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Kinetics, thermodynamics, and combustion characteristics of Poinciana pods using TG/DTG/DTA techniques

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Abstract

The combustion behavior, chemical kinetics, and thermodynamic parameters of Poinciana cover and Poinciana seeds were investigated using TGA at different heating rates in the air atmosphere. Kinetic characteristic parameters were estimated by adopting five traditional and parallel kinetic models besides the DTA technique. Functional group properties using FTIR were presented and discussed. The physicochemical characteristics of these materials assured their bioenergy potential for conversion into valuable, sustainable, and renewable energy resources. The activation energy values calculated from DTA measurements for Poinciana cover and seeds were found to be in good agreement with the kinetic data obtained by parallel methods using TGA data. The significant variations of the values of the pre-exponential factor of the Poinciana cover confirm the presence of a complex multi-step reaction during its combustion. DTG profiles of the Poinciana cover showed one sharp peak with a high mass loss rate value in a short time required high energy and resulted in high activation energy values. Also, the high ash content of this material resisted the oxygen diffusion and delayed the ignition which in turn played a key role in raising the activation energy values. The higher volatile content of Poinciana seeds and its high IR absorbance helped in lowering the activation energy values obtained from various models. Advanced ignition and delayed burnout give the Poinciana seeds superiority over Poinciana cover as a new alternative source of energy. The Gibbs free energy (ΔG) values of Poinciana seed material are higher than those of Poinciana cover either for the total conversion process of the volatiles and char conversion. This result reflects the bioenergy potential of Poinciana seeds through oxidation. The resulted high entropy change (\(\Delta S\)) values for the poinciana cover material ensure that this material is far from its thermodynamic equilibrium and its reactivity is high.

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Abbreviations

\({\alpha }_{cal}\) :

The conversion value calculated from the regression equation

\({\alpha }_{exp,i}\) :

Experimental fractional conversion corresponding to the temperature \((T_{i})\) 

\({\alpha }_{model,i}\) :

The conversion value calculated from the model at temperature \(T_{i}\) 

\({\left({~}^{dm}\!\left/ \!\!{~}_{dt}\right.\right)}_{ av}\) :

Average mass loss rate under oxidative atmosphere at temperatures ranged from \(T_{ig}\) to \(T_{bo}\), \(\%/min\)   

\({\left({~}^{dm}\!\left/ \!\!{~}_{dt}\right.\right)}_{ peak}\) :

Maximum combustion rate, \(\%/min\) 

\({\left({~}^{dm}\!\left/ \!\!{~}_{dt}\right.\right)}_{DTG, peak}\) :

Maximum rate of mass loss, \(\%/min\) 

\({\Delta T}_{0.5}\) :

Temperature range of \(({(dm/dt)}_{DTG,peak}/{(dm/dt)}_{peak})=0.5\), °C

\({\Delta t}_{0.5}\) :

Time range \(({(dm/dt)}_{DTG,peak}/{(dm/dt)}_{peak})=0.5\) , \(min\) 

\({{\alpha }}_{\text{vol}}\) :

Volatiles conversion fraction, %

\({{\alpha }}_{ch}\) :

Char conversion fraction, %

\({C}_{si}\) :

Combustion stability index, \(\%/min\;^\circ C^2\)  

\({D}_{bo}\) :

Burnout index, \(\%/min^4\) 

\({D}_{i}\) :

Ignition index, \(\%/min^3\) 

E :

Activation energy \((kJ/mole)\) 

\({E}_{ch}\) :

Char activation energy, kJ/mole

\({E}_{dir}\) :

Direct activation energy of the decomposition reaction, kJ /mole

\({E}_{fit}\) :

Activation energy of the decomposition reaction obtained from the fitting method, kJ /mole

\({E}_{vol}\) :

Volatiles activation energy, kJ/mole

\({H}_{f}\) :

Combustion intensity \(^\circ C\) 

\({K}_{B}\) :

Boltzmann constant, \(1.381\times10^{-23}\;J/K\) 

\({P}_{g}\) :

Partial pressure of the reactive gas, Pa

\({R}_{M}\) :

Reactivity, \(\%/min\;^\circ C\) 

S :

Comprehensive combustion index \((\%/{min}^2\;^\circ C^3)\) ,

\({S}_{c, o}\) :

Initial specific surface area of raw material, \(cm^2/gm\) 

\({S}_{c}\) :

Specific surface area of the produced char, \(cm^2/gm\) 

T o :

Initial temperature, °C

\({T}_{bo}\) :

Burnout temperature, °C 

\({T}_{ig}\) :

Ignition temperature, ℃

\({T}_{in}\) :

Temperature of the beginning of the phase transition process, K

\({T}_{peak}\) :

Temperature corresponding to the maximum rate of mass loss, ℃

\({c}_{ch}\) :

Mass fraction of char in the biomass material, %

\({c}_{vol}\) :

Mass fraction of volatiles in the biomass material, %

\({k}_{o, ch}\) :

Char frequency factor, min−1

\({k}_{o, vol}\) :

Volatiles frequency factor, min−1

\({k}_{o}\) :

Frequency factor, min−1

\({max \alpha }_{exp,i}\) :

Highest absolute value of experimental fractional conversion

\({m}_{f}\) :

Final mass of any zone, mg

\({m}_{i}\) :

Initial mass of any zone, mg

\({m}_{v}\) :

Instantaneous mass of volatiles at any time (t), mg

\({m}_{v}\) :

Mass of volatiles at a time (t), mg

\({m}_{vf}\) :

Final mass of volatile zone, mg

\({m}_{vi}\) :

Initial mass of volatile zone, mg

t :

Time corresponding to conversion \((min)\) 

\({t}_{0.9}\) :

Time for 90% conversion of the combustible substances, \(min\) 

\({t}_{bo}\) :

Time corresponding to the burnout temperature, \(min\) 

\({t}_{ig}\) :

Time corresponding to the ignition temperature, \(min\) 

\({t}_{peak}\) :

Time corresponding to the maximum combustion rate, \(min\) 

\({\alpha }_{model,i}\) :

Conversion value calculated from the model at temperature \((T_i)\) 

\(\Delta G\) :

Gibbs free energy, \((kJ/mole)\) 

\(\Delta H\) :

Enthalpy change, \((kJ/mole)\) 

\(\Delta S\) :

Entropy change, \((kJ/mole)\;K\) 

\(h\) :

Plank constant, \(6.626\times10^{-34}\;J.s\) 

S :

Comprehensive combustion index, \(\%/{min}^2\;^\circ C^3\) 

τ:

Duration time of the transition process, \(min\) 

\(E\) :

Activation energy, kJ/mole

\(M\) :

Moisture content, %

\(N\) :

Number of data points

\(R\) :

Universal gas constant, \(8.314J/mole\;K\) 

\(T\) :

Reaction temperature, K

\(f\)(\({\alpha }\)):

The change in the physical and chemical characteristics of the fuel sample during the conversion process

\(k\) :

The apparent reaction rate, min−1

P g :

Partial pressure of gas, Pa

\(p\left(x\right)\) :

Reaction model function

\(t\) :

Time corresponding to conversion,\(min\) 

DRPM:

Double random pore model

DVM:

Double parallel volumetric model

MVRPM:

Mixed volumetric random pore model

RPM:

Random pore model

RSS:

Residual sum of squares

TGA:

Thermal gravimetric analysis

VM:

Volumetric model

GM:

Grain model

α :

Degree of conversion, %

β :

Heating rate, °C/min

\(\psi\) :

Structural parameter

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  1. Mechanical Power Engineering Department, Faculty of Engineering, Zagazig University, Zagazig, 44519, Egypt

    Saad A. EL-Sayed & Mohamed E. Mostafa

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EL-Sayed, S.A., Mostafa, M.E. Kinetics, thermodynamics, and combustion characteristics of Poinciana pods using TG/DTG/DTA techniques. Biomass Conv. Bioref. 13, 11583–11607 (2023). https://doi.org/10.1007/s13399-021-02021-8

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