Thermodynamics, kinetics and thermal decomposition characteristics of sewage sludge during slow pyrolysis.

Pyrolysis has shown great potential for sewage sludge valorisation and management by producing value-added chemicals. Although the product process yields are extensively studied, a few studies exist without consensus on the kinetic properties of sewage sludge pyrolysis. As a result, a study to investigate the thermal decomposition characteristics of Gauteng sewage sludge (GSS) at various heating rates (10, 20, and 30 °C/min), its pyrolysis kinetic parameters, reaction mechanism and thermodynamic properties was meticulously conducted. The results show that sewage sludge decomposition occurs in three stages, whereby the main decomposition (active pyrolysis) takes place at 150-570 °C. Fourier transform infrared spectroscopy (FTIR) analysis results confirm progression of thermal decomposition of GSS and drive off volatile compounds and formation of aromatic structures during TGA studies of GSS. An increase in heating rate shifts the characteristic temperatures towards higher temperatures with the highest decomposition rate of 1.10%/min.mg at 30 °C/min. The activation energies of GSS pyrolysis were calculated using Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose and Starink methods and averaged as 225.92, 218.04 and 218.97 kJ/mol, respectively. GSS pyrolysis involves complex reaction chemistry with high reactivity whereby reactions that follow third order and three-dimensional diffusion-reaction mechanisms dominated the process. However, these mechanisms cannot be used explicitly to define the global pyrolysis kinetics due to the occurrence of multiple simultaneous reactions. The obtained thermodynamic and kinetic data will advance and amplify the design, simulation and optimisation of global energy pyrolysis units for production of value-added chemicals.