Abstract
This work aims to present an industrial perspective on Catalytic Wet Peroxide Oxidation (CWPO) technology. Herein, process simulation and experimental design have been coupled to study the optimal process conditions to ensure high-performance oxidation, minimum H2O2 consumption and maximum energetic efficiency in an industrial scale CWPO unit. The CWPO of phenol in the presence of carbon black catalysts was studied as a model process in the Aspen Plus® v11 simulator. The kinetic model implemented, based on 30 kinetic equations with 11 organic compounds and H2O2 involvement, was valid to describe the complex reaction network and to reproduce the experimental results. The computer experiments were designed on a six-factor Doehlert Matrix in order to describe the influence of the operating conditions (i.e., the different process temperatures, inlet chemical oxygen demands, doses of H2O2 and space time) on each selected output response (conversion, efficiency of H2O2 consumption and energetic efficiency) by a quadratic model. The optimization of the WPO performance by a multi-criteria function highlighted the inlet chemical oxygen demand as the most influential operating condition. It needed to have values between 9.5 and 24 g L−1 for autothermal operation to be sustained under mild operating conditions (reaction temperature: 93–130 °C and pressure: 1–4 atm) and with a stoichiometric dose of H2O2.
Highlights
Advanced oxidation processes (AOPs) are technologies that involve the generation of hydroxyl radicals in sufficient quantities to mineralize recalcitrant pollutants to carbon dioxide, water and inorganics or, at least, to transform them into harmless products
Based on the elementary reaction set introduced in the simulator (Table S1), the empirical kinetic equation was defined for each organic species, shown in Equation (1), with the kinetic constants estimated for the Catalytic Wet Peroxide Oxidation (CWPO) with a carbon black catalyst [40] and the thermodynamic data selected (Table S2 of the Supplementary Material); calculations were performed in a batch reactor with Aspen Plus under the following selected operating that the results obtained reproduced the experimental ones
Based on the elementary reaction set introduced in the simulator (Table S1), the empirical kinetic equation was defined for each organic species, shown in Equation (1), with the kinetic constants estimated for the CWPO with a carbon black catalyst [40] and the thermodynamic data selected (Table S2 of the Supplementary Material); Catalysts
Summary
Advanced oxidation processes (AOPs) are technologies that involve the generation of hydroxyl radicals in sufficient quantities to mineralize recalcitrant pollutants to carbon dioxide, water and inorganics or, at least, to transform them into harmless products. Wastewater with relative low chemical oxygen demand (COD < 5 g L−1 ) is suitably treated under near ambient conditions by different types of oxidant i.e., H2 O2 , O2 and O3. These processes can be photo and electro assisted. The selection of each technology depends on many factors, such as the technical effectiveness using real streams, the manageability and applicability to the specific operations and the cost, among others [2,3,4].
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