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The activity of monometallic (Pd or Rh) and bimetallic (iron-bearing) catalysts has been tested in the HDC of 4-chlorophenol (4-CP) in aqueous phase. The catalysts were prepared by a simple procedure consisting of incipient wetness impregnation followed by calcination and reduction at different temperatures. This allowed controlling the size, dispersion and oxidation state of the metallic nanoparticles. Increasing the temperature of calcination led to a higher dispersion of the active phase (from 21 to 46% by increasing the calcination temperature from 200 to 400 °C) and a higher ratio of zerovalent to electrodefficient palladium (M 0 /M n + values from 1.15 to 2.17) in the case of the Pd-catalysts. Those calcined in air at 400 °C and reduced with H 2 at 350 °C yielded the highest values of the pseudo-first-order rate constant of 4-CP dechlorination (16.2 L h −1 g cat −1 ). The introduction of iron reduced the metal dispersion of both Pd and Rh but the catalysts maintained their dechlorination activity and showed magnetic properties useful for further separation from the liquid phase. [ABSTRACT FROM AUTHOR]

Abstract: A ferromagnetic γ-Al2O3-supported iron catalyst has been prepared and its activity and stability in catalytic wet peroxide oxidation (CWPO) have been compared with those of a previous iron-based conventional catalyst using the same support. Both catalysts were characterized by nitrogen adsorption–desorption isotherms, ICP, TXRF, XRD, XPS, elemental analysis and Mössbauer spectroscopy. The behavior of these catalysts in CWPO of chlorophenols has been related with the nature of the dominant iron species (magnetite or hematite). The results showed that the magnetic catalyst improved significantly the decomposition of H2O2 leading to an increased degradation and mineralization of chlorophenols. Complete conversion of those target pollutants and more than 75% TOC reduction were achieved after 4h under stoichiometric H2O2 dose, 100mgL−1 initial chlorophenol concentration, 1gL−1 catalyst, pH 3 and 50°C temperature. Moreover, complete dechlorination of all the chlorophenols tested was achieved, being the residual organic by-products short-chain acids without significance in terms of ecotoxicity. The catalyst showed a remarkable stability in long-term continuous experiments with limited Fe leaching, below 5% of the initial loading after 100h on stream. An additional clear advantage of the new catalyst is its easy separation and recovery from the reaction medium by applying an external magnetic field. [Copyright &y& Elsevier]

Abstract: Degradation of chlorophenols by a sequential combination of hydrodechlorination (HDC) and catalytic wet peroxide oxidation (CWPO) using a new magnetic Pd–Fe/γ-Al2O3 catalyst has been studied. This catalyst is active in both hydrodechlorination of chlorophenols and decomposition of H2O2 for the oxidation of organic compounds. The sequential combination of HDC and CWPO allows overcoming some of the drawbacks of both treatments applied independently. The HDC step achieves the complete dechlorination of chlorophenols, so that the subsequent CWPO does not lead to the formation of highly toxic chlorinated by-products and reduces significantly the organic load of the effluent. The results showed that the presence of iron in the Pd catalyst improved significantly its hydrodechlorination rate, achieving the complete dechlorination of chlorophenols in a short reaction time (≈15 min), giving rise to phenol and cyclohexanone. The CWPO of synthetic mixtures of phenol and cyclohexanone showed that a high phenol concentration promotes the oxidation of all the organic species, but the presence of cyclohexanone seems to hinder the formation of aromatic radicals limiting the effectiveness of the CWPO step. Therefore, the effective combination of HDC and CWPO requires that the HDC step achieves the complete dechlorination of chlorophenols but no further hydrogenation is needed. The Pd–Fe/γ-Al2O3 catalyst showed a high activity in both HDC and subsequent CWPO of chlorophenols being easily separated and recovered from the reaction medium due to its ferromagnetic properties. In spite of a moderate loss of activity, the complete dechlorination of chlorophenol and a negligible ecotoxicity of the final effluents were maintained upon successive applications of HDC + CWPO in a four-cycles test. [Copyright &y& Elsevier]

Abstract: Homogeneous Fenton-like (H2O2/Fe3+) oxidation proved to be highly efficient in the degradation of monochlorophenols but some important issues need to be considered depending on the operating conditions. When using the stoichiometric amount of H2O2 and a dose of Fe3+ in the range of 10–20mg/L, complete breakdown of 4-CP up to CO2 and short-chain acids was achieved. Nevertheless, when substoichiometric amounts of H2O2 or lower concentrations of iron were used, significant differences between the TOC measured and the calculated from the identified species were found. These differences were attributed to condensation byproducts, including chlorinated species, formed by oxidative coupling reactions. PCBs, dioxins and dichlorodiphenyl ethers were identified. A solid residue was also formed consisting mainly in carbon, oxygen and chlorine including also Fe. The occurrence of these highly toxic species must be carefully considered in the application of Fenton oxidation to wastewaters containing chlorophenols. The possibility of reducing costs by lowering the H2O2 dose below the stoichiometric one needs to tke this into account. [Copyright &y& Elsevier]

Abstract: Hydrodechlorination of 4-chlorophenol using Pd/A2O3 as catalyst at mild conditions (30°C, 1atm) was carried out in plain water, buffered (CH3COOH/NaCH3COO, NaH2PO4/Na2HPO4 and NaHCO3/Na2CO3) and alkaline NaOH media at different pH. The highest reaction rate was achieved when the process was carried out at alkaline NaOH solution of pH=8.5. Continuous long term experiments (τ: 5.4kgcat h/mol) were performed in plain water and alkaline medium using Pd/Al2O3 and Pd/AC as catalysts. The former showed an appreciable loss of activity upon time on stream, which was associated with the formation of palladium chloride complexes. However, a residual activity remained practically stable, reaching very similar 4-chlorophenol conversion (36%) in both reaction media. The Pd/AC catalyst maintained a constant activity at a 70% 4-chlorophenol conversion once the steady state was reached. This suggests that the AC supported catalyst is less susceptible to the chloride poisoning produced during the reaction. [Copyright &y& Elsevier]