scholarly journals Determination of Thermodynamic Parameters of Polylactic Acid by Thermogravimetry under Pyrolysis Conditions

2021 ◽  
Vol 11 (21) ◽  
pp. 10192
Author(s):  
Paul Palmay ◽  
Melissa Mora ◽  
Diego Barzallo ◽  
Joan Carles Bruno
Keyword(s):  
Activation Energy ◽  
Heating Rate ◽  
Thermodynamic Parameters ◽  
Polylactic Acid ◽  
Reaction Model ◽  
Raw Material ◽  
Heating Rates ◽  
Statistical Validation ◽  
Exponential Factor ◽  
Degradation Temperature

In the present study, the thermodynamic parameters of Polylactic Acid (PLA) under conditions of thermal degradation were determined. The PLA material, previously sampled and characterized, was analyzed by dynamic thermogravimetry (TG) at heating rates of 5, 10 and 15 °C min−1 with a nitrogen flow of 20 mL min−1 from a temperature of 25 to 900 °C. The data were treated using isoconversional kinetic models to obtain the activation energy and the pre-exponential factor of each model. To fit the DTG curves, the Arrhenius equation was used applying the Contraction Sphere reaction model: two-dimensional phase limit reaction (R2). The thermodynamic parameters such as enthalpy, Gibbs free energy and entropy were determined from the kinetic parameters of suitable models for each heating rate after statistical validation and comparison with other studies. The results showed that as the heating rate increases, the degradation temperature also increases, while the activation energy, enthalpy and pre-exponential factor decrease. According to the value of ∆G (171.65 kJ mol−1), PLA has a significant potential to be used as a raw material to produce bioenergy/biofuels by pyrolysis.

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 A Modified Model for Kinetic Analysis of Petroleum Coke

2019 ◽  
Vol 2019 ◽  
pp. 1-8
Author(s):  
Iman Eslami Afrooz ◽  
Dennis Ling Chuan Ching
Keyword(s):  
Activation Energy ◽  
Distribution Function ◽  
Normal Distribution ◽  
Heating Rate ◽  
Reaction Model ◽  
Normal Distribution Function ◽  
Gravimetric Analysis ◽  
Heating Rates ◽  
Shrinking Core ◽  
Volume Reaction

In this study, a nonisothermal kinetics analysis of petcoke was performed at heating rates of 10, 15, and 20°C/min using thermal gravimetric analysis (TGA). The behaviour of petcoke at different gasification stages (dewatering, volatilization, char burning, and burnout) was studied. The effect of heating rate on the activation energy of petcoke gasification was also investigated. The activation energy of petcoke was estimated using different kinetic models that include volume reaction model (VRM), shrinking core model (SCM), random pore model (RPM), Coats and Redfern model (CRM), and normal distribution function (NDF). The NDF model was modified in this study. It was found that the experimental data were best fitted with the modified normal distribution function (MNDF) and SCM. The results also showed that activation energy decreases as heating rate increases, leading to reduction in gasification completion time.

Thermogravimetric Analysis of Superabsorbing Polyacrylic Hydrogel

2005 ◽  
Vol 494 ◽  
pp. 193-198 ◽  
Author(s):  
B. Janković ◽  
B. Adnadjević ◽  
J. Jovanović ◽  
D. Minić ◽  
Lj. Kolar-Anić
Keyword(s):  
Activation Energy ◽  
Distribution Function ◽  
Thermogravimetric Analysis ◽  
Weibull Distribution ◽  
Heating Rate ◽  
Rate Constant ◽  
Heating Rates ◽  
Exponential Factor ◽  
Weibull Distribution Function ◽  
Thermogravimetric Curve

The thermogravimetric analysis of superabsorbing polyacrylic hydrogel dehydration, performed under non-isothermal conditions at different heating rates was discussed. Particularly, the influence of the heating rate on the obtained results is given in detail. For this purpose the Weibull distribution function was applied. The thermogravimetric curve when the heating rate tends to zero was evaluated. The activation energy E = 63 kJ/mol, pre-exponential factor A = 2.97 × 108 min−1, and rate constant k = 2.76 × 10−3 min−1 were determined on the basis of this curve.

scholarly journals Apparent Pyrolysis Kinetics and Index-Based Assessment of Pretreated Peach Seeds

Processes ◽  
2021 ◽  
Vol 9 (6) ◽  
pp. 905
Author(s):  
Angelos-Ikaros Altantzis ◽  
Nikolaos-Christos Kallistridis ◽  
George Stavropoulos ◽  
Anastasia Zabaniotou
Keyword(s):  
Activation Energy ◽  
Industrial Sector ◽  
Reaction Model ◽  
Specific Rate ◽  
Atmospheric Conditions ◽  
Pyrolysis Kinetics ◽  
Heating Rates ◽  
Hexane Extraction ◽  
Exponential Factor ◽  
Different Temperatures

To better understand pyrolysis for upscaling purposes, a kinetic characterization of the process is necessary for every feedstock. Laboratory experiments allow identification of apparent kinetic models. This paper aims at the apparent kinetic investigation of peach seeds’ slow pyrolysis. Peach seeds from Greek peach fruits pyrolyzed under inert atmospheric conditions at different temperatures (475–785 °C), heating rates (100–250 °C/min) and N2 flow rates (25–200 cc/min). Prior to pyrolysis, they submitted to hexane extraction for the recovery of 36.8% wt. of the contained oils. Determination of the specific rate constant (k) and activation energy (Ea) for each considered reaction was made by using the Coats–Redfern integral non-isothermal fitting model that requires an assumption of the reaction order (n). Results revealed that a 3rd order reaction model best fits the process, the increasing of the pyrolysis temperature leads to a decrease of the activation energy (E) and pre-exponential factor (A), while nitrogen flow rate and heating rate had an opposite impact. E and A values ranged from 23 to 56 kJ/mol and 1.82 × 106 to 1.13 × 106 min−1, respectively, at different pyrolysis conditions. Furthermore, estimation of combustion and pyrolysis indexes were made to assess the suitability of peach seeds as a fuel, using isothermal thermogravimetric analyses (TGA). Results revealed that peach seeds are a suitable feedstock for pyrolysis, while prior submission of peach seeds to oils extraction, in a cascade biorefinery approach, can increase the energy and material recovery efficiency and potentially the environmental and economic benefit of the agri-food industrial sector.

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.

Studies on the Thermal Decomposition Kinetic of an Nitrate Ester

2012 ◽  
Vol 182-183 ◽  
pp. 1575-1580 ◽  
Author(s):  
Juan Wang ◽  
Da Bin Liu ◽  
Xin Li Zhou
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Decomposition Mechanism ◽  
Thermal Decomposition Mechanism ◽  
Decomposition Kinetic ◽  
Heating Rates ◽  
Exponential Factor ◽  
Nitrate Ester ◽  
Dynamic Function ◽  
Thermal Decomposition Kinetic

The certain nitrate ester explosive has been tested by TG at the heating rates of 10, 15, 20, 25K•min-1. Basing on the TG experiment results the thermal decomposition activation energy has been calculated by the methods of Ozawa, KAS and iteration. And the thermal decomposition mechanism function of the explosive with 38 kinds of dynamic function was deduced by the method of integration. The results show that the thermal decomposition mechanism of the nitrate ester is chemical reaction mechanism. The thermal decomposition kinetic parameters such as average activation energy Ea and pre-exponential factor A are 133.23×103 J•mol-1 and 3.191×107 s-1 respectively.

scholarly journals Investigation of Non-Isothermal Kinetics and Thermodynamic Parameters for the Pyrolysis of Different Date Palm Parts

Energies ◽  
2020 ◽  
Vol 13 (24) ◽  
pp. 6553
Author(s):  
Emmanuel Galiwango ◽  
Ali H. Al-Marzuoqi ◽  
Abbas A. Khaleel ◽  
Mahdi M. Abu-Omar
Keyword(s):  
Activation Energy ◽  
Thermodynamic Parameters ◽  
Date Palm ◽  
Energy Content ◽  
High Energy ◽  
Biomass Energy ◽  
Isothermal Kinetics ◽  
Potential Candidate ◽  
Heating Rates ◽  
Average Percentage

Using the thermalgravimetric technique, we investigated the non-isothermal combustion kinetics of abundant and low-cost date palm wastes (leaflet, rachis, fibers, and their composite) as potential biomass energy sources. The kinetic and thermodynamic parameters were determined by Flynn–Wall–Ozawa (FWO), Kissinger–Akahila–Sunose (KAS), and Starink methods. Thermogravimetric analysis results showed a major peak for the degradation of volatiles between 127–138 °C with average percentage mass loss of 68.04 ± 1.5, 65.57 ± 0.6, 62.97 ± 5.5, and 59.26 ± 3.2, for rachis, composite, leaflet, and fibers, respectively. The FWO model showed the lowest activation energy, Eα, of 157 ± 25.6, 158 ± 25.7, 164 ± 40.1, and 169 ± 51.8 kJ mol−1 for the composite, rachis, leaflet, and fibers, respectively. The positive enthalpy values confirmed an endothermic pyrolysis reaction. For all models, a minimal difference of 4.40, 5.57, 6.55, and 7.51 kJ mol−1 between activation energy and enthalpy for rachis, fibers, composite, and leaflet ensued, respectively. The KAS model was best suited to describe chemical equilibrium with average ΔG values of 90.3 ± 28.8, 99.3 ± 34.9, 178.9 ± 27.3, and 186.5 ± 38.2 kJ mol−1 for rachis, fibers, composite, and leaflet, respectively. The reaction mechanism by the Malek and Popescu methods was ((g(α)=[−ln(1−α)]14) across the conversion range of 0.1–0.9 for all heating rates. The high energy content and volatile matter combined with low energy barriers make date palm waste a potential candidate in a biorefinery.

scholarly journals Kinetic Analysis of the Thermal Degradation of Recycled Acrylonitrile-Butadiene-Styrene by non-Isothermal Thermogravimetry

Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 281 ◽  
Author(s):  
Rafael Balart ◽  
David Garcia-Sanoguera ◽  
Luis Quiles-Carrillo ◽  
Nestor Montanes ◽  
Sergio Torres-Giner
Keyword(s):  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Acrylonitrile Butadiene Styrene ◽  
Isoconversional Methods ◽  
Reaction Model ◽  
Integral Model ◽  
Heating Rates ◽  
Exponential Factor ◽  
Model Free ◽  
Butadiene Styrene

This work presents an in-depth kinetic study of the thermal degradation of recycled acrylonitrile-butadiene-styrene (ABS) polymer. Non-isothermal thermogravimetric analysis (TGA) data in nitrogen atmosphere at different heating rates comprised between 2 and 30 K min−1 were used to obtain the apparent activation energy (Ea) of the thermal degradation process of ABS by isoconversional (differential and integral) model-free methods. Among others, the differential Friedman method was used. Regarding integral methods, several methods with different approximations of the temperature integral were used, which gave different accuracies in Ea. In particular, the Flynn-Wall-Ozawa (FWO), the Kissinger-Akahira-Sunose (KAS), and the Starink methods were used. The results obtained by these methods were compared to the Kissinger method based on peak temperature (Tm) measurements at the maximum degradation rate. Combined Kinetic Analysis (CKA) was also carried out by using a modified expression derived from the general Sestak-Berggren equation with excellent results compared with the previous methods. Isoconversional methods revealed negligible variation of Ea with the conversion. Furthermore, the reaction model was assessed by calculating the characteristic and functions and comparing them with some master plots, resulting in a nth order reaction model with n = 1.4950, which allowed calculating the pre-exponential factor (A) of the Arrhenius constant. The results showed that Ea of the thermal degradation of ABS was 163.3 kJ mol−1, while ln A was 27.5410 (A in min−1). The predicted values obtained by integration of the general kinetic expression with the calculated kinetic triplet were in full agreement with the experimental data, thus giving evidence of the accuracy of the obtained kinetic parameters.

scholarly journals Thermal Analysis On The Kinetics Of Magnesium-Aluminum Layered Double Hydroxides In Different Heating Rates

2015 ◽  
Vol 60 (2) ◽  
pp. 1357-1359 ◽  
Author(s):  
Y. Hongbo ◽  
C. Meiling ◽  
W. Xu ◽  
G. Hong
Keyword(s):  
Activation Energy ◽  
Thermal Analysis ◽  
Layered Double Hydroxides ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Exponential Factor ◽  
Thermal Kinetic Parameters ◽  
Double Hydroxides ◽  
Kinetics Of ◽  
Dsc Curves

Abstract The thermal decomposition of magnesium-aluminum layered double hydroxides (LDHs) was investigated by thermogravimetry analysis and differential scanning calorimetry (DSC) methods in argon environment. The influence of heating rates (including 2.5, 5, 10, 15 and 20K/min) on the thermal behavior of LDHs was revealed. By the methods of Kissinger and Flynn-Wall-Ozawa, the thermal kinetic parameters of activation energy and pre-exponential factor for the exothermic processes under non-isothermal conditions were calculated using the analysis of corresponding DSC curves.

scholarly journals Thermodynamic model and kinetic compensation effect of oil sludge pyrolysis based on thermogravimetric analysis

2020 ◽  
pp. 350-350
Author(s):  
Hui Liu ◽  
Chenglang Xiang ◽  
Jie Mu ◽  
Jieyu Yao ◽  
Dong Ye ◽  
...  
Keyword(s):  
Activation Energy ◽  
Apparent Activation Energy ◽  
Compensation Effect ◽  
Thermodynamic Characteristics ◽  
Oil Sludge ◽  
High Heating Rate ◽  
Thermodynamic Models ◽  
Heating Rates ◽  
Kinetic Compensation Effect ◽  
Exponential Factor

Oil sludge (OS) is an organic solid waste in the petrochemical industry and improper treatment of OS will cause environmental pollution. Pyrolysis is an effective way to realize its resource reuse. In order to understand the pyrolysis behavior and thermodynamic characteristics of OS, four OS samples from storage tanks were used as the research object, and pyrolysis experiments were carried out at heating rates of 5, 10, and 15?/min under a nitrogen atmosphere. The kinetic parameters of pyrolysis of OS are calculated by three equal conversion methods (Friedman method (FR), Flynn-Wall-Ozawa method (FWO) and Distributed activation energy model (DAEM)), and the most possible thermodynamic models for the main pyrolysis phase were analyzed and discussed by introducing the Malek method. The results show: High heating rate can promote the pyrolysis of OS; In the pyrolysis stage, the apparent activation energy increases with the increase of the conversion rate. The apparent activation energy calculated by the FR method is more reliable. The average apparent activation energies of the four OS are 221.23, 84.71, 94.67 and 116.56 kJ/mol, respectively. The apparent activation energy and the pre-exponential factor are positively correlated, indicating that there is a kinetic compensation effect in the pyrolysis process. The thermodynamic models of the four OS samples are all three-dimensional diffusion models, but their integral functions are different. The research results can provide theoretical support for the industrialization, harmlessness and resource utilization of OS pyrolysis.

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