Pyrolysis and auto-gasification of black liquor in presence of ZnO: An integrated process for Zn/ZnO nanostructure production and bioenergy generation

This study presents a new process for valorisation of black liquor into gases that are used to reduce ZnO and promote zinc nanosheet synthesis, besides energy generation. During the black liquor pyrolysis and auto-gasification, gases evolve, especially carbon monoxide, and promote ZnO reduction with Zn(v) release. The metal is condensed yielding zinc nanosheets, with partial surface re-oxidation in presence of carbon dioxide. The process was investigated at the micro scale using thermal analyses (TG/DTG/DTA) and the gases evolved were analysed by FTIR spectroscopy (TG/FTIR). The process was also studied in laboratory scale using a tubular electric furnace. The black liquor/ZnO mixture was placed at the quartz tube and the sample was heated to 900 °C at 10 °C/min, and the temperature was held at 900 °C for 1 h. The nanostructures growth was catalyst-free, without pressure reduction or a template, at temperatures lower than those required in the classical carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and infrared spectroscopy (FTIR). One mechanism was presented in an attempt to explain the synthesis of Zn/ZnO nanosheets that are crystalline. This green and innovative process has potential use at the industry due to its operational conditions, low costs and technological importance of Zn and ZnO nanostructures.

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► Black liquor and ZnO mixture were submitted to a heat treatment until 900 °C.
► The black liquor suffered pyrolysis and auto-gasification.
► ZnO is reduced by CO yielding Znv, that is condensed generating Zn/ZnO nanosheets.
► The nanostructures are characterized and a mechanism of reactions is presented.
► The new process can produce energy and nanostructures in large scale.