Systematic study on dynamic pyrolysis behaviors, products, and mechanisms of weathered petroleum-contaminated soil with Fe2O3.

Weathered petroleum-contaminated soil (WPCS) with a high proportion of heavy hydrocarbons is difficult to remediate. Our previous research demonstrated that Fe2O3-assisted pyrolysis was a cost-effective technology for the remediation of WPCS. However, the pyrolysis behaviors, products, and mechanisms of the WPCS with Fe2O3 are still unclear. In this study, a combination of Thermogravimetric-Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) techniques were used to explore these pyrolysis characteristics. The thermal desorption/degradation of light and heavy hydrocarbons in the WPCS mainly occurred at 200-400 °C and 400-550 °C, respectively. The activation energy of thermal reaction of heavy hydrocarbons was decreased in the presence of Fe2O3 during the WPCS pyrolysis processes. In the process, the released inorganic gaseous products were mainly H2O and CO2, while the released organic gaseous compounds were primarily cycloalkanes, alkanes, acids/esters, alcohols, and aldehydes. Compared with the WPCS pyrolysis without Fe2O3, the yields of gaseous products released during the WPCS pyrolysis with Fe2O3 were reduced significantly, and some gaseous products were even not detected. This phenomenon was contributed by the following two reasons: 1) heavy hydrocarbons in the WPCS were more easily transformed into coke in the presence of Fe2O3 during pyrolysis; 2) some released gaseous products were reacted with Fe2O3 and fixed on the soil particles. Therefore, the WPCS pyrolysis with Fe2O3 can effectively reduce the burden of tail gas treatment. Criado method analysis results suggested that the reaction mechanism of heavy hydrocarbons during the WPCS pyrolysis with Fe2O3 was rendered as the synergic effects of diffusion, order-based, and random nucleation and growth reactions.

Catalytic oxidation of PCDD/F on a V2O5-WO3/TiO2 catalyst: Effect of chlorinated benzenes and chlorinated phenols.

Catalytic oxidation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) is a well-proven technique, applied in a rising number of Municipal Solid Waste Incineration plants, yet the simultaneous and possibly competitive co-oxidation of other compounds, such as chlorinated benzenes (CBz) or phenols (CP), is still poorly documented. In this study, a grinded commercial catalyst (vanadium-tungsten supported on titanium dioxide) was submitted to exploratory testing: the PCDD/F present in a gas test flow were catalytically oxidised (200°C, 10,000h-1), either as such or in the presence of benzene (Bz), monochlorobenzene (MCBz), and 1,2-dichlorobenzene (DCBz) and the effect of these additions on the catalytic destruction of PCDD/F was verified experimentally. Both removal efficiency (RE) and destruction efficiency (DE) declined during the exploratory testing and, importantly, some DCBz even converted into supplemental PCDD/F. Also, the occurrence of carbon deposition negatively influenced catalytic oxidation activity. Regeneration with oxygen or air allowed to remove the deposited carbon and the original catalytic activity was largely restored after calcination. In a second part of this study, the PCDD/F-formation from DCBz, hexachlorobenzene (HCBz), o-monochlorophenol (o-MCP) and pentachlorophenol (PeCP) was demonstrated and tentatively explored. To prepare for further elucidation of the reaction mechanism, a complete isomer-specific analysis was prepared.

Catalytic oxidation of 1,2-DCBz over V2O5/TiO2-CNTs: effect of CNT diameter and surface functional groups.

A series of V2O5/TiO2-carbon nanotube (CNT) catalysts were prepared and tested to decompose gaseous 1,2-dichlorobenzene (1,2-DCBz). Several physicochemical methods, including nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (TPR) were employed to characterise their physicochemical properties. To better understand the effect of CNT properties on the reactivity of V2O5/TiO2-CNT catalysts, the 1,2-DCBz residue remaining in the off-gas and on the catalyst surface were both collected and analysed. The results indicate that the outer diameter and the surface functional groups (hydroxide radical and carboxyl) of CNTs significantly influence upon the catalytic activity of CNT-containing V2O5/TiO2 catalysts: the CNT outer diameter mainly affects the aggregation of CNTs and the π-π interaction between the benzene ring and CNTs, while the introduction of -OH and -COOH groups by acid treatment can further enlarge specific surface area (SSA) and contribute to a higher average oxidation state of vanadium (V aos) and supplemental surface chemisorbed oxygen (Oads). In addition, the enhanced mobility of lattice oxygen (Olatt) also improves the oxidation ability of the catalysts.