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A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials

The thermal kinetic modeling is crucial for development of sustainable processes where lignocellulosic fuels are a part of chemical system and their thermal degradation eventuates. In this paper, thermal decomposition of three lignocellulosic materials (bagasse, rice husk, and wheat straw) was obtai...

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Autores principales: Mahmood, Hamayoun, Shakeel, Ahmad, Abdullah, Ammar, Khan, Muhammad Ilyas, Moniruzzaman, Muhammad
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8348937/
https://www.ncbi.nlm.nih.gov/pubmed/34372105
http://dx.doi.org/10.3390/polym13152504
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author Mahmood, Hamayoun
Shakeel, Ahmad
Abdullah, Ammar
Khan, Muhammad Ilyas
Moniruzzaman, Muhammad
author_facet Mahmood, Hamayoun
Shakeel, Ahmad
Abdullah, Ammar
Khan, Muhammad Ilyas
Moniruzzaman, Muhammad
author_sort Mahmood, Hamayoun
collection PubMed
description The thermal kinetic modeling is crucial for development of sustainable processes where lignocellulosic fuels are a part of chemical system and their thermal degradation eventuates. In this paper, thermal decomposition of three lignocellulosic materials (bagasse, rice husk, and wheat straw) was obtained by the thermogravimetric (TG) technique and kinetics was analyzed by both model-fitting and isoconversional (model-free) methods to compare their effectiveness. Two models selected from each class include Arrhenius and Coats–Redfern (model-fitting), and Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) (model-free). The formal model-fitting approach simulating the thermal decomposition of solids by assuming a fixed mechanism was found to be unduly facile. However, activation energy (E) values calculated from two model-fitting techniques were considerably different from each other with a percentage difference in the range of 1.36% to 7.65%. Particularly, both model-fitting methods predicted different reaction mechanism for thermal disintegration of lignocellulosic materials (two-dimensional diffusion (D2) by Arrhenius and one-dimensional diffusion (D1) by Coat–Redfern method). Conversely, the model-free routine offers a transformation of mechanism and activation energy values throughout reaction and is, therefore, more authentic to illustrate the complexity of thermal disintegration of lignocellulosic particles. Based on the model-free kinetic analysis, the lignocellulosic materials may be devised in following order of activation energy: rice husk > bagasse > wheat straw, by both KAS and FWO methods with a percentage difference no more than 0.84% for fractional conversion up to 0.7. Isoconversional approach could be recommended as more realistic and precise for modeling non-isothermal kinetics of lignocellulosic residues compared to model-fitting approach.
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spelling pubmed-83489372021-08-08 A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials Mahmood, Hamayoun Shakeel, Ahmad Abdullah, Ammar Khan, Muhammad Ilyas Moniruzzaman, Muhammad Polymers (Basel) Article The thermal kinetic modeling is crucial for development of sustainable processes where lignocellulosic fuels are a part of chemical system and their thermal degradation eventuates. In this paper, thermal decomposition of three lignocellulosic materials (bagasse, rice husk, and wheat straw) was obtained by the thermogravimetric (TG) technique and kinetics was analyzed by both model-fitting and isoconversional (model-free) methods to compare their effectiveness. Two models selected from each class include Arrhenius and Coats–Redfern (model-fitting), and Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) (model-free). The formal model-fitting approach simulating the thermal decomposition of solids by assuming a fixed mechanism was found to be unduly facile. However, activation energy (E) values calculated from two model-fitting techniques were considerably different from each other with a percentage difference in the range of 1.36% to 7.65%. Particularly, both model-fitting methods predicted different reaction mechanism for thermal disintegration of lignocellulosic materials (two-dimensional diffusion (D2) by Arrhenius and one-dimensional diffusion (D1) by Coat–Redfern method). Conversely, the model-free routine offers a transformation of mechanism and activation energy values throughout reaction and is, therefore, more authentic to illustrate the complexity of thermal disintegration of lignocellulosic particles. Based on the model-free kinetic analysis, the lignocellulosic materials may be devised in following order of activation energy: rice husk > bagasse > wheat straw, by both KAS and FWO methods with a percentage difference no more than 0.84% for fractional conversion up to 0.7. Isoconversional approach could be recommended as more realistic and precise for modeling non-isothermal kinetics of lignocellulosic residues compared to model-fitting approach. MDPI 2021-07-29 /pmc/articles/PMC8348937/ /pubmed/34372105 http://dx.doi.org/10.3390/polym13152504 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Mahmood, Hamayoun
Shakeel, Ahmad
Abdullah, Ammar
Khan, Muhammad Ilyas
Moniruzzaman, Muhammad
A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title_full A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title_fullStr A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title_full_unstemmed A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title_short A Comparative Study on Suitability of Model-Free and Model-Fitting Kinetic Methods to Non-Isothermal Degradation of Lignocellulosic Materials
title_sort comparative study on suitability of model-free and model-fitting kinetic methods to non-isothermal degradation of lignocellulosic materials
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8348937/
https://www.ncbi.nlm.nih.gov/pubmed/34372105
http://dx.doi.org/10.3390/polym13152504
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