Abdellatif El-Ghenymy

Optimization of the electro-Fenton and solar photoelectro-Fenton treatments of sulfanilic acid solutions using a pre-pilot flow plant by response surface methodology

A central composite rotatable design and response surface methodology were used to optimize the experimental variables of the electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) degradations of 2.5L of sulfanilic acid solutions in 0.05M Na(2)SO(4). Electrolyses were performed with a pre-pilot flow plant containing a Pt/air diffusion reactor generating H(2)O(2). In SPEF, it was coupled with a solar photoreactor under an UV irradiation intensity of ca. 31Wm(-2). Optimum variables of 100mAcm(-2), 0.5mM Fe(2+) and pH 4.0 were determined after 240min of EF and 120min of SPEF. Under these conditions, EF gave 47% of mineralization, whereas SPEF was much more powerful yielding 76% mineralization with 275kWh kg(-1) total organic carbon (TOC) energy consumption and 52% current efficiency. Sulfanilic acid decayed at similar rate in both treatments following a pseudo-first-order kinetics. The final solution treated by EF contained a stable mixture of tartaric, acetic, oxalic and oxamic acids, which form Fe(III) complexes that are not attacked by hydroxyl radicals formed from H(2)O(2) and added Fe(2+). The quick photolysis of these complexes by UV light of sunlight explains the higher oxidation power of SPEF. NH(4)(+) was the main inorganic nitrogen ion released in both processes.

Mineralization of sulfanilamide by electro-Fenton and solar photoelectro-Fenton in a pre-pilot plant with a Pt/air-diffusion cell

The mineralization of sulfanilamide solutions at pH 3.0 was comparatively studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) using a 2.5 L pre-pilot plant containing a Pt/air-diffusion cell coupled with a solar photoreactor. Organics were primordially oxidized by hydroxyl radical (OH) formed from Fentons reaction between H₂O₂ generated at the cathode and added Fe(2+) and/or under the action of sunlight. A mineralization up to 94% was achieved using SPEF, whereas EF yielded much poorer degradation. The effect of current density and Fe(2+) and drug concentrations on the degradation rate, mineralization current efficiency and energy cost per unit DOC mass of EF and/or SPEF was examined. The sulfanilamide decay always followed a pseudo first-order kinetics, being more rapid in SPEF due to the additional generation of OH induced by sunlight on Fe(III) species. Catechol, resorcinol, hydroquinone and p-benzoquinone were identified as aromatic intermediates. The final solutions treated by EF contained Fe(III) complexes of maleic, fumaric, oxamic and mainly oxalic acids, which are hardly destroyed by OH. The quick photolysis of Fe(III)-oxalate complexes by sunlight explains the higher oxidation ability of SPEF. The N content of sulfanilamide was mainly mineralized as NH₄⁺ ion and in much lesser extent as NO₃⁻ ion, whereas most of its initial S was converted into SO₄²⁻ ion.

Electro-Fenton and Photoelectro-Fenton Degradation of Sulfanilic Acid Using a Boron-Doped Diamond Anode and an Air Diffusion Cathode

The mineralization of sulfanilic acid has been studied by electro-Fenton (EF) and photoelectro-Fenton (PEF) reaction with UVA light using an undivided electrochemical cell with a boron-doped diamond (BDD) anode and an air diffusion cathode able to generate H(2)O(2). Organics were then oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fentons reaction between generated H(2)O(2) and added Fe(2+). The UVA irradiation in PEF enhanced the production of hydroxyl radicals in the bulk, accelerating the removal of organics and photodecomposed intermediates like Fe(III)-carboxylate complexes. Partial decontamination of 1.39 mM sulfanilic acid solutions was achieved by EF until 100 mA cm(-2) at optimum conditions of 0.4 mM Fe(2+) and pH 3.0. The increase in current density and substrate content led to an almost total mineralization. In contrast, the PEF process was more powerful, yielding almost complete mineralization in less electrolysis time under comparable conditions. The kinetics for sulfanilic acid decay always followed a pseudo-first-order reaction. Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic, and oxamic acids were identified as generated carboxylic acids. NH(4)(+) ion was preferentially released in both treatments, along with NO(3)(-) ion in smaller proportion.

Salicylic acid degradation by advanced oxidation processes. Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis

A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fentons reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.

Electrochemical incineration of sulfanilic acid at a boron-doped diamond anode

The anodic oxidation of sulfanilic acid solutions has been studied in acidic medium using a divided cell with a boron-doped diamond (BDD) anode and a stainless steel cathode. Overall mineralization was achieved under all experimental conditions tested due to the efficient destruction of sulfanilic acid and all its by-products with hydroxyl radicals generated at the BDD anode from water oxidation. The alternative use of an undivided cell with the same electrodes gave rise to the coating of the cathode with polymeric compounds, thus preventing the complete electrochemical incineration of sulfanilic acid. The solutions treated in the anodic compartment of the divided cell were degraded at similar rate under pH regulation within the pH interval 2.0-6.0. The mineralization current efficiency was enhanced when the applied current decreased and the initial substrate concentration increased. The decay of sulfanilic acid was followed by reversed-phase HPLC, showing a pseudo first-order kinetics. Hydroquinone and p-benzoquinone were identified as aromatic intermediates by gas chromatography-mass spectrometry and/or reversed-phase HPLC. Maleic, acetic, formic, oxalic and oxamic acids were detected as generated carboxylic acids by ion-exclusion HPLC. Ionic chromatographic analysis of electrolyzed solutions revealed that the N content of sulfanilic acid was mainly released as NH(4)(+) ion and in much smaller proportion as NO(3)(-) ion.