Understanding and modeling of coal pyrolysis assume particular importance, since it is the first step of combustion and gasification processes. The complex reactions occurring during pyrolysis lead to difficulties in the process modeling. The aim of this work is to find a global kinetic model that well represents the pyrolysis of two different coals with opposite rank, a sub-bituminous and an anthracite coal, in order to carry out the kinetic parameters of the process. The Distributed Activation Energy Model (DAEM) was used to fit experimental data obtained with a thermogravimetric analysis. The model assumes that a series of first order parallel reactions occurs sharing the same pre-exponental factor, k(0), and having a continuous distribution of the activation energy. One of the limits of the standard Gaussian DAEM is that with this model is not possible to distinguish the primary from the secondary pyrolysis. A two Gaussians DAEM was developed considering that two classes of reactions take place having the same k(0) and different distribution of activation energy. Since in the model k0 is highly correlated with the mean activation energies, it was fixed at characteristic values taken from literature

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Understanding and modeling of coal and biomass pyrolysis assume particular importance being the first step occurring in both gasification and combustion processes. The complex chemical reaction network occurring in this step leads to a necessary effort in developing a suitable model framework capable of grasping the physics of the phenomenon and allowing a deeper comprehension of the sequence of events. The aim of this work is to show how the intrinsic flexibility of a model based on a double distribution of the activation energy is able to properly describe the two separate steps of primary and secondary pyrolysis, which characterize the thermochemical processing of most of the energetic materials. The model performance was tested by fitting the kinetic parameters from experimental data obtained by thermogravimetric analysis of two materials, which represent very different classes of energy source: a microalgae biomass and a sub-bituminous coal. The model reproduces with high accuracy the pyrolysis behavior of both the materials and adds important information about the relative occurring of the two pyrolysis steps.

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