4.7 Article

Insights into the Morphology Effect of Ceria on the Catalytic Performance of NiO-PdO/CeO2 Nanoparticles for Thermo-oxidation of n-C7 Asphaltenes under Isothermal Heating at Different Pressures

Journal

ENERGY & FUELS
Volume 35, Issue 22, Pages 18170-18184

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.energyfuels.1c01424

Keywords

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Funding

  1. Universidad Nacional de Colombia

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This study evaluates the catalytic activity of different morphologies of ceria nanoparticles doped with Ni and Pd oxides for n-C-7 asphaltene thermo-oxidation. The results show that cubic CeO2 nanoparticles exhibit the highest conversion rate for asphaltene.
The overall objective of this study is to evaluate the effect of morphologies (C, cubic; O, orthorhombic; and S, spherical) of ceria in the catalytic activity for n-C-7 asphaltene thermo-oxidation. In this way, cubic (C-CeO2), orthorhombic (O-CeO2), and spherical (S-CeO2) ceria nanoparticles were synthesized using the hydrothermal method and doped with 1.0% in a mass fraction of Ni and Pd oxides by incipient wetness impregnation. The catalytic activity of the systems was evaluated through nonisothermal and isothermal thermogravimetric analyses at different pressures. The non-isothermal thermogravimetric results evidenced an increase in the n-C-7 asphaltene mass as the temperature increases between 100 and 230 degrees C for all systems and operating conditions. At 3.0 MPa, n-C-7 asphaltene gains 3.6, 5.8, and 3.2% for O-CO2, C-CeO2, and S-CeO2, respectively, while at 6.0 MPa, there is an increase of 7.3, 10.4, and 5.9% for the same systems, respectively. The Ni and Pd phases increase the amount of oxygen chemisorbed in all systems in the order S-NiPdCe < O-NiPdCe < C-NiPdCe and reduce the temperature required for the total n-C-7 asphaltene decomposition at temperatures lower than 200 degrees C at 6.0 MPa in the same order. Also, isothermal thermogravimetric analysis demonstrates that the asphaltene conversion increased with ceria-based nanocatalysts in the increasing order S-CeO2 < O-CeO2 < C-CeO2. Cubic CeO2 doped with Ni and Pd presents the highest yield, reaching 100% conversion at 170 degrees C and 6.0 MPa at 60 min. The data confirm that the presence of Ni and Pd facilitate the transference oxygen vacancies between the bulk and surface of the nanocatalyst, and therefore, the catalytic activity is enhanced. The catalytic activity, in turn, is improved by the presence of {110}, {100} and {111}, oxygen vacancies, and Ce3+ and NiO-Ce species. This work reveals the benefits of structured cubic ceria nanocatalysts as a promising support for nickel- and palladium-containing materials for n-C-7 asphaltene decomposition.

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