore network. The optimized ZnY catalyst inspires the formation of toluene and xylenes, inhibiting the formation of benzene and gaseous alkanes.

Keywords: Zn zeolites; aromatization; bioaromatics; neem oil; sustainable chemicals; tree-borne oils.