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Elucidating the thermal decomposition mechanism and pyrolysis characteristics of biorefinery-derived humins from sugarcane bagasse and rice husk

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Abstract

Biomass-derived humins produced in the biorefining of biomass represent an attractive feedstock for thermochemical processes. This work examines the purification and characterization of humins derived from sugarcane bagasse and rice husks (H-SCB and H-RH, respectively), followed by the kinetic and thermodynamic analysis of its pyrolysis. Pyrolysis was assessed via thermogravimetric analysis, and a global reaction model was adopted to address pyrolysis kinetics. To boost the quality of fit between the kinetic model and thermoanalytical data, the analyses are based on Vyazovkin's method. The activation energy of H-SCB increased from 166.09 to 329.76 kJ mol−1. In contrast, the activation energy of H-RH decreased from 163.31 to 84.99 kJ mol−1. According to the results of the generalized master-plot approach, the governing reaction mechanism shifted among order-based models, nucleation, and diffusion-controlled particle mechanisms. Thermodynamic properties showed that the process is endothermic, with the thermal decomposition of H-SCB being more reactive (ΔSaverage = -0.004 kJ mol−1 K−1) compared to H-RH (ΔSaverage = -0.05 kJ mol−1 K−1). Also, the heat absorbed helps the humins to achieve a more ordered state close to a conversion of 0.50. Furthermore, a difference of about 7 kJ mol−1 between the enthalpy of the reaction and the average activation energy indicates the formation of favorable product with humins’ considerable bioenergy potential. These findings are the first reported data on the forecast kinetic curves and pyrolysis mechanism of biorefinery-derived humins, and these results will enable process design for the thermochemical conversion of these emerging materials to produce energy and other products.

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Acknowledgements

The authors would like to thank Centro de Equipamentos e Serviços Multiusuários—CESM (Institute of Environmental, Chemical and Pharmaceutical Sciences at Federal University of São Paulo) for the support with TGA and the Laboratory of Recycling, Waste Treatment and Extraction—LAREX (Department of Chemical Engineering, Escola Politécnica of the University of São Paulo) for the support with TG-QMS.

Funding

This work was supported by National Council for Scientific and Technological Development—CNPq [grants 408149/2018–3 and 162373/2020–1] and São Paulo Research Foundation—FAPESP [grants 2020/11347–5, 2015/17592–3, and 2015/20630–4].

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Authors and Affiliations

  1. Department of Chemical Engineering, Federal University of São Paulo, ZIP Code, Diadema, SP, 09913-030, Brazil

    Julio César de Jesus Gariboti, Marina Gontijo Souza Macedo, Vinícius Matheus Silva Macedo, Eliezer Ladeia Gomes, Romilda Fernandez Felisbino & Laura Plazas Tovar

  2. Department of Mechanical Engineering, Industrial University of Santander, ZIP code 680002, Bucaramanga, Colombia

    Yesid Javier Rueda-Ordóñez

  3. School of Chemical Engineering, University of Campinas, ZIP code 13083-852, Campinas , SP, Brazil

    Emília Savioli Lopes

  4. Department of Chemical Engineering, University of São Paulo, ZIP Code, São Paulo, SP, 05508-080, Brazil

    Jonathan Tenorio Vinhal & Jorge Alberto Soares Tenório

  5. Department of Chemical Engineering, Federal University of Alfenas, ZIP Code, Poços de Caldas, MG, 37715-400, Brazil

    Melina Savioli Lopes

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  1. Julio César de Jesus Gariboti
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  2. Marina Gontijo Souza Macedo
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Contributions

Julio César de Jesus Gariboti was involved in conceptualization, methodology (kinetic analysis), validation, formal analysis, data curation, writing - original draft; Marina Gontijo Souza Macedo helped in conceptualization, methodology (purification and physicochemical characteristics), data curation, writing - original draft; Vinícius Matheus Silva Macedo contributed to methodology (purification and physicochemical characteristics), Yesid Javier Rueda was involved in conceptualization, validation (kinetic analysis), writing- reviewing and editing; Emília Savioli Lopes helped in methodology (production of agro-industrial acid hydrolysis residue); Jonathan Tenorio Vinhal contributed to methodology (TG-QMS analysis), validation, writing - original draft, Eliezer Ladeia Gomes was involved in conceptualization, validation, writing - original draft, supervision; Jorge Alberto Soares Tenório helped in validation, writing - reviewing and editing; Romilda Fernandez Felisbino contributed to validation, writing - original draft, supervision; Melina Savioli Lopes was involved in conceptualization, validation (thermodynamic analysis), writing- reviewing and editing; Laura Plazas Tovar helped in conceptualization, validation, writing - original draft, writing - reviewing and editing, resources, visualization, supervision, funding acquisition and project administration

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Correspondence to Laura Plazas Tovar.

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de Jesus Gariboti, J.C., Macedo, M.G.S., Macedo, V.M.S. et al. Elucidating the thermal decomposition mechanism and pyrolysis characteristics of biorefinery-derived humins from sugarcane bagasse and rice husk. Bioenerg. Res. 15, 2026–2044 (2022). https://doi.org/10.1007/s12155-022-10412-6

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