RESUMEN
The growing ubiquity of recalcitrant organic contaminants in the aqueous environment poses risks to effective and efficient water treatment and reuse. A novel three-dimensional (3D) electrochemical flow-through reactor employing activated carbon (AC) encased in a stainless-steel (SS) mesh as a cathode is proposed for the removal and degradation of a model recalcitrant contaminant p-nitrophenol (PNP), a toxic compound that is not easily biodegradable or naturally photolyzed, can accumulate and lead to adverse environmental health outcomes, and is one of the more frequently detected pollutants in the environment. As a stable 3D electrode, granular AC supported by a SS mesh frame as a cathode is hypothesized to 1) electrogenerate H2O2 via a 2-electron oxygen reduction reaction on the AC surface, 2) initiate decomposition of this electrogenerated H2O2 to form hydroxyl radicals on catalytic sites of the AC surface 3) remove PNP molecules from the waste stream via adsorption, and 4) co-locate the PNP contaminant on the carbon surface to allow for oxidation by formed hydroxyl radicals. Additionally, this design is utilized to electrochemically regenerate the AC within the cathode that is significantly saturated with PNP to allow for environmentally friendly and economic reuse of this material. Under flow conditions with optimized parameters, the 3D AC electrode is nearly 20% more effective than traditional adsorption in removing PNP. 30 grams of AC within the 3D electrode can remove 100% of the PNP compound and 92% of TOC under flow. The carbon within the 3D cathode can be electrochemically regenerated in the proposed flow system and design thereby increasing the adsorptive capacity by 60%. Moreover, in combination with continuous electrochemical treatment, the total PNP removal is enhanced by 115% over adsorption. It is anticipated this platform holds great promises to eliminate analogous contaminants as well as mixtures.
RESUMEN
Both legacy munitions compounds (e.g., RDX) and new insensitive high explosives (e.g. DNAN, NQ) are being manufactured and utilized concurrently, and there exists a need for wastewater treatment systems that are able to degrade both classes of explosives. Electrochemical systems offer treatment possibilities using inexpensive materials and no chemical additions. Electrochemically induced removal of RDX, NQ, and DNAN were separately studied within an electrochemical plug flow reactor hosting a stainless steel (SS) cathode and downstream Ti/MMO anode. Varying wire mesh cathodes and operating conditions were evaluated in an effort to identify the optimal cathode material, to determine the relative contributions of cathodically-induced removal processes, to shorten time to steady-state removal conditions, and to find practical ranges of operating conditions. Applied current allowed the cathode to support munitions removal mainly by direct reduction at the cathode surface, and the secondary reactions of cathodically-induced alkaline hydrolysis and catalytic hydrogenation by adsorbed H on Ni-containing cathode surfaces might contribute to some munitions degradation. The optimal cathode material was identified as SS grade 316, possibly due to its superior Ni content and lack of corrosion protection coating. Higher current, longer cathode length, and smaller mesh pore sizes resulted in slightly greater removal extents and shorter acclimation times to steady state removal conditions, but there are practical upper limits to these properties. Higher Ni content within SS improved RDX and NQ removal but does not affect DNAN removal. Prolonged use of SS grade 316 showed no debilitating changes in electrical performance or chemical content.
RESUMEN
New insensitive high explosives pose great challenges to conventional explosives manufacturing wastewater treatment processes and require advanced methods to effectively and efficiently mineralize these recalcitrant pollutants. Oxidation processes that utilize the fundamental techniques of Fenton chemistry optimized to overcome conventional limitations are vital to provide efficient degradation of these pollutants while maintaining cost-effectiveness and scalability. In this manner, utilizing heterogeneous catalysts and in-situ generated H2O2 to degrade IHEs is proposed. For heterogeneous catalyst optimization, varying the surface chemistry of activated carbon for use as a catalyst removes precipitation complications associated with iron species in Fenton chemistry while including removal by adsorption. Activated carbon impregnated with 5% MnO2 in the presence of H2O2 realized a high concentration of hydroxyl radical formation - 140 µM with 10 mM H2O2 - while maintaining low cost and relative ease of synthesis. This AC-Mn5 catalyst performed effectively over a wide pH range and in the presence of varying H2O2 concentrations with a sufficient effective lifetime. In-situ generation of H2O2 removes the logistical and economic constraints associated with external H2O2, with hydrophobic carbon electrodes utilizing generated gaseous O2 for 2-electron oxygen reduction reactions. In a novel flow-through reactor, gaseous O2 is generated on a titanium/mixed metal oxide anode with subsequent H2O2 electrogeneration on a hydrophobic microporous-layered carbon cloth cathode. This reactor is able to electrogenerate 2 mM H2O2 at an optimized current intensity of 150 mA and over a wide range of flow rates, influent pH values, and through multiple iterations. Coupling these two optimization methods realizes the production of highly oxidative hydroxyl radicals by Fenton-like catalysis of electrogenerated H2O2 on the surface of an MnO2-impregnated activated carbon catalyst. This method incorporates electrochemically induced oxidation of munitions in addition to removal by adsorption while maintaining cost-effectiveness and scalability. It is anticipated this platform holds great promise to eliminate analogous contaminants.