Exploring the pyrolysis process of simulated oily sludge: Kinetics, mechanism, product distribution, and S/N elements migration

Abstract

Pyrolysis is an important method for energy recovery and harmless treatment of oily sludge, definite reaction mechanism and the transformation of S and N elements is a key to improve the pyrolysis products. In this paper, a simulated oil sludge (SOS) was pyrolyzed at various temperatures of 400–700 °C in a tube furnace focusing on pyrolysis process, kinetic parameters, reaction mechanisms, S and N element migration patterns and product distributions. Kinetic parameters were deducted by FWO, KAS, Friedman and Starink methods, and the activation energy were 186.23–231.20 kJ/mol (Avg. 210.71 kJ/mol), 190.18–233.80 kJ/mol (Avg. 212.02 kJ/mol), 196.93–242.01 kJ/mol (Avg. 209.88 kJ/mol) and 184.82–230.95 kJ/mol (Avg. 218.67 kJ/mol), respectively, showed high similarity. All the pre-exponential factors were higher than 10⁹ s⁻¹, which indicated high reactivity of SOS during pyrolysis, and the pyrolysis process followed the nucleation growth model (A3). Pyrolysis temperatures had a significant influence on products distribution. The maximum yields of pyrolysis tar and gas were observed at 550 °C and 700 °C, respectively. Pyrolysis tar was dominated by aromatics and acids, while pyrolysis gas was mainly composed of H₂ and CH₄. Additionally, high temperatures could facilitate the transfer of more S and N into tar or gas products, and S and N compounds were mainly thiophene-S, sulfoxide-S, pyridine-N and pyrrole-N in char and CS₂, CH₃SH, COS, SO₂, H₂S, NH₃, HCN and NO_x in gas.