RESUMEN

Transition metal catalysts can significantly enhance the pyrolytic remediation of soils contaminated with polycyclic aromatic hydrocarbons (PAHs). Significantly higher pyrene removal efficiency was observed after the pyrolytic treatment of Fe-enriched bentonite (1.8% wt ion-exchanged content) relative to natural bentonite or soil (i.e., 93% vs 48% and 4%) at the unprecedentedly low temperature of 150 °C with only 15 min treatment time. DFT calculations showed that bentonite surfaces with Fe3+ or Cu2+ adsorb pyrene stronger than surfaces with Zn2+ or Na+. Enhanced pyrene adsorption results from increased charge transfer from its aromatic π-bonds to the cation site, which destabilizes pyrene allowing for faster degradation at lower temperatures. UV-Vis and GC-MS analyses revealed pyrene decomposition products in extracts of samples treated at 150 °C, including small aromatic compounds. As the pyrolysis temperature increased above 200 °C, product distribution shifted from extractable compounds to char coating the residue particles. No extractable byproducts were detected after treatment at 400 °C, indicating that char was the final product of pyrene decomposition. Tests with human lung cells showed that extracts of samples pyrolyzed at 150 °C were toxic; thus, high removal efficiency by pyrolytic treatment does not guarantee detoxification. No cytotoxicity was observed for extracts from Fe-bentonite samples treated at 300 °C, inferring that char is an appropriate treatment end point. Overall, we demonstrate that transition metals in clay can catalyze pyrolytic reactions at relatively low temperatures to decrease the energy and contact times required to meet cleanup standards. However, mitigating residual toxicity may require higher pyrolysis temperatures.

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RESUMEN

We developed a novel methodology that combines thermo-analytical measurements and mathematical methods to inform the reliable pyrolytic treatment of specific soil/contaminant systems. Our approach improves upon current "black-box" design methods that may overestimate the required treatment intensity and hinder cost efficacy. We used thermogravimetry and evolved gas analysis to characterize the complex network of soil mineral transformations, contaminant desorption, and pyrolytic reactions occurring when contaminated soils are heated in an anoxic atmosphere. The kinetics of these reactions were quantified using a distributed activation energy (DAE) approach with six pseudocomponents and used in a mathematical model for continuous-flow reactors to predict the removal of hydrocarbon contaminants without other fitting parameters. This model was tested with pilot-scale data from pyrolytic treatment of soils contaminated with crude oil and found to be a good predictor of the total petroleum hydrocarbon (TPH) removal for temperatures between 370 and 470 °C and residence times from 15 to 60 min. The light hydrocarbon fraction desorbed quickly, and over 99.7% removal was achieved at 420 °C and 15 min residence time. However, 95% removal of the heavy hydrocarbon fraction, which is a good proxy for polyaromatic hydrocarbons (PAHs), required 470 °C with 15 min residence time. This model can be employed to select operating conditions (e.g., reactor size, treatment time, and temperature) to reliably achieve remediation objectives for specific hydrocarbon/soil mixtures without inflating energy requirements, which would lower operating costs and decrease the process carbon footprint on a system-specific basis.

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This study evaluates the performance of continuous flow adsorbers for adsorptive desulfurization. JP-8 fuel with 2,230 ppmw of sulfur was treated in a flow-through adsorber packed with CuNa-Y zeolite pellets and operating at 180 °C and 200 psig with liquid hourly space velocities (LHSV) from 0.13 to 3.24 h-1. Our results showed that a flow-through adsorber operating at these conditions can effectively reduce the sulfur content of JP-8 to ultra-low values (1-10 ppmw) over the entire LHSV range tested, although the overall performance of the adsorber declined with increasing flow rates as expected. We also observed that the total sulfur removal exceeded the theoretical adsorption limit of our zeolite adsorbent. Detailed characterization of the treated fuel and spent adsorbent via chromatographic and surface analysis techniques revealed that desulfurization occurs in two stages. Sulfur is initially removed via adsorption (chemisorption) on the CuNa-Y zeolite, an assertion supported by simulations with a transient heterogeneous model. As the adsorbent becomes saturated, however, surface chemical reactions start taking place leading to the formation of hydrogen sulfide and polymerization products, and depositing carbon residue on the zeolite. The spent adsorbent was regenerated by treating it with air at 550 or 600 °C, which restored the adsorption capacity of the material to about 90% of its initial value.