Upcycling of the Used Cigarette Butt Filters through Pyrolysis Process: Detailed Kinetic Mechanism with Bio-Char Characterization

Polymers (Basel). 2023 Jul 15;15(14):3054. doi: 10.3390/polym15143054.

Abstract

Thermo-chemical conversion via the pyrolysis of cigarette butt (CB) filters was successfully valorized and upcycled in the pre-carbonization and carbonization stages. The pre-carbonization stage (devolatilization) of the precursor material (cellulose acetate filter, r-CAcF) was analyzed by micro-scale experiments under non-isothermal conditions using TG-DTG-DTA and DSC techniques. The results of a detailed kinetic study showed that the decomposition of r-CAcF takes place via complex mechanisms, including consecutive reaction steps and two single-step reactions. Consecutive stages include the α-transition referred to as a cellulose polymorphic transformation (cellulose I → II) through crystallization mechanism changes, where a more thermodynamically ordered system was obtained. It was found that the transformation rate of cellulose I → II ('cellulose regeneration') is strongly affected by the presence of alkali metals and the deacetylation process. Two single-step reactions showed significant overlapping behavior, which involves a nucleation-controlled scission mechanism (producing levoglucosan, gaseous products, and abundant radicals) and hydrolytic decomposition of cellulose by catalytic cleavage of glycosidic bonds with the presence of an acidic catalyst. A macro-scale experiment showed that the operating temperature and heating rate had the most notable effects on the total surface area of the manufactured carbon. A substantial degree of mesoporosity with a median pore radius of 3.1695 nm was identified. The presence of macroporosity on the carbon surface and acidic surface functional groups was observed.

Keywords: autocatalysis; carbonization; cellulose triacetate; devolatilization; kinetics modeling; mesoporous charred carbon.

Grants and funding

This research was funded by financial support of Ministry of Science, Technological Development and Innovation of the Republic of Serbia, under Contract numbers 451-03-47/2023-01/200017 (“Vinča” Institute of Nuclear Sciences—National Institute of the Republic of Serbia), 451-03-47/2023-01/200026 (Institute of Chemistry, Technology, and Metallurgy—National Institute of the Republic of Serbia), 451-03-47/2023-01/200051 (Institute of General and Physical Chemistry), 451-03-47/2023-01/200105 (Faculty of Mechanical Engineering).