An iterative model-free method to determine the activation energy of heterogeneous processes under arbitrary temperature programs

2011 ◽  
Vol 523 (1-2) ◽  
pp. 84-89 ◽  
Author(s):  
P. Budrugeac
Keyword(s):  
Activation Energy ◽  
Arbitrary Temperature ◽  
Model Free ◽  
Iterative Model ◽  
Heterogeneous Processes

Thermo-catalytic decomposition of polystyrene waste: Comparative analysis using different kinetic models

2019 ◽  
Vol 38 (2) ◽  
pp. 202-212 ◽  
Author(s):  
Ghulam Ali ◽  
Jan Nisar ◽  
Munawar Iqbal ◽  
Afzal Shah ◽  
Mazhar Abbas ◽  
...  
Keyword(s):  
Activation Energy ◽  
Copper Oxide ◽  
Solid Waste ◽  
Thermodynamic Parameters ◽  
Model Fitting ◽  
Catalytic Decomposition ◽  
Decomposition Reaction ◽  
Inert Atmosphere ◽  
Heating Rates ◽  
Model Free

Due to a huge increase in polymer production, a tremendous increase in municipal solid waste is observed. Every year the existing landfills for disposal of waste polymers decrease and the effective recycling techniques for waste polymers are getting more and more important. In this work pyrolysis of waste polystyrene was performed in the presence of a laboratory synthesized copper oxide. The samples were pyrolyzed at different heating rates that is, 5°Cmin−1, 10°Cmin−1, 15°Cmin−1 and 20°Cmin−1 in a thermogravimetric analyzer in inert atmosphere using nitrogen. Thermogravimetric data were interpreted using various model fitting (Coats–Redfern) and model free methods (Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman). Thermodynamic parameters for the reaction were also determined. The activation energy calculated applying Coats–Redfern, Ozawa–Flynn–Wall, Kissinger–Akahira–Sunose and Friedman models were found in the ranges 105–148.48 kJmol−1, 99.41–140.52 kJmol−1, 103.67–149.15 kJmol−1 and 99.93–141.25 kJmol−1, respectively. The lowest activation energy for polystyrene degradation in the presence of copper oxide indicates the suitability of catalyst for the decomposition reaction to take place at lower temperature. Moreover, the obtained kinetics and thermodynamic parameters would be very helpful in determining the reaction mechanism of the solid waste in a real system.

Physicochemical Characterization and Pyrolysis Kinetic Study of Sugarcane Bagasse Using Thermogravimetric Analysis

2016 ◽  
Vol 138 (5) ◽  
Author(s):  
Anil Kumar Varma ◽  
Prasenjit Mondal
Keyword(s):  
Activation Energy ◽  
Sugarcane Bagasse ◽  
Physicochemical Characterization ◽  
Maximum Error ◽  
Proximate Analysis ◽  
Pyrolysis Kinetics ◽  
Exponential Factor ◽  
Physiochemical Properties ◽  
Model Free ◽  
Complex Process

The present study was conducted to investigate the physicochemical properties and pyrolysis kinetics of sugarcane bagasse (SB). The physiochemical properties of SB were determined to examine its potential for pyrolysis. The physiochemical properties such as proximate analysis, ultimate analysis, heating values, lignocellulosic composition, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) of SB were investigated. The pyrolysis experiments were conducted in a nonisothermal thermogravimetric analyzer (TGA) to understand the thermal degradation behavior of SB. The activation energy (Ea) of SB pyrolysis was calculated by model-free Kissinger–Akahira–Sunose (KAS) and Ozawa–Flynn–Wall (OFW) methods. Average values of activation energy determined through KAS and OFW methods are found as 91.64 kJ/mol and 104.43 kJ/mol, respectively. Variation in the activation energy with degree of conversion was observed, which shows that pyrolysis is a complex process composed of several reactions. Coats–Redfern method was used to calculate the pre-exponential factor and reaction order. Conversion of SB due to heat treatment computed by using the kinetic parameters is found to be in good agreement with the experimental conversion data, and the maximum error limit between the experimental and predicted conversions is 8.5% for 5 °C/min, 6.0% for 10 °C/min, and 11.6% for 20 °C/min. The current investigation proves the suitability of SB as a potential feedstock for pyrolysis.

scholarly journals Dynamic Model-Free and Model-Fitting Kinetic Analysis during Torrefaction of Oil Palm Frond Pellets

2020 ◽  
Vol 15 (1) ◽  
pp. 253-263
Author(s):  
Sharmeela Matali ◽  
Norazah Abd Rahman ◽  
Siti Shawalliah Idris ◽  
Nurhafizah Yaacob
Keyword(s):  
Activation Energy ◽  
Thermal Degradation ◽  
Oil Palm ◽  
Model Fitting ◽  
Integral Model ◽  
Model Free ◽  
Solid Biofuel ◽  
Oil Palm Frond ◽  
Kinetics Of ◽  
Palm Frond

Torrefaction is a thermal conversion method extensively used for improving the properties of biomass. Usually this process is conducted within a temperature range of 200-300 °C under an inert atmosphere with residence time up to 60 minutes. This work aimed to study the kinetic of thermal degradation of oil palm frond pellet (OPFP) as solid biofuel for bioenergy production. The kinetics of OPFP during torrefaction was studied using frequently used iso-conversional model fitting (Coats-Redfern (CR)) and integral model-free (Kissinger-Akahira-Sunose (KAS)) methods in order to provide effective apparent activation energy as a function of conversion. The thermal degradation experiments were conducted at four heating rates of 5, 10, 15, and 20 °C/min in a thermogravimetric analyzer (TGA) under non-oxidative atmosphere. The results revealed that thermal decomposition kinetics of OPFP during torrefaction is significantly influenced by the severity of torrefaction temperature. Via Coats-Redfern method, torrefaction degradation reaction mechanism follows that of reaction order with n = 1. The activation energy values were 239.03 kJ/mol and 109.28 kJ/mol based on KAS and CR models, respectively. Copyright © 2020 BCREC Group. All rights reserved 

scholarly journals The Glass Transition Temperature and Temperature Dependence of Activation Energy of Viscous Flow of Ovalbumin

2016 ◽  
Vol 39 (1) ◽  
pp. 13-25
Author(s):  
Karol Monkos
Keyword(s):  
Activation Energy ◽  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Viscous Flow ◽  
Solvent Interactions ◽  
Model Free ◽  
Free Volume Model ◽  
Wide Range ◽  
Different Temperatures

Abstract The paper presents the results of viscosity determinations on aqueous solutions of ovalbumin at a wide range of concentrations and at temperatures ranging from 5°C to 55°C. On the basis of these measurements and three models of viscosity for glass-forming liquids: Avramov’s model, free-volume model and power-law model, the activation energy of viscous flow for solutions and ovalbumin molecules, at different temperatures, was calculated. The obtained results show that activation energy monotonically decreases with increasing temperature both for solutions and ovalbumin molecules. The influence of the energy of translational heat motion, protein-protein and protein-solvent interactions, flexibility and hydrodynamic radius of ovalbumin on the rate of decrease in activation energy with temperature has been discussed. One of the parameters in the Avramov’s equation is the glass transition temperature Tg. It turns out that the Tg of ovalbumin solutions increases with increasing concentration. To obtain the glass transition temperature of the dry ovalbumin, a modified Gordon-Taylor equation is used. Thus determined the glass transition temperature for dry ovalbumin is equal to (231.8 ± 6.1) K.

scholarly journals Pyrolytic characteristics and kinetics of Guanzhong wheat straw and its components for high-value products

BioResources ◽  
2021 ◽  
Vol 16 (1) ◽  
pp. 1958-1979
Author(s):  
Bingtao Hu ◽  
Zhaolin Gu ◽  
Junwei Su ◽  
Zhijian Li
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Wheat Straw ◽  
Pyrolysis Products ◽  
Transportation Fuels ◽  
Temperature Range ◽  
Model Free ◽  
System A ◽  
Gas Products ◽  
Kinetics Of

Wheat straw produced annually in the Shaanxi Guanzhong region is a potential biomass feedstock for the production of transportation fuels and specialized chemicals through combustion, pyrolysis, or gasification. In this work, the pyrolytic characteristics, evolved gas products, and kinetics of Guanzhong wheat straw and its components were first investigated with a thermogravimetry-Fourier infrared spectroscopy (TG-FTIR) system. A comparative kinetic study was conducted using different model-free methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Kissinger, and the Coats-Redfern methods. The main pyrolysis products identified by FTIR include H2O, CH4, CO2, and CO as well as aromatics, acids, ketones, and aldehydes. Kinetic results showed that the pyrolytic apparent activation energy of the straw is approximately 200 kJ/mol obtained via FWO and KAS methods at the conversion range of 0.4 to 0.75, which was 30 kJ/mol higher than the value 171.1 kJ/mol obtained by the Kissinger method. The apparent activation energy of cellulose in its main pyrolysis region is 135.5 kJ/mol and is about three times larger than that of hemicellulose (49.5 kJ/mol). The apparent activation energy of lignin at the temperature range of 45 to 116 °C was 34.5 kJ/mol, while that value at the temperature range of 120 to 252 °C was 6.64 kJ/mol.

MODEL FREE KINETICS ANALYSIS OF IMPERATA CYLINDRICA (LALANG)

2016 ◽  
Vol 78 (8-3) ◽  
Author(s):  
Olagoke Oladokun ◽  
Arshad Ahmad ◽  
Tuan Amran Tuan Abdullah ◽  
Bemgba Bevan Nyakuma ◽  
Syie Luing Wong
Keyword(s):  
Activation Energy ◽  
Biomass Conversion ◽  
Frequency Factor ◽  
Isoconversional Methods ◽  
Green Energy ◽  
Imperata Cylindrica ◽  
Heating Rates ◽  
Model Free ◽  
Solid Biofuel ◽  
Kinetics Of

This study is the first attempt at investigating the solid state decomposition and the devolatilization kinetics of Imperata cylindrica (lalang) grass termed the “farmer’s nightmare weed” as a potential solid biofuel of the future. Biomass conversion technologies such as pyrolysis and gasification can be utilized for future green energy needs. However an important step in the efficient utilization and process optimizing of biomass conversion processes is understanding the thermal decomposition kinetics of the feedstock. Consequently, thermogravimetric analysis (TGA) of Imperata cylindrica was carried out in the temperature range of 30-1000 °C at four heating rates of 5, 10, 15, and 20 K min-1 using Nitrogen at a flow rate of 20 L min-1 as purge gas. Using the TGA results, the kinetic parameters activation energy (Ea) and pre-exponential frequency factor (ko) of the grass were estimated via the model free or isoconversional methods of Kissinger and Starink. The results obtained for Kissinger model were 151.36 kJ moI-1 and 5.83 x 109 min-1 for activation energy and pre-exponential frequency factor respectively. However, Starink model activation energy and pre-exponential frequency factor were a function of conversion (α) with average values of 159.93 kJ mol-1 and 6.33 x 1022 min-1 respectively. 

scholarly journals Thermal Decomposition Behavior of Melaminium Benzoate Dihydrate

2013 ◽  
Vol 2013 ◽  
pp. 1-6 ◽  
Author(s):  
N. Kanagathara ◽  
M. K. Marchewka ◽  
K. Pawlus ◽  
S. Gunasekaran ◽  
G. Anbalagan
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Effective Activation Energy ◽  
Preexponential Factor ◽  
Effective Activation ◽  
Heating Rates ◽  
Monoclinic System ◽  
Model Free ◽  
Thermal Decomposition Behavior ◽  
Decomposition Behavior

Crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by slow solvent evaporation method at room temperature. Powder X-ray diffraction analysis confirms that MBDH crystallizes in the monoclinic system (C2/c). Thermal decomposition behavior of MBDH has been studied by thermogravimetric analysis at three different heating rates: 10, 15, and 20°C/min. Nonisothermal studies of MBDH revealed that the decomposition occurs in three stages. The values of effective activation energy (Ea) and preexponential factor (ln A) of each stage of thermal decomposition for all heating rates were calculated by model free methods: Arrhenius, Flynn-Wall, Friedman, Kissinger, and Kim-Park methods. A significant variation of effective activation energy (Ea) with conversion (α) indicates that the process is kinetically complex. The linear relationship between the A and Ea values was established (compensation effect). Avrami-Erofeev model (A3), contracting cylinder (R2), and Avrami-Erofeev model (A4) were accepted by stages I, II, and III, respectively. DSC has also been performed.

Evaluation of Kinetic Parameter Calculation Methods for Non-Isothermal Experiments in Case of Varying Activation Energy in Solid-State Transformations / Neizotermisko Eksperimentu Kinētisko Parametru Noteikšanas Metožu Izvērtēšana Mainīgas Aktivācijas Enerģijas Gadījumā Cietfāžu Pārvērtībām

2012 ◽  
Vol 51 (3) ◽  
pp. 209-227 ◽  
Author(s):  
A. Bērziņš ◽  
A. Actiņš
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Kinetic Model ◽  
Kinetic Models ◽  
Frequency Factor ◽  
Conversion Degree ◽  
Model Free ◽  
Determination Methods ◽  
Model Determination ◽  
Energy Determination

Simulations of solid-state transformation kinetics were carried out calculating temperature and conversion degree for non-isothermal experiments with different heating rates. Simulations were divided in two parts: with constant and with variable activation energy. Simulations were analyzed with widely used model-based and model-free activation energy determination methods, frequency factor and kinetic model determination methods. Much of the attention was devoted to the calculation of kinetic models and frequency factors, as a more difficult and less developed step. For simulations where activation energy did not change all activation energy determination methods were found to give correct results. However, much attention should be devoted to frequency factor determination, because incorrect results would lead to problems in determination of kinetic models. For simulations where activation energy changes, correct activation energy can be determined only by differential methods or integral methods using numerical integration over small intervals. Isokinetic relationship coefficients b and c were more accurately determined with the average linear integral method. Correct kinetic model determination was possible only when coefficients b and c were accurate, and only by analyzing results of all available methods.

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