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Model-free rate expression for thermal decomposition processes: The case of microcrystalline cellulose pyrolysis
KTH Royal Institute of Technology.
KTH Royal Institute of Technology.ORCID iD: 0000-0002-0252-337X
KTH Royal Institute of Technology.ORCID iD: 0000-0001-7995-3151
KTH Royal Institute of Technology.
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2015 (English)In: Fuel, ISSN 0016-2361, E-ISSN 1873-7153, Vol. 143, p. 438-447Article in journal (Refereed) Published
Abstract [en]

We explore the possibility to derive a completely model-free rate expression using isoconversional methods. The Friedman differential method (Friedman, 1964) and the incremental integral method by Vyazovkin (2001) were both extended to allow for an estimation of not only the apparent activation energy but also the effective kinetic prefactor, defined as the product of the pre-exponential factor and the conversion function. Analyzing experimental thermogravimetric data for the pyrolytic decomposition of microcrystalline cellulose, measured at six different heating rates and three different initial sample masses (1.5-10 mg), revealed the presence of secondary char forming reactions and thermal lag, both increasing with increased sample mass. Conditioning of the temperature function enables extraction of more reliable prefactors and we found that the derived kinetic parameters show weak dependence on initial sample mass. Finally, by successful modeling of quasi-isothermal experimental curves, we show that the discrete rate expression estimated from linear heating rate experiments enables modeling of the thermal decomposition rate without any assumptions regarding the chemical process present. These findings can facilitate the design and optimization of industrial isothermal biomass fed reactors.

Place, publisher, year, edition, pages
2015. Vol. 143, p. 438-447
Keywords [en]
Model-free, Isoconversional, Kinetics, Thermogravimetric analysis, Pyrolysis, Cellulose
National Category
Energy Engineering
Identifiers
URN: urn:nbn:se:his:diva-15872DOI: 10.1016/j.fuel.2014.11.079ISI: 000347688700052Scopus ID: 2-s2.0-84918767293OAI: oai:DiVA.org:his-15872DiVA, id: diva2:1228964
Funder
Swedish Energy AgencyAvailable from: 2015-02-27 Created: 2018-06-29 Last updated: 2018-08-15Bibliographically approved

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Moriana, Rosana

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CiteExportLink to record
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