Bulletin of the Chemical Society of Japan

Целью данного исследования является проверка корреляционного метода Коутса Редферна и разработка нового метода анализа кинетических характеристик для брутто процесса термического разложения пиролизной смолы при неизотермических условиях. Указанный процесс термического преобразования был исследован экспериментально методом термогравиметрического анализа. Существует несколько кинетических моделей, чтобы анализировать механизм пиролиза в терминах формальных реакций. В рамках этого подхода кинетические параметры процесса пиролиза могут быть оценены по данным полной потери массы в процессе нагрева (термогравиметрический анализ – ТГА). Процедура термогравиметрического анализа может проводиться как в изотермических, так и в неизотермических условиях, но всегда экспериментальные данные, полученные в ее процессе, должны быть преобразованы в подходящие корреляционные соотношения. Полученные результаты показали, что реакция пиролиза протекает в диапазоне температур от 540 К до 700, К и индукционный период процесса составляет примерно 224 мин. Кинетические параметры были установлены традиционным методом Коутса –Редферна. Для снижения трудоемкости идентификационных процедур по сравнению с методом Коутса–Редферна и учета наличия индукционного периода реакции был предложен новый метод расчета кинетических параметров. В результате исследования было показано, что по сравнению с методом Коутса –Редферна предложенный способ дает более достоверную зависимость для расчета кинетических параметров. Предложенный метод использует алгоритм Коутса–Редферна для оценки механизма реакции, но величина постоянной скорости реакции определяется непосредственно из получаемых экспериментальных данных о скорости термического превращения.

/pdf/an-innovate-method-of-thermogravimetric-data-analysis-2a3zk6zp69.pdf

An innovate method of thermogravimetric data analysis

This work is pivoted on the implementation of Monte Carlo simulation technique in the thermal decomposition of biomass. Evaluation of kinetic parameters and their effect on the biomass pyrolysis is investigated through proposed integral scheme. Activation energy modeling relies upon the pairing of random points generated through the MATLAB program. The numerical solution of the multireaction model is based on the ratio of numbers of pair points (xi, yi) and the points (i) generated. Thermoanalytical data of chir pine waste are obtained at different heating rates of 5, 10, and 15 °C min–1. The scheme involves the inverse formulation of kinetic model; thus, the kinetic parameters can be more precisely computed than the hit-and trail-methodologies. Rather than speculating the behavior through regression analysis, the experimental thermogravimetric plane provides more correct information. So, the conversion of biomass is converted into the area of curve bounded by the experimental data. For experimental purpo...

Application of Monte Carlo Simulation for Energy Modeling

Experimental and Modeling Investigation on Pyrolysis of Agricultural Biomass Residues: Khat Stem and Coffee Husk for Bio-oil Application

The waste generated by the cocoa industry consists of lignocellulosic material that can be used as a source of energy. To investigate this potential, the pyrolysis of cacao bean shell (CBS) was analyzed through thermogravimetric analysis (TGA) using nitrogen as the carrier gas. The process was performed at four different heating rates (β1 = 20 °C min−1, β2 = 30 °C min−1, β3 = 40 °C min−1, and β4 = 50 °C min−1) from 40 to 600 °C. The CBS degradation process was found to be similar to lignocellulosic biowaste, and the Friedman, Osawa-Flynn-Wall (OFW), and Kissinger-Akahira-Sunose (KAS) isoconversion methods were used to obtain kinetic parameters. The Friedman model had the best fit for the experimental data, and the activation energy (Ea) of the overall process increased with the conversion ratio due to changes from the broken bond reaction in the early stages to the secondary cracking response in the later stages. Due to the complexity of the thermal degradation of CBS, a detailed analysis was made by Fourier deconvolution to analyze the process in each stage of its pseudocomponents. The drying Ea (26.8–58.6 kJ/mol) was determined, along with the Ea of P-extractives (38.2–81.9 kJ/mol), P-hemicellulose (59.5–128.6 kJ/mol), P-cellulose (74.2–159.4 kJ/mol), P-lignin (79.8–173.4 kJ/mol), and carbonaceous degradation (102.2–186.2 kJ/mol). FTIR analysis showed that compounds such as CO2, esters, hydrocarbons, and phenols are released in the gas fraction during CBS pyrolysis. These results are useful for developing phenomenological models of the process and designing reactors to exploit the energetic potential of CBS through pyrolysis. 

Non-isothermal kinetics of cellulose, hemicellulose, and lignin degradation during cocoa bean shell pyrolysis

Thermal behaviour of pine needles (Pinus Roxburghii) is examined through a thermogravimetry technique. The dried samples of pine needles undergo the non isothermal decomposition at temperature range of 308 - 1173 K. The heating rates used for experimental purposes are: 5 °C min-1, 10 °C min-1 and 15 °C min-1. Kinetic parameters of thermal decomposition reactions of pine needles are obtained through the model-free schemes. The estimated values of activation energy and frequency factor derived from Kissinger method are 132.77 kJ mol-1 and 13.15 x107 min-1, respectively. Furthermore, the averaged values of the same kinetics parameters retrieved from the isoconversional methods are 82.38 kJ mol-1 and 74.833 kJ mol-1, 25.42 x1013 min-1 and 13.449 x1010 min-1, respectively. Instead of the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira Sunrose (KAS) schemes, the kinetic parameters derived from the Kissinger method are relatively promising for the thermal decomposition process, since the kinetic parameters are highly affected by intermediate stages and overlapping of the concurrent reaction occurred during pyrolysis.

/pdf/thermo-kinetics-of-forest-waste-using-model-free-methods-26i1kb11hu.pdf

Thermo-kinetics of Forest Waste Using Model-Free Methods

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Thermo-kinetics of Forest Waste Using Model-Free Methods