Iron-rich rolling sludge (FeRS) represents a kind of typical solid waste produced in the iron and steel industry, containing a certain amount of oil and large amounts of iron-dominant minerals. Pyrolysis under anaerobic environment can effectively eliminate organics at high temperatures without oxidation of Fe. This paper firstly investigated comprehensively the pyrolysis characteristics of FeRS. The degradation of organics in FeRS mainly occurred before 400 °C. The activation energy for pyrolysis of FeRS was extremely low, ca. 5.44 kJ/mol. The effects of pyrolytic temperature, atmosphere, heating rate, and stirring on pyrolysis characteristics were conducted. Commonly, the yield of solid residues maintained around 85 wt.%, with approximately 13 wt.% oil and 2 wt.% gas. Due to the low yield of oil and gas, their further utilization remains difficult despite CO₂ introduction which could upgrade their quality. The solid residues after pyrolysis exhibited porous properties with co-existence of micropores and mesopores. Combined with the high content of zero-valent iron, magnetic property, hydrophobic characteristic, and low density, the solid residues could be further utilized for water pollution control and soil remediation. Moreover, the solid residues were suitable for sintering to recover valuable iron resources. However, the solid residues also contained certain heavy metals, such as Cd, Cr, Cu, Ni, Pb, and Zn, which might cause secondary pollution during their utilization. In particular, the toxic Cr possessed high content, which should be treated with detoxification and removal. This paper provides fundamental information for pyrolysis of FeRS and utilization of solid residues.

Thermal treatment has significant advantages in resource recovery for oily sludge (OS). However, the instability of heavy metals (HMs) within the residue poses a considerable risk of secondary pollution. This study explored the migration and transformation of HMs from OS under varying conditions (i.e., temperature, constant-temperature duration time, and different ratios of O₂ and CO₂). The elevation of the pyrolysis temperature augmented the decomposition of organic matter and total petroleum hydrocarbons (TPHs). However, the increased temperature also diminished the stabilization of HMs, and facilitating the HM’s transfer to oil and gas, particularly for HMs (i.e., As and Pb) with low boiling points. The constant-temperature duration time exhibited a weak impact on HM transformation, but the internal heating mechanism of microwave pyrolysis promoted the stabilization of HMs through vitrification. The existing O₂ with oxidizing properties facilitated the oxidation of organic matter and TPHs to CO₂ and H₂O, which also promoted the transformation of HMs into oxidized states for stabilization. Comparatively, CO₂ promoted the thermal cracking and disrupted the stability of HMs to a certain extent. Above all, this work revealed the migration and transformation of HMs in OS varied with the thermochemical methods and possessed an important significance for the immobilization and stabilization of HMs.