Synthesis of Phthalic Anhydride: Catalysts, Kinetics, and Reaction Modeling

Abstract

Information concerning the oxidation of o-xylene and naphthalene, the two main processes for producing phthalic anhydride, is updated and analyzed. New techniques for the preparation of catalysts, all based in the impregnation method and involving the control of parameters such as pH and ionic strength of solutions, are described; the performance of the resulting catalysts is compared with that of catalysts prepared by other methods. Sulfur-containing substances and promoters such as Ag, P, Nb, and Sb have been shown to enhance catalyst performance; studies of their effect on the surface area, acidic properties, and stabilization of the oxidation state of vanadium in supported V2O5 catalysts are described. The latest attempts to correlate the physicochemical characteristics of the catalysts with their catalytic features are analyzed. FTIR, Raman spectroscopy, adsorption of bases, 51V-NMR, XRD, XPS, SIMS, and electrical conductivity have been used in the study of V2O5/TiO2 catalysts, allowing further understanding of the effects of the properties such as acidity and the state of oxidation of the surface. Particular emphasis has been given to the presence of VIV, which is thought to cause lower selectivity to phthalic anhydride. For o-xylene oxidation, the formation of involatile by-products has been established as a secondary reaction, accounting for the poor carbon balances obtained under some experimental conditions. Involatile by-products, whose formation has been associated with the presence of strong acid sites, can adsorb on the catalyst surface, leading to deactivation, or undergo total combustion, acting as a source of CO2. Attempts to quantify and characterize those by-products are described. The modeling of the reaction using both fixed- and fluidized-bed reactors, including the study of parameters such as the inlet temperature and the bath temperature, is analyzed. Models considering catalyst deactivation have been also developed; for o-xylene oxidation, deactivation has been associated with processes both reversible, such as changes in the oxidation state of vanadium, deposition of involatile compounds, and irreversible, such as structural changes, decrease in surface area, sintering, and variation of the promoter concentration at the catalyst surface. The study of V2O5/TiO2 EUROCAT catalysts, involving a number of European laboratories, is reviewed, and their performance is compared with that of other V2O5/TiO2 catalysts.