Kinetics study of pyrolysis of petroleum sludge and characterization of char

Abstract

Thermochemical conversion (or pyrolysis) has emerged as an effective technique for the disposal of sludge generated in process industries. This paper reports physicochemical characterization and kinetic analysis of pyrolysis of sludge from a petroleum refinery and characterization of resultant char. The sludge had high volatile matter (>70 wt%) and low ash content (15 wt%). Pyrolysis of sludge was studied using a thermo-gravimetric analyzer (TGA). The TGA data was analyzed using two isoconversional models, viz. KAS and Vyazovkin AIC are used for the deduction of kinetic triplets, viz. activation energy, pre-exponential factor, and reaction mechanism. The activation energy (Ea ) of sludge pyrolysis varied in the 64.79–190.37 kJ/mol range. The pre-exponential factor varied from 1.18E + 07 to 4.29E + 12 s−1. The predominant solid-state mechanism of thermal conversion was an order-based reaction (F2/F3). The thermodynamic factors (viz. ΔH, ΔS, ΔG) of sludge pyrolysis were also determined. Relatively small values of (Ea – ΔH) ∼ 5 kJ/mol revealed high susceptibility of sludge for thermal conversion. Residual char after pyrolysis was characterized for physicochemical properties. The char properties were fixed carbon = 54.37%, calorific value = 22.48 MJ/kg, and BET surface area = 18.35 m2/g. These properties make char suitable for numerous applications.