Fenton-Like Oxidation of 4−Chlorophenol: Homogeneous or Heterogeneous?

Heterogeneous Fenton-like catalysts have received considerable research attention because they could potentially be attractive for oxidative removal of organic contaminants from tertiary wastewater. However, process design is still hampered by insufficient understanding of the chemical pathways involved, and especially whether oxidation activity stems from heterogeneous surface chemistry or minute concentrations of dissolved metal ions in the homogeneous phase. Using inductively coupled plasma-optical emission spectroscopy (ICP-OES) in combination with pH monitoring and ultraviolet–visible spectroscopy (UV–vis) we have monitored the degradation of 4-chlorophenol (4-CP) over two Fenton-like heterogeneous systems, namely FeOx supported on TiO2 and CuFe2O4. We show conclusively that these systems proceed predominantly through a homogeneous route via dissolved metal ions from the solid phase catalysts. Control experiments with homogeneous Fe3+ or Cu2+ systems reveal that even minute concentrations (μM/subppm) of dissolved metal ions leached from the solid phases account for the observed 4-CP degradation rates in the heterogeneous systems. ICP-OES revealed that metal leaching was time-dependent and variable because of pH variations associated with changing acid release rates. Buffering solutions at pH 7.4 suppressed metal leaching (and hence 4-CP degradation) in the FeOx/TiO2 system, but not in others. For example, pH buffering did not entirely suppress metal leaching from CuFe2O4, for which 4-CP degradation was retained through small concentrations of Fe and Cu ions in solution. Our results highlight the importance of careful monitoring of metal content in the aqueous phase, certainly with analytical sensitivity below ppm concentrations of the dissolved metals, and also the crucial influence of time-dependent pH variations on the reaction process. Recyclability of catalysts, pH buffering of solutions or monitoring of metal content in the solid phase by less sensitive analytical methods, for example, chemical analysis, gravimetry, X-ray fluorescence, or energy dispersive X-ray analysis in electron microscopes, cannot exclude the homogeneous Fenton route in the presence of solid catalysts

Application of a compact trickle-bed bioreactor for the removal of odor and volatile organic compounds emitted from a wastewater treatment plant

A compact trickle-bed bioreactor (CTBB) was tested for the removal of volatile organic compounds (VOCs) and hydrogen sulphide (H 2 S) present in the exhaust air of a wastewater treatment plant. At gas-flow rates varying between 2.0 and 30.0 m 3 /h and for specific pollutant loads up to 20 g/(m 3 ·h), removal efficiencies for H 2 S and VOC were >95%. The CTBB was designed for a maximum H 2 S concentration of ~200 ppm and removal efficiencies >97% were noticed. VOC concentrations were in the range of 25–240 ppm v and the removal efficiency was in the range of 85–99%. Possible consequences of an excessive pollutant overload and the time required for regenerating the microbial activity and reviving stable process conditions in the CTBB were also investigated. An increase in the H 2 S concentration from 400 to 600 ppm v for a few hours caused bioreactor poisoning; however, when original H 2 S concentrations were restored, stable CTBB operation was ascertained within 3 h. © 2019 Elsevier Ltd0000-0003-1166-198