scholarly journals Kinetic Analysis of Low-Rank Coal Pyrolysis by Model-Free and Model-Fitting Methods

2019 ◽  
Vol 2019 ◽  
pp. 1-7 ◽  
Author(s):  
Qiuli Zhang ◽  
Min Luo ◽  
Long Yan ◽  
Aiwu Yang ◽  
Xiangrong Hui
Keyword(s):  
Model Fitting ◽  
Decomposition Reaction ◽  
Low Rank ◽  
Coal Pyrolysis ◽  
Pyrolysis Kinetics ◽  
Heating Rates ◽  
Pyrolysis Characteristics ◽  
Model Free ◽  
Thermal Analyzer ◽  
Thermogravimetric Data

Coal SJC, coal WJG, coal ZJM, and coal HCG were selected to investigate the pyrolysis kinetics of northern Shaanxi coals. TG and DSC experiments of four coals were carried out with a synchronous thermal analyzer at heating rates 5, 10, 15, and 20 C/min, respectively. The pyrolysis characteristics were described by thermogravimetric data, and the kinetic parameters were calculated by Flynn–Wall–Ozawa (FWO), Kissinger, general integration, and MacCallum–Tanner methods. The results show that coal SJC, coal ZJM, and coal HCG all conform to the reaction series equation, the thermal decomposition reaction rate is controlled by chemical reaction, and coal WJG conforms to Avrami–Erofeev equation. The activation energies of the four coals are 177.53 kJ/mol, 200.34 kJ/mol, 158.59 kJ/mol, and 240.47 kJ/mol, respectively.

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.

Comparative study on the pyrolysis kinetics of polyurethane foam from waste refrigerators

2019 ◽  
Vol 38 (3) ◽  
pp. 271-278 ◽  
Author(s):  
Zhitong Yao ◽  
Shaoqi Yu ◽  
Weiping Su ◽  
Weihong Wu ◽  
Junhong Tang ◽  
...  
Keyword(s):  
Activation Energy ◽  
Polyurethane Foam ◽  
Model Fitting ◽  
Energy Model ◽  
Pyrolysis Kinetics ◽  
Ozawa Method ◽  
Heating Rates ◽  
Distributed Activation Energy Model ◽  
Model Free ◽  
Kinetics Of

Thermal treatment offers advantages of significant volume reduction and energy recovery for the polyurethane foam from waste refrigerators. In this work, the pyrolysis kinetics of polyurethane foam was investigated using the model-fitting, model-free and distributed activation energy model methods. The thermogravimetric analysis indicated that the polyurethane foam decomposition could be divided into three stages with temperatures of 38°C–400°C, 400°C–550°C and 550°C–1000°C. Peak temperatures for the major decomposition stage (<400°C) were determined as 324°C, 342°C and 344°C for heating rates of 5, 15 and 25 K min-1, respectively. The activation energy ( Eα) from the Friedman, Flynn–Wall–Ozawa and Tang methods increased with degree of conversion ( α) in the range of 0.05 to 0.5. The coefficients from the Flynn–Wall–Ozawa method were larger and the resulted Eα values fell into the range of 163.980–328.190 kJ mol-1 with an average of 206.099 kJ mol-1. For the Coats–Redfern method, the diffusion models offered higher coefficients, but the E values were smaller than that from the Flynn–Wall–Ozawa method. The Eα values derived from the distributed activation energy model method were determined as 163.536–334.231 kJ mol-1, with an average of 206.799 kJ mol-1. The peak of activation energy distribution curve was located at 205.929 kJ mol-1, consistent with the thermogravimetric results. The Flynn–Wall–Ozawa and distributed activation energy model methods were more reliable for describing the polyurethane foam pyrolysis process.

scholarly journals Pyrolysis Kinetic Properties of Thermal Insulation Waste Extruded Polystyrene by Multiple Thermal Analysis Methods

Materials ◽  
2020 ◽  
Vol 13 (24) ◽  
pp. 5595
Author(s):  
Ang Li ◽  
Wenlong Zhang ◽  
Juan Zhang ◽  
Yanming Ding ◽  
Ru Zhou
Keyword(s):  
Reaction Mechanism ◽  
Thermal Insulation ◽  
Conversion Rate ◽  
Model Fitting ◽  
Pso Algorithm ◽  
Energy Utilization ◽  
Kinetic Properties ◽  
Insulation Material ◽  
Heating Rates ◽  
Model Free

Extruded polystyrene (XPS) is a thermal insulation material extensively applied in building systems. It has attracted much attention because of outstanding thermal insulation performance, obvious flammability shortcoming and potential energy utilization. To establish the reaction mechanism of XPS’s pyrolysis, thermogravimetric experiments were performed at different heating rates in nitrogen, and multiple methods were employed to analyze the major kinetics of pyrolysis. More accurate kinetic parameters of XPS were estimated by four common model-free methods. Then, three model-fitting methods (including the Coats-Redfern, the iterative procedure and masterplots method) were used to establish the kinetic model. Since the kinetic models established by the above three model-fitting methods were not completely consistent based on different approximations, considering the effect of different approximates on the model, the reaction mechanism was further established by comparing the conversion rate based on the model-fitting methods corresponding to the possible reaction mechanisms. Finally, the accuracy of the above model-fitting methods and Particle Swarm Optimization (PSO) algorithm were compared. Results showed that the reaction function g(α) = (1 − α)−1 − 1 might be the most suitable to characterize the pyrolysis of XPS. The conversion rate calculated by masterplots and PSO methods could provide the best agreement with the experimental data.

scholarly journals Kinetic studies on the pyrolysis of plastic waste using a combination of model-fitting and model-free methods

2020 ◽  
Vol 38 (1_suppl) ◽  
pp. 77-85 ◽  
Author(s):  
Zhitong Yao ◽  
Shaoqi Yu ◽  
Weiping Su ◽  
Weihong Wu ◽  
Junhong Tang ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Thermogravimetric Analysis ◽  
Compensation Effect ◽  
Model Fitting ◽  
Plastic Waste ◽  
Plastic Shell ◽  
Ozawa Method ◽  
Heating Rates ◽  
Helium Atmosphere ◽  
Model Free

In this work, the pyrolysis behavior of plastic waste—TV plastic shell—was investigated, based on thermogravimetric analysis and using a combination of model-fitting and model-free methods. The possible reaction mechanism and kinetic compensation effects were also examined. Thermogravimetric analysis indicated that the decomposition of plastic waste in a helium atmosphere can be divided into three stages: the minor loss stage (20–300°C), the major loss stage (300–500°C) and the stable loss stage (500–1000°C). The corresponding weight loss at three different heating rates of 15, 25 and 35 K/min were determined to be 2.80–3.02%, 94.45–95.11% and 0.04–0.16%, respectively. The activation energy ( Ea) and correlation coefficient ( R2) profiles revealed that the kinetic parameters calculated using the Friedman and Kissinger–Akahira–Sunose method displayed a similar trend. The values from the Flynn–Wall–Ozawa and Starink methods were comparable, although the former gave higher R2 values. The Eα values gradually decreased from 269.75 kJ/mol to 184.18 kJ/mol as the degree of conversion ( α) increased from 0.1 to 0.8. Beyond this range, the Eα slightly increased to 211.31 kJ/mol. The model-fitting method of Coats–Redfern was used to predict the possible reaction mechanism, for which the first-order model resulted in higher R2 values than and comparable Eα values to those obtained from the Flynn–Wall–Ozawa method. The pre-exponential factors (ln A) were calculated based on the F1 reaction model and the Flynn–Wall–Ozawa method, and fell in the range 59.34–48.05. The study of the kinetic compensation effect confirmed that a compensation effect existed between Ea and ln A during the plastic waste pyrolysis.

Pyrolysis Characteristics and Kinetics of Low Rank Coal

2011 ◽  
Vol 695 ◽  
pp. 493-496 ◽  
Author(s):  
Yong Hui Song ◽  
Jian Mei She ◽  
Xin Zhe Lan ◽  
Jun Zhou
Keyword(s):  
Weight Loss ◽  
Heating Rate ◽  
Frequency Factor ◽  
Low Rank ◽  
Coal Pyrolysis ◽  
Pyrolysis Characteristics ◽  
Second Stage ◽  
Thermo Gravimetric Analyzer ◽  
Kinetics Of ◽  
Pyrolysis Kinetic

The pyrolysis characteristics of Jianfanggou(JFG) coal was studied using a thermo-gravimetric analyzer and the pyrolysis kinetic parameters were calculated at the different heating rate. The results showed the DTG curves under different heating rate had three peaks and the corresponding temperature were 100°C, 470°C and 750°C, the pyrolysis process can be divided into three stages conclusively. The maximum weight loss rate at 470°C indicated the major weight loss occurred in the second stage. The Tb, Tf and T∞ obtained under experiment situation. The results of the JFG coal pyrolysis kinetic showed the Tb, Tf and T∞ increased gradually with the accretion of the heating rate. In the meantime, the variation of frequency factor was consistent with the trend of activation energy.

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.

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 Determination of Kinetic Parameters for the Thermal Decomposition of Parthenium hysterophorus

2018 ◽  
Vol 22 (1) ◽  
pp. 5-21 ◽  
Author(s):  
Alok Dhaundiyal ◽  
Suraj B. Singh ◽  
Muammel M. Hanon ◽  
Rekha Rawat
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Model Fitting ◽  
Frequency Factor ◽  
Heating Rates ◽  
Model Free ◽  
Higher Temperature ◽  
Good Agreement ◽  
Maximum Weight Loss

Abstract A kinetic study of pyrolysis process of Parthenium hysterophorous is carried out by using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation and determination of the kinetic parameters such as activation E and the frequency factor A using model-free methods given by Flynn Wall and Ozawa (FWO), Kissinger-Akahira-Sonuse (KAS) and Kissinger, and model-fitting (Coats Redfern). The results derived from thermal decomposition process demarcate decomposition of Parthenium hysterophorous among the three main stages, such as dehydration, active and passive pyrolysis. It is shown through DTG thermograms that the increase in the heating rate caused temperature peaks at maximum weight loss rate to shift towards higher temperature regime. The results are compared with Coats Redfern (Integral method) and experimental results have shown that values of kinetic parameters obtained from model-free methods are in good agreement. Whereas the results obtained through Coats Redfern model at different heating rates are not promising, however, the diffusion models provided the good fitting with the experimental data.

Study on the Pyrolysis Characteristics and Mechanism of KCl-Pretreated Sunflower Stalk

2013 ◽  
Vol 448-453 ◽  
pp. 1665-1674
Author(s):  
Dong Yu Chen ◽  
Qing Yu Liu ◽  
Yan Qing Hu
Keyword(s):  
Activation Energy ◽  
Heating Rate ◽  
Three Dimensional ◽  
Kinetic Mechanism ◽  
Metal Salts ◽  
Pyrolysis Kinetics ◽  
Heating Rates ◽  
Energy Value ◽  
Pyrolysis Characteristics ◽  
Mechanism Model

To study the influence of KCl pretreating on the pyrolysis kinetics of sunflower stalk, the pyrolysis of sunflower stalk pretreated by different concentration KCl solutions were performed by nonisothermal thermogravimetric analysis (TGA) at five different heating rates. The Ozawa and Kissinger methods were employed to calculate the activation energy and the Šatava method was used to obtain the kinetic mechanism model. The results showed that the pyrolysis process of the sunflower stalk pretreated by 3% and 10% KCl solution can be separated into four stages (water loss, depolymerization and vitrification, thermal decomposition, and carbonization). With the heating rate increasing, the main pyrolysis zone of the TG (thermogravimetric) and DTG curves move to the higher temperature direction, and the maximum pyrolysis rate and its corresponding temperature increase too. Adding a small amount of metal salts is conducive to the formation of volatile, and a certain amount of metal salts can improve the charcoal yield. More KCl additive makes the lower activation energy value, and the obtained activation energy value increases with the heating rate increasing. By means of the Šatava method, the kinetic mechanism model for the pyrolysis of KCl-pretreated sunflower stalk is Zhuralev-Lesakin-Tempelman equation, which is three-dimensional diffusion.

scholarly journals Catalytic Pyrolysis Kinetic Behavior and TG-FTIR-GC–MS Analysis of Metallized Food Packaging Plastics with Different Concentrations of ZSM-5 Zeolite Catalyst

Polymers ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 702 ◽  
Author(s):  
Justas Eimontas ◽  
Nerijus Striūgas ◽  
Mohammed Ali Abdelnaby ◽  
Samy Yousef
Keyword(s):  
Food Packaging ◽  
Catalytic Pyrolysis ◽  
Zeolite Catalyst ◽  
Chemical Degradation ◽  
Pyrolysis Process ◽  
Pyrolysis Kinetics ◽  
Heating Rates ◽  
High Concentration ◽  
Model Free ◽  
Energy Products

Recently, the pyrolysis process has been adapted as a sustainable strategy to convert metallized food packaging plastics waste (MFPW) into energy products (paraffin wax, biogas, and carbon black particles) and to recover aluminum. Usually, catalysts are used in pyrolysis treatment to refine pyrolysis products and to increase their yield. In order to study the effect of a catalyst on the formulated volatile products, this work aims to study the pyrolysis behavior of MFPW in presence of catalyst, using TG-FTIR-GC–MS system. The pyrolysis experiments were conducted with ZSM-5 Zeolite catalyst with different concentrations (10, 30, and 50 wt.%) at different heating rates (5, 10, 15, 20, 25, and 30 °C/min). In addition, TG-FTIR system and GC-MS unit were used to observe and analyze the thermal and chemical degradation of the obtained volatile compounds at maximum decomposition peaks. In addition, the kinetic results of catalytic pyrolysis of ZSM-5/MFPW samples matched when model-free methods, a distributed activation energy model (DAEM), and an independent parallel reaction kinetic model (IPR) were used. The TGA-DTG results showed that addition of a catalyst did not have a significant effect on the features of the TGA-DTG curves with similar weight loss of 87–90 wt.% (without taking the weight of the catalyst into account). Meanwhile, FTIR results manifested strong presence of methane and high-intensity functional group of carboxylic acid residues, especially at high concentration of ZSM-5 and high heating rates. Likewise, GC-MS measurements showed that Benzene, Toluene, Hexane, p-Xylene, etc. compounds (main flammable liquid compounds in petroleum oil) generated catalysts exceeding 50%. Finally, pyrolysis kinetics showed that the whole activation energies of catalytic pyrolysis process of MFPW were estimated at 289 kJ/mol and 110, 350, and 174 kJ/mol for ZSM-5/MFPW samples (10, 30, and 50 wt.%, respectively), whereas DAEM and IPR approaches succeeded to simulate TGA and DTG profiles with deviations below <1.

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