scholarly journals Kinetic analysis of CO2 gasification of biochar and anthracite based on integral isoconversional nonlinear method

2020 ◽  
Vol 39 (1) ◽  
pp. 527-538
Author(s):  
Bing Dai ◽  
Jia-Yong Qiu ◽  
Shan Ren ◽  
Bu-Xin Su ◽  
Xiang Ding ◽  
...  
Keyword(s):  
Activation Energy ◽  
Early Stage ◽  
Model Fitting ◽  
Preexponential Factor ◽  
Single Step ◽  
Conversion Degree ◽  
Nonlinear Method ◽  
Gasification Reactivity ◽  
Model Free ◽  
Gasification Process

AbstractThe nonisothermal thermogravimetric analysis was implemented for gasification of sawdust char (SD-char), wheat straw char (WS-char), rice husk char (RH-char), bamboo char (BB-char) and anthracite coal (AC) in the presence of CO2. The dependence of activation energy upon conversion for different biochars and AC was obtained by the integral isoconversional nonlinear (NL-INT) method which is a model-free method. Based on the activation energy values from the NL-INT method, a model-fitting method called random pore model (RPM) was used to estimate the kinetic parameters including the preexponential factor and pore structure parameter from the experimental data. The results are shown that the gasification reactivity of different samples from high to low can be sorted as that of WS-char, SD-char, BB-char, RH-char and AC. In the early stage of gasification, the activation energy values of biochars increase generally with an increase in the conversion degree, whereas the value of AC decreases. Thereafter, the activation energy values remain almost unchanged when the conversion is up to some extent. When the conversion degree varies between about 0.3 and 0.9, these carbon materials can be sorted in the order of average activation energy from low to high as WS-char, SD-char, AC, RH-char and BB-char, respectively, 134.3, 143.8, 168.5, 184.8 and 193.0 kJ/mol. It is shown that a complex multistep mechanism occurs in the initial stage of gasification, while a single-step gasification mechanism exists in the rest of the gasification process. The RPM is suitable for describing the gasification of biomass chars and AC except the initial gasification. Additionally, it is found that the kinetic compensation effect (KCE) still exists in the gasification reactions of biochars and AC. However, the AC deviates markedly from the KCE curve. This may be caused by the similarity of carbonaceous structure of biochars and the difference in reactivity between biochars and AC.

scholarly journals Kinetic Analysis of Digestate Slow Pyrolysis with the Application of the Master-Plots Method and Independent Parallel Reactions Scheme

Molecules ◽  
2019 ◽  
Vol 24 (9) ◽  
pp. 1657 ◽  
Author(s):  
Pietro Bartocci ◽  
Roman Tschentscher ◽  
Ruth Elisabeth Stensrød ◽  
Marco Barbanera ◽  
Francesco Fantozzi
Keyword(s):  
Activation Energy ◽  
Kinetic Analysis ◽  
Single Step ◽  
Conversion Degree ◽  
Pyrolysis Process ◽  
Average Value ◽  
Model Free ◽  
Master Plots Method ◽  
Master Plots ◽  
Parallel Reactions

The solid fraction obtained by mechanical separation of digestate from anaerobic digestion plants is an attractive feedstock for the pyrolysis process. Especially in the case of digestate obtained from biogas plants fed with energy crops, this can be considered a lignin rich residue. The aim of this study is to investigate the pyrolytic kinetic characteristics of solid digestate. The Starink model-free method has been used for the kinetic analysis of the pyrolysis process. The average Activation Energy value is about 204.1 kJ/mol, with a standard deviation of 25 kJ/mol, which corresponds to the 12% of the average value. The activation energy decreased along with the conversion degree. The variation range of the activation energy is about 99 kJ/mol, this means that the average value cannot be used to statistically represent the whole reaction. The Master-plots method was used for the determination of the kinetic model, obtaining that n-order was the most probable one. On the other hand, the process cannot be modeled with a single-step reaction. For this reason it has been used an independent parallel reactions scheme to model the complete process.

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.

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 Kinetic analysis of the pyrolysis of apricot stone and its main components via distributed activation energy mode

BioResources ◽  
2020 ◽  
Vol 15 (1) ◽  
pp. 1187-1204
Author(s):  
Huanhuan Ma ◽  
Yimeng Zhang ◽  
Liangcai Wang ◽  
Zhengxiang Zhu ◽  
Yu Chen ◽  
...  
Keyword(s):  
Activation Energy ◽  
Energy Distribution ◽  
Apparent Activation Energy ◽  
Early Stage ◽  
Conversion Degree ◽  
Heating Rates ◽  
Continuous Increase ◽  
Thermogravimetric Analyzer ◽  
Energy Mode ◽  
Main Components

The kinetics of pyrolysis of apricot stone and its main components, i.e., lignin, cellulose, and hemicellulose, were investigated via distributed activation energy mode. Experiments were done in a thermogravimetric analyzer at heating rates of 10, 20, 30, and 40 K·min-1 under nitrogen. The activation energy distribution peaks for the apricot stone, lignin, cellulose, and hemicellulose were centered at 246, 318, 364, and 170 kJ·mol-1, respectively. The activation energy distribution for the apricot stone slightly changed; lignin exhibited the widest distribution; and cellulose exhibited the highest activation energy at a conversion degree (α) of less than 0.75. At low pyrolysis temperatures (400 K to 600 K), the pyrolysis of hemicellulose was the main pyrolysis reaction. The apparent activation energy for the apricot stone mainly depended on the pyrolysis of hemicellulose and a small amount of lignin, and the activation energy was low in the early stage of pyrolysis. With the continuous increase in the pyrolysis temperatures (600 K to 660 K), the thermal weight loss of cellulose and lignin was intense. The apparent activation energy for the apricot stone mainly resulted from the pyrolysis of cellulose and lignin, and a higher activation energy was observed in the later stage of pyrolysis.

scholarly journals Thermal decomposition of potassium titanium oxalate

2011 ◽  
Vol 76 (7) ◽  
pp. 1015-1026 ◽  
Author(s):  
Karuvanthodi Muraleedharan ◽  
Labeeb Pasha
Keyword(s):  
Carbon Dioxide ◽  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Model Fitting ◽  
Nitrogen Atmosphere ◽  
Single Step ◽  
Heating Rates ◽  
Decomposition Stage ◽  
Model Free ◽  
Good Agreement

The thermal decomposition of potassium titanium oxalate (PTO) was studied using non-isothermal thermogravimetry at different heating rates under a nitrogen atmosphere. The thermal decomposition of PTO proceeds mainly through five stages forming potassium titanate. The theoretical and experimental mass loss data are in good agreement for all stages of the thermal decomposition of PTO. The third thermal decomposition stage of PTO, the combined elimination of carbon monoxide and carbon dioxide, were subjected to kinetic analyses both by the method of model fitting and by the model free approach, which is based on the isoconversional principle. The model free analyses showed that the combined elimination of carbon monoxide and carbon dioxide and formation of final titanate in the thermal decomposition of PTO proceeds through a single step with an activation energy value of about 315 kJ mol-1.

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.

Kinetic Studies on the Thermal Synthesis of Fluorapatite: Model Free and Model-Fitting Methods

2018 ◽  
Vol 28 ◽  
pp. 75-89
Author(s):  
Hamid Reza Javadinejad ◽  
Sayed Ahmad Hosseini ◽  
Mohsen Saboktakin Rizi ◽  
Eiman Aghababaei ◽  
Hossein Naseri
Keyword(s):  
Activation Energy ◽  
Model Fitting ◽  
Kinetic Studies ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Heating Rates ◽  
Thermal Synthesis ◽  
Exponential Factor ◽  
Model Free ◽  
Master Plots

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.

scholarly journals Determining Preexponential Factor in Model-Free Kinetic Methods: How and Why?

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3077
Author(s):  
Sergey Vyazovkin
Keyword(s):  
Activation Energy ◽  
Kinetic Analysis ◽  
Rate Constant ◽  
Condensed Phase ◽  
Compensation Effect ◽  
Preexponential Factor ◽  
Isoconversional Methods ◽  
Activation Entropy ◽  
Model Free ◽  
Kinetics Of

The kinetics of thermally stimulated processes in the condensed phase is commonly analyzed by model-free techniques such as isoconversional methods. Oftentimes, this type of analysis is unjustifiably limited to probing the activation energy alone, whereas the preexponential factor remains unexplored. This article calls attention to the importance of determining the preexponential factor as an integral part of model-free kinetic analysis. The use of the compensation effect provides an efficient way of evaluating the preexponential factor for both single- and multi-step kinetics. Many effects observed experimentally as the reaction temperature shifts usually involve changes in both activation energy and preexponential factor and, thus, are better understood by combining both parameters into the rate constant. A technique for establishing the temperature dependence of the rate constant by utilizing the isoconversional values of the activation energy and preexponential factor is explained. It is stressed that that the experimental effects that involve changes in the preexponential factor can be traced to the activation entropy changes that may help in obtaining deeper insights into the process kinetics. The arguments are illustrated by experimental examples.

scholarly journals Effect of Pyrolysis Atmosphere on the Gasification of Waste Tire Char

Energies ◽  
2021 ◽  
Vol 15 (1) ◽  
pp. 34
Author(s):  
Przemysław Grzywacz ◽  
Grzegorz Czerski ◽  
Wojciech Gańczarczyk
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Inert Atmosphere ◽  
Argon Atmosphere ◽  
Conversion Degree ◽  
Heating Rates ◽  
Mean Values ◽  
Co2 Gasification ◽  
Gasification Process ◽  
Lower Reactivity

The aim of the study is to assess the influence of the atmosphere during pyrolysis on the course of CO2 gasification of a tire waste char. Two approaches were used: the pyrolysis step was carried out in an inert atmosphere of argon (I) or in an atmosphere of carbon dioxide (II). The examinations were carried out in non-isothermal conditions using a Rubotherm DynTherm thermobalance in the temperature range of 20–1100 °C and three heating rates: 5, 10 and 15 K/min. Based on the results of the gasification examinations, the TG (Thermogravimetry) and DTG (Derivative Thermogravimetry) curves were developed and the kinetic parameters were calculated using the KAS (Kissinger-Akahira-Sunose) and FWO (Flynn-Wall-Ozawa) methods. Additionally, the CO2 gasification of tire chars reaction order (n), was evaluated, and the kinetic parameters were calculated with the use of Coats and Redfern method. Tire waste char obtained in an argon atmosphere was characterized by lower reactivity, which was reflected in shift of conversion and DTG curves to higher temperatures and higher mean values of activation energy. A variability of activation energy values with the progress of the reaction was observed. For char obtained in an argon atmosphere, the activation energy varied in the range of 191.1–277.2 kJ/mol and, for a char obtained in an atmosphere of CO2, in the range of 148.0–284.8 kJ/mol. The highest activation energy values were observed at the beginning of the gasification process and the lowest for the conversion degree 0.5–0.7.

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