In-depth insight into the effects of intrinsic calcium compounds on the pyrolysis of hazardous petrochemical sludge

To understand the potential effects of intrinsic calcium compounds on sludge pyrolysis, the pyrolysis behavior of petrochemical sludge (PS), calcium carbonate blend PS (CaPS), and decalcified PS (DePS) were investigated using thermogravimetric analysis (TGA) and in-situ Fourier-transform infrared spectroscopy coupled with pyrolysis-gas chromatography and mass spectrometry (Py–GC/MS). The TGA results indicated that decalcification increased and decreased the energy barriers of PS decomposition in ranges 200–350 °C and 350–600 °C, respectively. In contrast, copyrolysis with CaCO₃ decreased the activation energy (E) of the pseudoreaction phase 2 (PH2) and altered the mechanism model. Meanwhile, during copyrolysis, char deposition and interaction hindered CaCO₃ decomposition. The two-dimensional correlation spectroscopy results, on the other hand, showed that the reaction priority of O-containing groups and CH– vibration of methyl groups were affected by both decalcification and CaCO₃ copyrolysis. The Py–GC/MS results indicated that the three sludges mainly released hydrocarbons, N-containing organics, alcohols, aldehydes, and acids. During pyrolysis, CaCO₃ also played a neutralization role, which reduced the release of pyrolytic acidic products. In addition, the increase of the pyrolysis temperature increased the hydrocarbon content. This research will guide the industrial application of sludge pyrolysis.