Selective deoxygenation of biomass volatiles into light oxygenates catalysed by S-doped, nanosized zinc-rich scrap tyre char with in-situ formed multiple acidic sites

Abstract

In this paper, we report the unique properties and catalytic performance of scrap tyre char, an otherwise low-value waste derivative on the selective deoxygenation of biomass volatiles (derived from flash pyrolysis of lignocellulosic biomass at 500 °C) into value-added light oxygenates including furfural and phenol. Due to the inclusion of sulphur (S) and zinc oxide (ZnO) as additives during the prior tyre manufacturing process, the pyrolysis-derived tyre char is rich in both organically bound S and nano-sized zinc sulphide (ZnS) that are highly dispersed within the carbonaceous matrix. Detailed characterisations of the fresh and spent catalysts have been conducted to elaborate the unique mechanisms, upon the use of XPS, TEM-SAED, XAS, NEXAFS, Pyridine-FTIR, and NH3-TPD. As has been confirmed, multiple acidic sites are present in tyre char, including organically bound S serving as a weak Brønsted acid and nano-sized ZnS being a strong Lewis acid. The former acid is active for dehydration, whilst the latter one mainly catalyses the decarboxylation and decarbonylation reactions. Upon the interaction with adsorbed oxygen-bearing species and water molecules, the ZnS-centered active acid site can in-situ transform into a ZnSOx-centered super strong acid site, which is a Brønsted acid that is able to enhance the deoxygenation extent remarkably. More interestingly, the organic S enables an in-situ sulphidation of the less active ZnO on the catalyst surface, thereby enabling a continuous exposure of bio-oil vapour to the highly active ZnS and its sulphate derivative. This in turn enlarges the lifetime of the catalyst and its strong stability upon cyclic tests.