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.

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.

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 Application of Artificial Neural Networks to Predict the Catalytic Pyrolysis of HDPE Using Non-Isothermal TGA Data

Polymers ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1813 ◽  
Author(s):  
Mohammed Al-Yaari ◽  
Ibrahim Dubdub
Keyword(s):  
Thermogravimetric Analysis ◽  
Catalytic Pyrolysis ◽  
Model Fitting ◽  
Main Reaction ◽  
Ann Model ◽  
Heating Rates ◽  
Highly Efficient ◽  
Model Free ◽  
Artificial Neural ◽  
Artificial Neural Network Ann

This paper presents a comprehensive kinetic study of the catalytic pyrolysis of high-density polyethylene (HDPE) utilizing thermogravimetric analysis (TGA) data. Nine runs with different catalyst (HZSM-5) to polymer mass ratios (0.5, 0.77, and 1.0) were performed at different heating rates (5, 10, and 15 K/min) under nitrogen over the temperature range 303–973 K. Thermograms showed clearly that there was only one main reaction region for the catalytic cracking of HDPE. In addition, while thermogravimetric analysis (TGA) data were shifted towards higher temperatures as the heating rate increased, they were shifted towards lower temperatures and polymer started to degrade at lower temperatures when the catalyst was used. Furthermore, the activation energy of the catalytic pyrolysis of HDPE was obtained using three isoconversional (model-free) models and two non-isoconversional (model-fitting) models. Moreover, a set of 900 input-output experimental TGA data has been predicted by a highly efficient developed artificial neural network (ANN) model. Results showed a very good agreement between the ANN-predicted and experimental values (R2 > 0.999). Besides, A highly-efficient performance of the developed model has been reported for new input data as well.

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 Thermal Decomposition Kinetic Study of Non-Recyclable Paper and Plastic Waste by Thermogravimetric Analysis

2021 ◽  
Vol 5 (3) ◽  
pp. 54
Author(s):  
Ahmad Mohamed S. H. Al-Moftah ◽  
Richard Marsh ◽  
Julian Steer
Keyword(s):  
Power Generation ◽  
Thermal Decomposition ◽  
Thermogravimetric Analysis ◽  
Thermal Treatment ◽  
Solid Waste ◽  
Heating Rate ◽  
Heating Rates ◽  
Exponential Factor ◽  
Model Free ◽  
Treatment Processes

The global net emissions of the Kyoto Protocol greenhouse gases (GHG), such as carbon dioxide (CO2), fluorinated gases, methane (CH4), and nitrous oxide (N2O), remain substantially high, despite concerted efforts to reduce them. Thermal treatment of solid waste contributes at least 2.8–4% of the GHG in part due to increased generation of municipal solid waste (MSW) and inefficient treatment processes, such as incineration and landfill. Thermal treatment processes, such as gasification and pyrolysis, are valuable ways to convert solid materials, such as wastes into syngas, liquids, and chars, for power generation, fuels, or for the bioremediation of soils. Subcoal™ is a commercial product based on paper and plastics from the source segregated waste that is not readily recyclable and that would otherwise potentially find its way in to landfills. This paper looks at the kinetic parameters associated with this product in pyrolysis, gasification, and combustion conditions for consideration as a fuel for power generation or as a reductant in the blast furnace ironmaking process. Thermogravimetric Analysis (TGA) in Nitrogen (N2), CO2, and in air, was used to measure and compare the reaction kinetics. The activation energy (Ea) and pre-exponential factor A were measured at different heating rates using non-isothermal Ozawa Flynn Wall and (OFW) and Kissinger-Akahira-Sonuse (KAS) model-free techniques. The TGA curves showed that the thermal degradation of Subcoal™ comprises three main processes: dehydration, devolatilization, and char and ash formation. In addition, the heating rate drifts the devolatilization temperature to a higher value. Likewise, the derivative thermogravimetry (DTG) results stated that Tm degradation increased as the heating rate increased. Substantial variance in Ea was noted between the four stages of thermal decomposition of Subcoal™ on both methods. The Ea for gasification reached 200.2 ± 33.6 kJ/mol by OFW and 179.0 ± 31.9 kJ/mol by KAS. Pyrolysis registered Ea values of 161.7 ± 24.7 kJ/mol by OFW and 142.6 ± 23.5 kJ/mol by KAS. Combustion returned the lowest Ea values for both OFW (76.74 ± 15.4 kJ/mol) and KAS (71.0 ± 4.4 kJ/mol). The low Ea values in combustion indicate shorter reaction time for Subcoal™ degradation compared to gasification and pyrolysis. Generally, TGA kinetics analysis using KAS and OFW methods show good consistency in evaluating Arrhenius constants.

Thermogravimetric Analysis and Kinetic Study on Catalytic Pyrolysis of Rice Husk Pellet using Its Ash as a Low-cost In-situ Catalyst

2021 ◽  
Vol 11 (1) ◽  
pp. 207-219
Author(s):  
Wusana Agung Wibowo ◽  
Rochim Bakti Cahyono ◽  
Rochmadi Rochmadi ◽  
Arief Budiman
Keyword(s):  
Thermogravimetric Analysis ◽  
Rice Husk ◽  
Catalytic Effect ◽  
Low Cost ◽  
Weight Ratio ◽  
Nitrogen Atmosphere ◽  
Energy Of Activation ◽  
Heating Rates ◽  
Decomposition Stage ◽  
Model Free

The thermogravimetric behaviors and the kinetic parameters of uncatalyzed and catalyzed pyrolysis processes of a mixture of powdered raw rice husk (RRH) and its ash (RHA) in the form of pellets were determined by thermogravimetric analysis at three different heating rates, i.e., 5, 10, and 20 K/min, from 303 to 873 K. This research aimed to prove that the rice husk ash has a catalytic effect on rice husk pyrolysis. To investigate the catalytic effect of RHA, rice husk pellets (RHP) with the weight ratio of RRH:ARH of 10:2 were used as the sample. Model-free methods, namely Friedman (FR), Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO), were used to calculate the apparent energy of activation ( ). The thermogravimetric analysis showed that the decomposition of RHP in a nitrogen atmosphere could be divided into three stages: drying stage (303-443 K), the rapid decomposition stage (443-703 K), and the slow decomposition stage (703-873 K). The weight loss percentages of each stage for both uncatalyzed and catalyzed pyrolysis of RHP were 2.4-5.7%, 35.5-59.4%, and 2.9-12.2%, respectively. Using the FR, FWO, and KAS methods, the values of  for the degrees of conversion (a) of 0.1 to 0.65 were in the range of 168-256 kJ/mol for the uncatalyzed pyrolysis and 97-204 kJ/mol for the catalyzed one. We found that the catalyzed pyrolysis led the  to have values lower than those got by the uncatalyzed one. This phenomenon might prove that RHA has a catalytic effect on RHP pyrolysis by lowering the energy of activation.

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.

Thermogravimetric Analysis of KCl-Pretreated Soybean Stalk

2015 ◽  
Vol 1092-1093 ◽  
pp. 118-121
Author(s):  
Dong Yu Chen ◽  
Qing Yu Liu
Keyword(s):  
Activation Energy ◽  
Thermogravimetric Analysis ◽  
Metal Salts ◽  
Pyrolysis Kinetics ◽  
Ozawa Method ◽  
Heating Rates ◽  
Energy Value ◽  
Lower Activation ◽  
Higher Temperature ◽  
Kinetics Of

To study the influence of KCl pretreating on the pyrolysis kinetics of soybean stalk, the pyrolysis of soybean stalk pretreated by different concentration KCl solutions were performed by nonisothermal thermogravimetric analysis (TGA) at five different heating rates. The Ozawa method was employed to calculate the activation energy. The results showed that the pyrolysis process of the soybean 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 region, and the maximum pyrolysis rate and its corresponding temperature increase too. A small amount of metal salts addition 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 reaction degree.

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.

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