Catalytic Wet Oxidation of Acrylic Acid: Studies with Manganese-based Oxides

Abstract

Development of active, stable and economical catalysts for oxidation of acrylic acid contained in industrial effluents is nowadays of great importance. Several manganese-based solids catalysts supported in Ce, Zr, Ti and Al oxides were prepared in our laboratory by incipient wetness impregnation for oxidation of acrylic acid in a batch high-pressure reactor at slurry conditions under 200°C and 15 bar of oxygen partial pressure. The Mn-Ce-O catalyst was the most active leading to high conversions (92.3%) in terms of total organic carbon (TOC) and total degradation of acrylic acid in the first 30 min of reaction. The TOC reductions were lower with Mn-Zr-O (45.6%), Mn-Ti-O (43.6%) and Mn-Al-O (28.2%) as well as acrylic acid was not completely degraded even after 180 min of reaction. The impregnation method used for catalyst preparation was compared with the co-precipitation procedure, being the last one less effective for TOC reduction (87.0%) although the same activity to oxidation of acrylic acid was observed. Acetic and formic acids were found as reaction intermediates being refractory compounds for the catalysts supported in Zr, Ti and Al. Catalyst stability was also evaluated and Mn-Ce-O prepared by impregnation showed low leaching of Mn to the liquid phase as well as carbon adsorption was not found strengthening the catalyst potentialities in the treatment of wastewaters containing acrylic acid. Since under non-catalytic conditions acrylic acid is refractory up to high temperatures (260°C), this work offers a step forward in the design of an economical catalyst able to promote acrylic acid oxidation in the liquid-phase at lower operating conditions than those used in non-catalytic systems.