scholarly journals Comparative Kinetic Analysis of CaCO3/CaO Reaction System for Energy Storage and Carbon Capture

2019 ◽  
Vol 9 (21) ◽  
pp. 4601 ◽  
Author(s):  
Fedunik-Hofman ◽  
Bayon ◽  
Donne
Keyword(s):  
Activation Energy ◽  
Energy Storage ◽  
Kinetic Analysis ◽  
Kinetic Parameters ◽  
Carbon Capture ◽  
Model Fitting ◽  
Reaction System ◽  
Reaction Model ◽  
Activation Energies ◽  
Exponential Factor

The calcium carbonate looping cycle is an important reaction system for processes such as thermochemical energy storage and carbon capture technologies, which can be used to lower greenhouse gas emissions associated with the energy industry. Kinetic analysis of the reactions involved (calcination and carbonation) can be used to determine kinetic parameters (activation energy, pre-exponential factor, and the reaction model), which is useful to translate laboratory-scale studies to large-scale reactor conditions. A variety of methods are available and there is a lack of consensus on the kinetic parameters in published literature. In this paper, the calcination of synthesized CaCO3 is modeled using model-fitting methods under two different experimental atmospheres, including 100% CO2, which realistically reflects reactor conditions and is relatively unstudied kinetically. Results are compared with similar studies and model-free methods using a detailed, comparative methodology that has not been carried out previously. Under N2, an activation energy of 204 kJ mol-1 is obtained with the R2 (contracting area) geometric model, which is consistent with various model-fitting and isoconversional analyses. For experiments under CO2, much higher activation energies (up to 1220 kJ mol-1 with a first-order reaction model) are obtained, which has also been observed previously. The carbonation of synthesized CaO is modeled using an intrinsic chemical reaction rate model and an apparent model. Activation energies of 17.45 kJ mol-1 and 59.95 kJ mol-1 are obtained for the kinetic and diffusion control regions, respectively, which are on the lower bounds of literature results. The experimental conditions, material properties, and the kinetic method are found to strongly influence the kinetic parameters, and recommendations are provided for the analysis of both reactions.

scholarly journals The kinetics of the extraction of caffeine from guarana seed under the action of ultrasonic field with simultaneous cooling

2019 ◽  
Vol 9 (1) ◽  
pp. 26-36 ◽  
Author(s):  
Biljana Koturevic ◽  
Borivoj Adnadjevic ◽  
Jelena Jovanovic
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Reaction System ◽  
Ultrasonic Field ◽  
Conventional Heating ◽  
Isothermal Kinetics ◽  
Correlation Relationship ◽  
Exponential Factor ◽  
Caffeine Extraction ◽  
Kinetics Of

AbstractThe kinetics of isothermal extraction of caffeine from guarana seed under the action of ultrasonic field with simultaneous cooling (UESC) was investigated. The isothermal kinetics curves were measured at temperatures range T = 17-58°C. Using the model-fitting method it was determined that the kinetics of caffeine extraction can be described by a theoretical Jander three-dimensional diffusional model. The values of the rate constant were calculated for different temperatures, as well as the kinetic parameters (activation energy (Ea) and pre-exponential factor (lnA)). Based on the results obtained, it is concluded that the rate constants of caffeine extraction under UESC are about 2 times higher in comparison to the values obtained for the extraction in the conditions of conventional heating (CH). The activation energy of the caffeine extraction under the UESC $\left( E_{\text{a}}\,^{\text{UESC}}=19.4\,\text{kJ}\cdot \text{mo}{{\text{l}}^{-1}} \right)$is lower than the values are for CH $\left( E_{\text{a}}\,^{\text{CH}}=21.8\,\text{kJ}\cdot \text{mo}{{\text{l}}^{-1}} \right).$Energy consumption for UESC is four times lower than for CH conditions. It is shown that there is a linear correlation relationship between kinetic parameters obtained for UESC and CH conditions. The changes in the values of kinetic parameters are explained by the model of selective transfer of energy from the reaction system to the reactant molecules.

scholarly journals Kinetics of Solid-Gas Reactions and Their Application to Carbonate Looping Systems

Energies ◽  
2019 ◽  
Vol 12 (15) ◽  
pp. 2981 ◽  
Author(s):  
Larissa Fedunik-Hofman ◽  
Alicia Bayon ◽  
Scott W. Donne
Keyword(s):  
Kinetic Analysis ◽  
Kinetic Parameters ◽  
Carbon Capture ◽  
Large Scale ◽  
Chemical Engineering ◽  
Kinetic Method ◽  
Experimental Conditions ◽  
Exponential Factor ◽  
Model Free ◽  
Gas Reactions

Reaction kinetics is an important field of study in chemical engineering to translate laboratory-scale studies to large-scale reactor conditions. The procedures used to determine kinetic parameters (activation energy, pre-exponential factor and the reaction model) include model-fitting, model-free and generalized methods, which have been extensively used in published literature to model solid-gas reactions. A comprehensive review of kinetic analysis methods will be presented using the example of carbonate looping, an important process applied to thermochemical energy storage and carbon capture technologies. The kinetic parameters obtained by different methods for both the calcination and carbonation reactions are compared. The experimental conditions, material properties and the kinetic method are found to strongly influence the kinetic parameters and recommendations are provided for the analysis of both reactions. Of the methods, isoconversional techniques are encouraged to arrive at non-mechanistic parameters for calcination, while for carbonation, material characterization is recommended before choosing a specific kinetic analysis method.

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 Kinetics of the Release of Nicotinamide Absorbed on Partially Neutralized Poly(acrylic-co-methacrylic acid) Xerogel under the Conditions of Simultaneous Microwave Heating and Cooling

Gels ◽  
2021 ◽  
Vol 7 (4) ◽  
pp. 193
Author(s):  
Jelena D. Jovanovic ◽  
Borivoj K. Adnadjevic
Keyword(s):  
Kinetic Parameters ◽  
Microwave Heating ◽  
Model Fitting ◽  
Reaction System ◽  
Release Process ◽  
Exponential Factor ◽  
Heating And Cooling ◽  
Different Temperatures ◽  
First Order Chemical Reaction ◽  
Kinetics Of

The kinetics of release of nicotinamide (NIAM) that was absorbed on partially neutralized poly(acrylic-co-methacrylic) (PAM) xerogel/hydrogel, under the conditions of simultaneous microwave heating and cooling (SMHC) were examined. The kinetics curves of NIAM release into an aqueous solution at temperatures of 308–323 K were recorded. By applying the model-fitting method (MFM), it was found that the kinetics of NIAM release can be modeled by a kinetic model of a first-order chemical reaction. The values of the release rate constants (kM) at different temperatures were calculated, and their values were found to be within the range 8.4 10−3 s −1−15.7 10−3 s−1. It has been established that the Arrhenius equation was valid even in the conditions of SMHC. The values of the kinetic parameters (activation energy (Ea) and pre-exponential factor (A) of the NIAM release process adsorbed on PAM xerogel/hydrogel were calculated as follows: Ea = 25.6 kJ/mol and ln (A/s−1) = 5.21. It has been proven that the higher value of the rate constant at SMHC in relation to CH is not a consequence of the overheating of the reaction system or the appearance of “hot-points”. The values of change of the enthalpy of activation (ΔH*) and the change of entropy of activation (ΔS*) were calculated as follows: ΔH* = +23.82 kJ/mol and ΔS* = −201.4 J/mol K. The calculated higher values of the kinetic parameters and thermodynamic parameters of activation are explained by the formation of a specific activated complex under SMHC, whose structure and degree of order are different than in the one formed under CH.

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.

Thermal Cure and Ceramization Kinetics of Perhydropolysilazane

2013 ◽  
Vol 575-576 ◽  
pp. 81-86 ◽  
Author(s):  
Feng Ling Ma ◽  
Hui Min Qi ◽  
Ya Ping Zhu ◽  
Xiao Wen Ren ◽  
Fan Wang
Keyword(s):  
Activation Energy ◽  
Weight Loss ◽  
Thermogravimetric Analysis ◽  
Kinetic Parameters ◽  
Nitrogen Atmosphere ◽  
Thermal Cure ◽  
Exponential Factor ◽  
Kinetics Of

The kinetics of the thermal cure and ceramization of preceramic prehydropolysilazane (PHPS) was investigated by thermogravimetric analysis (TGA) under nitrogen atmosphere. The results indicated that the gases captured during the thermal cure and ceramization process of PHPS, which had three main weight loss events. The corresponding kinetic parameters including activation energy, pre-exponential factor and empirical order of the thermal cure and ceramization stages were evaluated by using Ozawa and Kissinger metnods, respectively.

scholarly journals Activation Energies and Temperature Dependencies of the Rates of Crystallization and Melting of Polymers

Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1070 ◽  
Author(s):  
Sergey Vyazovkin
Keyword(s):  
Experimental Data ◽  
Phase Transition ◽  
Activation Energy ◽  
Temperature Dependence ◽  
Kinetic Analysis ◽  
Review Paper ◽  
Isoconversional Methods ◽  
Activation Energies ◽  
Phase Transition Kinetics ◽  
Kinetic Treatment

The objective of this review paper is to survey the phase transition kinetics with a focus on the temperature dependence of the rates of crystallization and melting, as well as on the activation energies of these processes obtained via the Arrhenius kinetic treatment, including the treatment by isoconversional methods. The literature is analyzed to track the development of the basic models and their underlying concepts. The review presents both theoretical and practical considerations regarding the kinetic analysis of crystallization and melting. Both processes are demonstrated to be kinetically complex, and this is revealed in the form of nonlinear Arrhenius plots and/or the variation of the activation energy with temperature. Principles which aid one to understand and interpret such results are discussed. An emphasis is also put on identifying proper computational methods and experimental data that can lead to meaningful kinetic interpretation.

Kinetics of Carbothermic Reduction of Ilmenite

2016 ◽  
Vol 852 ◽  
pp. 315-322 ◽  
Author(s):  
Min Chen ◽  
Xuan Xiao ◽  
Xue Feng Zhang
Keyword(s):  
Activation Energy ◽  
Kinetic Parameters ◽  
Carbothermic Reduction ◽  
Reduction Process ◽  
Phase Evolution ◽  
Reduction Kinetics ◽  
Isokinetic Relationship ◽  
Exponential Factor ◽  
Morphology Change ◽  
Kinetics Of

The reduction kinetics of ilmenite was investigated. Phase evolution during the reduction process was identified by XRD and morphology change was observed using SEM. Kinetic parameters of the activation energy and pre-exponential factor were determined by Kissinger-Akahira-Sunose (KAS) method and Coast-Redfern method&artificial isokinetic relationship (IKP) respectively. Results showed that when the reaction of titanium suboxides makes a growing contribution, the conversion dependence of activation energy has an ascending trend. When the conversion exceeded 0.7, the reactants almost consumed, and the process was controlled by diffusion.

scholarly journals Thermal and kinetic analysis of pure and contaminated ionic liquid: 1-butyl-2.3-dimethylimidazolium chloride (BDMIMCl)

2016 ◽  
Vol 18 (2) ◽  
pp. 122-125 ◽  
Author(s):  
Ayyaz Muhammad
Keyword(s):  
Activation Energy ◽  
Thermal Stability ◽  
Thermal Decomposition ◽  
Ionic Liquid ◽  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Kinetic Parameters ◽  
Process Design ◽  
Research Work ◽  
Thermal Stability Of

Abstract In this research work, thermal decomposition and kinetic analysis of pure and contaminated imidazolium based ionic liquid (IL) has been investigated. As thermal decomposition and kinetics evaluation plays a pivotal role in effective process design. Therefore, thermal stability of pure 1-butyl-2,3-dimethylimidazolium chloride (BDMIMCl) was found to be higher than the sample of IL with the addition of 20% (wt.) NH4Cl as an impurity. The activation energy of thermal degradation of IL and other kinetic parameters were determined using Coats Redfern method. The activation energy for pure IL was reduced in the presence of NH4Cl as contaminant i.e., from 58.7 kJ/mol to 46.4 kJ/mol.

scholarly journals Kinetic Analysis of Pyrolysis and Thermo-Oxidative Decomposition of Tennis String Nylon Wastes

Materials ◽  
2021 ◽  
Vol 14 (24) ◽  
pp. 7564
Author(s):  
Haibo Wan ◽  
Zhen Huang
Keyword(s):  
Thermal Degradation ◽  
Kinetic Analysis ◽  
Model Fitting ◽  
Degradation Process ◽  
Nylon 6 ◽  
Reaction Model ◽  
Heating Rates ◽  
Model Free ◽  
Order Chemical Reaction ◽  
First Order Chemical Reaction

Thermal degradation of nylon-6 tennis string nylon wastes in inert nitrogen and air atmospheres was investigated by means of multiple heating-rate thermogravimetric analyses. The results obtained under the heating rates of 5–20 K/min are compared in terms of degradation feature and specific temperature for two atmospheres. Using nonisothermal data, kinetic analysis was thoroughly conducted using various isoconversional model-free methods, including Starink, Madhusudanan–Krishnan–Ninan, Tang, Coats–Redfern, and Flynn–Wall–Ozawa methods. With these kinetic analysis methods, the activation energy over the entire degradation process was successfully calculated. By means of the model-fitting master-plots method, the first-order chemical reaction model was determined to be the most appropriate mechanism function for describing pyrolysis and oxidative thermal degradation of nylon-6 waste. Using kinetic parameters, satisfactory matching against experimental data resulted using the Coats–Redfern method for both cases. Furthermore, thermodynamic parameters such as changes in entropy, enthalpy, and Gibbs free energy during thermal degradation processes were evaluated.

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