This study evaluates the characterization and treatability of 2,4-D production wastewaters. Wastewaters contain 20000-40000 mg/l COD, 17000-30000 mg/l chloride and pH is around 1.0. Chemical oxidation with hydrogen peroxide provided almost complete COD removal. The optimum conditions are 3:1 H2O2/COD oxidant dosage, 3000 mg/l Fe3+ as catalyst and pH 3. Partial oxidation at 0.5:1 H2O2//COD ratio is also effective providing 67% COD removal. A batch activated sludge system is used for biological treatability. Dilution is needed to maintain a tolerable chloride concentration which increases through COD removal. pH also increased during COD removal. 85% COD removal is obtained for the 50% dilution at an organic loading of 0.3 day‒1 on a COD basis. Completely and partially oxidized wastewaters are also treated in the activated sludge down to 30 mg/l BOD5.
Ni/ZrO2 catalysts, active and selective for the catalytic partial oxidation of methane to syngas (CH4-CPO), were prepared by the dry impregnation of zirconium oxyhydroxide (Zhy) or monoclinic ZrO2 (Zm), calcination at 1173 K and activation by different procedures: oxidation-reduction (ox-red) or direct reduction (red). The characterization included XRD, FESEM, in situ FTIR and Raman spectroscopies, TPR, and specific surface area measurements. Catalytic activity experiments were carried out in a flow apparatus with a mixture of CH4:O2 = 2:1 in a short contact time. Compared to Zm, Zhy favoured the formation of smaller NiO particles, implying a higher number of Ni sites strongly interacting with the support. In all the activated Ni/ZrO2 catalysts, the Ni–ZrO2 interaction was strong enough to limit Ni aggregation during the catalytic runs. The catalytic activity depended on the activation procedures; the ox-red treatment yielded very active and stable catalysts, whereas the red treatment yielded catalysts with oscillating activity, ascribed to the formation of Niδ+ carbide-like species. The results suggested that Ni dispersion was not the main factor affecting the activity, and that active sites for CH4-CPO could be Ni species at the boundary of the metal particles in a specific configuration and nuclearity.