Optimization of the Load of Transition Metal Oxides (Fe2O3 Co3O4 NiO and/or PdO) onto CeO2 Nanoparticles in Catalytic Steam Decomposition of n-C7 Asphaltenes at Low Temperatures

摘要

The main objective of this work is the catalyst optimization of Fe2O3-, Co3O4-, NiO- and/or PdO- (transition element oxides—TEO) functionalized CeO2 nanoparticles to maximize the conversion of asphaltenes under isothermal conditions at low temperatures (<250 °C) during steam injection processes. Adsorption isotherms and the subsequent steam decomposition process of asphaltenes for evaluating the catalysis were performed through batch adsorption experiments and thermogravimetric analyses coupled to Fourier-transform infrared spectroscopy (FTIR), respectively. The adsorption isotherms and the catalytic behavior were described by the solid-liquid equilibrium (SLE) model and isothermal model, respectively. Initially, three pairs of metal oxide combinations at a mass fraction of 1% of loading of CeNi1Pd1, CeCo1Pd1, and CeFe1Pd1 nanoparticles were evaluated based on the adsorption and catalytic activity, showing better results for the CeNi1Pd1 due to the Lewis acidity changes. Posteriorly, a simplex-centroid mixture design of experiments (SCMD) of three components was employed to optimize the metal oxides concentration (Ni and Pd) onto the CeO2 surface by varying the oxides concentration for mass fractions from 0.0% to 2.0% to maximize the asphaltene conversion at low temperatures. Results showed that by incorporating mono-elemental and bi-elemental oxides onto CeO2 nanoparticles, both adsorption and isothermal conversion of asphaltenes decrease in the order CeNi1Pd1 > CePd2 > CeNi0.66Pd0.66 > CeNi2 > CePd1 > CeNi1 > CeO2. It is worth mentioning that bi-elemental nanoparticles reduced the gasification temperature of asphaltenes in a larger degree than mono-elemental nanoparticles at a fixed amount of adsorbed asphaltenes of 0.02 mg·m⁻², confirming the synergistic effects between Pd and Fe, Co, and Ni. Further, optimized nanoparticles (CeNi0.89Pd1.1) have the best performance by obtaining 100% asphaltenes conversion in less than 90 min at 220 °C while reducing 80% the activation energy.