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.

In order to reveal the volatile release mechanisms under various conditions (pyrolysis temperature, particle size, coal rank and pyrolysis time), three typical Chinese coals with different ranks were pyrolyzed in a tubular furnace and the pyrolysis gas was analyzed by online balance and gas chromatography. Results suggest that increasing pyrolysis temperature causes increased release volume of volatile compounds and higher calorific value due to substantial increase of H2, an incremental increase of CH4 and the changes in molecule ingredients of C2-C4 structures. Meanwhile, larger particle size can significantly reduce the released volume for its longer diffusion distance and lower specific surface area. Compared with bituminite, lignite yielded more valuable pyrolysis gases and lower primary reaction temperature. The ideal pyrolysis temperature is 700~800 °C for low rank lignite and 800~900 °C for bituminites. Basically, the productions of CO and CO2 are associated with oxygen element content in coal while CO2 releases early mainly by the decarboxylation reaction. Based on the results in the whole pyrolysis process, the CH4 of higher rank coals is mostly produced by the rupture of fatty side chain while the main CH4 source in lignite is the rupture of alkyl side chains.