A comparative study on the slow pyrolysis of Miscanthus (Miscanthus×giganteus Greef et Deu.) cultivated on agricultural and contaminated soils: Assessment of distribution of final products

Abstract

This study aims to investigate the slow pyrolysis behavior of uncontaminated (MSC-I - reference) and heavy metals contaminated (MSC-R) samples with heavy metals from the tailings of a Pb-Zn-Cu flotation mine, consisting of whole stems of Miscanthus. Physicochemical properties of raw materials were investigated through instrumental characterization techniques (Atomic Absorption Spectrometry (AAS), Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD)), while the pyrolysis process was monitored by simultaneous thermal analysis techniques (thermogravimetry (TG) – derivative thermogravimetry (DTG)), coupled with Mass spectrometry (MS), for evolved gas analysis. After determination of the lignocellulose content (cellulose, hemicellulose, and lignin) and extractive of the MSC-I and MSC-R samples, it was found that Pb, Zn, Fe, and Mn in MSC-R lead to very fast decomposition of extractive fraction, which facilitates their distribution in formed bio-char, together with lignin char-participation, acting catalytically. It was established that a much greater fraction of extractives decomposition products and non-volatile heavy metals are incorporated in MSC-R bio-char increasing its yield (23 %), compared to MSC-I bio-char yield (21.5 %). It was identified that MSC-R has increased production of H2, CO, and CO2, while decreased production of CH4, influenced by Fe (Fe has a significant positive effect on CO2 evaluation during MSC-R pyrolysis, enhancing decarboxylation process). It was established that CH4 reforming reactions catalyzed by iron additionally affect methane reduction, and increase production of H2, compared to the reference sample. Isoconversional kinetic analysis showed that pyrolysis reactions profile was strongly conditioned by the presence of heavy metals, such as Cd, Pb, and Zn, because they affect the modification of biomass lignocellulosic structure. Also, it was found that small amounts of Cd present in MSC-R can increase pyrolysis activation energy of three pseudo-components, and inhibit their deoxygenation, thus increasing yield of bio-char.