Kinetic Modeling of Lignite Devolatilization: Comparative Perspectives of DAEM and Iso-conversional Methods
Keywords:
activation energy, DAEM, Gaussian, kinetic modeling, lignite, TGAAbstract
DAEM and iso-conversional methods are reviewed for kinetically modeling lignite devolatilization, a critical initial stage in coal utilization that profoundly impacts energy efficiency and emissions. Lignite presents unique challenges due to its high volatile content () and complex multi-stage decomposition reactions. DAEM addresses this by assuming devolatilization as a series of parallel, first-order reactions with a continuous distribution of activation energies, mostly Gaussian or Weibull; multi-Gaussian DAEM extensions further enhance accuracy for intricate decomposition profiles. Conversely, iso-conversional methods like Friedman, FWO, and KAS estimate effective activation energies () at various conversions, offering a robust way to analyze kinetic data from multiple heating rates. Comparative analyses indicate that multi-Gaussian DAEM more effectively captures the staged devolatilization of lignite, with reported for low-rank coal ranging from 142 to and significantly improved sum of squared error (SSE) ratios (e.g., ). While iso-conversional methods are computationally efficient and provide consistent profiles (), DAEM yields more complete kinetic parameters. Both require quality TGA data and primarily describe chemical kinetics, often neglecting physical transport limitations pertinent to reactor design. Future research focuses on refining these models and integrating them with broader system simulations.
Downloads
References
IEA, “Accelerating Just Transitions for the Coal Sector,” IEA, Paris, 2024. [Online]. Available: https://www.iea.org/reports/accelerating-just-transitions-for-the-coal-sector
IEA, “Coal 2024: Analysis and forecast to 2027,” 2024.
D. B. Anthony, J. B. Howard, H. C. Hottel, and H. P. Meissner, “Rapid devolatilization of pulverized coal,” Symp. Int. Combust., vol. 15, no. 1, pp. 1303–1317, 1975, doi: 10.1016/S0082-0784(75)80392-4.
A. Bliek, W. M. Van Poelje, W. P. M. Van Swaaij, and F. P. H. Van Beckum, “Effects of intraparticle heat and mass transfer during devolatilization of a single coal particle,” AIChE J., vol. 31, no. 10, pp. 1666–1681, Oct. 1985, doi: 10.1002/aic.690311010.
V. T. Trinh, B.-H. Lee, T.-Y. Jeong, and C.-H. Jeon, “Pyrolysis of different rank fuels: characteristics and kinetic parameter study using nonlinear optimization and artificial neural network,” J. Therm. Anal. Calorim., vol. 148, no. 12, pp. 5493–5507, Jun. 2023, doi: 10.1007/s10973-023-12084-6.
O. Authier, E. Thunin, P. Plion, and L. Porcheron, “Global Kinetic Modeling of Coal Devolatilization in a Thermogravimetric Balance and Drop-Tube Furnace,” Energy Fuels, vol. 29, no. 3, pp. 1461–1468, Mar. 2015, doi: 10.1021/ef502600t.
R. C. Borah, P. Ghosh, and P. G. Rao, “A review on devolatilization of coal in fluidized bed,” Int. J. Energy Res., vol. 35, no. 4, pp. 929–963, 2011, doi: 10.1002/er.
P. R. Solomon, D. G. Hamblen, R. M. Carangelo, M. A. Serio, and G. V. Deshpande, “A General Model of Coal Devolatilization,” 1987. [Online]. Available: https://www.researchgate.net/publication/260904874
J. Wang et al., “Kinetics Modeling of Low-Rank Coal Pyrolysis Based on a Three-Gaussian Distributed Activation Energy Model (DAEM) Reaction Model,” Energy Fuels, vol. 30, no. 11, pp. 9693–9702, Nov. 2016, doi: 10.1021/acs.energyfuels.6b01599.
A. A. El-Tawil, H. M. Ahmed, L. S. Ökvist, and B. Björkman, “Devolatilization Kinetics of Different Types of Bio-Coals Using Thermogravimetric Analysis,” Metals, vol. 9, no. 2, p. 168, Feb. 2019, doi: 10.3390/met9020168.
R. Lemaire, W. Wang, and S. Menanteau, “Kinetic Modeling of the Devolatilization of Pulverized Coal, Poplar Wood, and Their Blends in a Thermogravimetric Analyzer and a Flat Flame Reactor,” ACS Omega, vol. 8, no. 32, pp. 29455–29467, Aug. 2023, doi: 10.1021/acsomega.3c03110.
S. Sommariva, T. Maffei, G. Migliavacca, T. Faravelli, and E. Ranzi, “A predictive multi-step kinetic model of coal devolatilization,” Fuel, vol. 89, no. 2, pp. 318–328, Feb. 2010, doi: 10.1016/j.fuel.2009.07.023.
S. Iavarone, C. Galletti, F. Contino, L. Tognotti, P. J. Smith, and A. Parente, “CFD-aided benchmark assessment of coal devolatilization one-step models in oxy-coal combustion conditions,” Fuel Process. Technol., vol. 154, pp. 27–36, Dec. 2016, doi: 10.1016/j.fuproc.2016.07.013.
J. Mularski, H. Pawlak-Kruczek, and N. Modlinski, “A review of recent studies of the CFD modelling of coal gasification in entrained flow gasifiers, covering devolatilization, gas-phase reactions, surface reactions, models and kinetics,” Fuel, vol. 271, p. 117620, Jul. 2020, doi: 10.1016/j.fuel.2020.117620.
A. Tchapda and S. Pisupati, “A Review of Thermal Co-Conversion of Coal and Biomass/Waste,” Energies, vol. 7, no. 3, pp. 1098–1148, Feb. 2014, doi: 10.3390/en7031098.
H. Kobayashi, J. B. Howard, and A. F. Sarofim, “Coal Devolatilization at High Temperature,” Energy Prod. Coal, 1977.
S. K. Ubhayakar, D. B. Stickler, C. W. Von Rosenberg, and R. E. Gannon, “Rapid devolatilization of pulverized coal in hot combustion gases,” Symp. Int. Combust., vol. 16, no. 1, pp. 427–436, 1977, doi: 10.1016/S0082-0784(77)80342-1.
J. H. Flynn, “THE ISOCONVERSlONAL METHOD FOR DETERMINATION OF Corrections for the Doyle approximation,” J. Therm. Anal., vol. 27, pp. 95–102, 1983.
H. L. Friedman, “Kinetics of thermal degradation of char‐forming plastics from thermogravimetry. Application to a phenolic plastic,” J. Polym. Sci. Part C Polym. Symp., vol. 6, no. 1, pp. 183–195, 1964, doi: 10.1002/polc.5070060121.
H. E. Kissinger, “Reaction Kinetics in Differential Thermal Analysis,” Anal. Chem., vol. 29, no. 11, pp. 1702–1706, 1957, doi: 10.1021/ac60131a045.
T. Ozawa, “A New Method of Analyzing Thermogravimetric Data,” Bull. Chem. Soc. Jpn., vol. 38, no. 11, pp. 1881–1886, Nov. 1965, doi: 10.1246/bcsj.38.1881.
V. Vand, “A theory of the irreversible electrical resistance changes of metallic films evaporated in vacuum,” Proc. Phys. Soc., vol. 55, no. 3, pp. 222–246, May 1943, doi: 10.1088/0959-5309/55/3/308.
B. De Caprariis, P. De Filippis, C. Herce, and N. Verdone, “Double-gaussian distributed activation energy model for coal devolatilization,” Energy Fuels, vol. 26, no. 10, pp. 6153–6159, 2012, doi: 10.1021/ef301092r.
J. Cai et al., “Processing thermogravimetric analysis data for isoconversional kinetic analysis of lignocellulosic biomass pyrolysis: Case study of corn stalk,” Renew. Sustain. Energy Rev., vol. 82, pp. 2705–2715, Feb. 2018, doi: 10.1016/j.rser.2017.09.113.
C. Zou, X. Li, M. Ren, W. Wang, and H. Wu, “Thermal Behavior and Kinetics of Shenmu Coal Pyrolyzed under Hydrogen-Rich or Methane-Gas-Rich Atmosphere,” Energies, vol. 16, no. 5, p. 2339, Feb. 2023, doi: 10.3390/en16052339.
V. R. Patel, R. N. Patel, and V. J. Rao, “Kinetic Study of Indian Lignite by Model-Free Methods,” J. Inst. Eng. India Ser. C, vol. 103, no. 4, pp. 837–845, Aug. 2022, doi: 10.1007/s40032-022-00859-z.
A. Lampropoulos, G. Varvoutis, M. A. Montes-Morán, J. A. Menéndez, M. Konsolakis, and G. E. Marnellos, “Detailed kinetic analysis and modelling of the dry gasification reaction of olive kernel and lignite coal chars,” Int. J. Hydrog. Energy, vol. 48, no. 32, pp. 11970–11983, Apr. 2023, doi: 10.1016/j.ijhydene.2022.08.246.
M. Heydari, M. Rahman, and R. Gupta, “Kinetic Study and Thermal Decomposition Behavior of Lignite Coal,” Int. J. Chem. Eng., vol. 2015, pp. 1–9, 2015, doi: 10.1155/2015/481739.
A. K. Burnham and L. N. Dinh, “A comparison of isoconversional and model-fitting approaches to kinetic parameter estimation and application predictions,” J. Therm. Anal. Calorim., vol. 89, no. 2, pp. 479–490, Aug. 2007, doi: 10.1007/s10973-006-8486-1.
S. A. Scott, J. S. Dennis, J. F. Davidson, and A. N. Hayhurst, “An algorithm for determining the kinetics of devolatilisation of complex solid fuels from thermogravimetric experiments,” Chem. Eng. Sci., vol. 61, no. 8, pp. 2339–2348, Apr. 2006, doi: 10.1016/j.ces.2005.11.002.
T. Maffei, A. Frassoldati, A. Cuoci, E. Ranzi, and T. Faravelli, “Predictive one step kinetic model of coal pyrolysis for CFD applications,” Proc. Combust. Inst., vol. 34, no. 2, pp. 2401–2410, 2013, doi: 10.1016/j.proci.2012.08.006.
S. Vyazovkin, “Computational aspects of kinetic analysis. Part C. The ICTAC Kinetics Project – the light at the end of the tunnel?”.
J. Li et al., “Comparative Study on Pyrolysis Kinetics Behavior and High-Temperature Fast Pyrolysis Product Analysis of Coastal Zone and Land Biomasses,” ACS Omega, vol. 7, no. 12, pp. 10144–10155, Mar. 2022, doi: 10.1021/acsomega.1c06363.
K. K. Dwivedi, A. K. Pramanick, M. K. Karmakar, and P. K. Chatterjee, “Synergistic effect on co-pyrolysis mechanism and kinetics of waste coal blended with high-rank coal and biomass,” J. Therm. Anal. Calorim., vol. 147, no. 15, pp. 8323–8343, Aug. 2022, doi: 10.1007/s10973-021-11123-4.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2025 ITB Graduate School Conference
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
