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Oxidative denitrogenation of quinoline using cobalt ferrite catalysts
* 1, 2 , 1, 3, 4 , 1 , 5
1  CIMO, LA SusTEC, Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal
2  Universidade Tecnológica Federal do Paraná (UTFPR), Campus Campo Mourão, Via Rosalina Maria dos Santos, 1233 - Vila Carolo, Campo Mourão - PR, 87301-899, Brasil
3  LSRE-LCM – Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
4  ALiCE - Associate Laboratory in Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
5  Universidade Tecnológica Federal do Paraná (UTFPR), Campus Medianeira, Av. Brasil, 4232 - Independência, Medianeira - PR, 85884-000, Brasil
Academic Editor: Jean-François Lamonier

Abstract:

The presence of nitrogenated compounds in fossil fuels leads to NOx formation during combustion; these are harmful pollutants that pose significant environmental and health challenges. Hydrotreatment, the conventional strategy for denitrogenation, requires severe conditions, which motivates the search for more environmentally friendly alternatives. Oxidative denitrogenation (ODN) requires milder operating conditions and explores the oxidative reactivity of nitrogen compounds. In this study, cobalt ferrite (CoFe2O4) catalysts were synthesized and coated with silica (SiO2) or carbon (C), and applied for the ODN of quinoline, common in fuels, using hydrogen peroxide as the oxidant.

The superparamagnetic CoFe2O4 (core) was synthesized using the sol–gel method and, using an adaptation of the Stöber method, further coated with SiO2 or C (shell). Characterization techniques, such as XRD, FTIR, and contact angle measurements, confirmed the core–shell structure of the developed catalyst and showed a remarkable change in the ferrite’s hydrophobic surface properties upon coating (a decrease from 130° to 40° with silica). Crystallite sizes in the range of 19-20 nm were obtained.

Quinoline adsorption tests showed the low adsorption capacity of the materials, in accordance with the low surface area and pore volume determined by N2 adsorption isotherms at 77 K (SBET = 9-10 m2 g-1). In oxidation reactions, CoFe2O4@SiO2 showed the best catalytic performance (XQN = 74%, 8 h), likely ascribed to its hydrophilic surface, favorable to the generation of oxygen reactive species through the decomposition of H2O2 and consequent higher quinoline removal. Quinoline degradation was verified by GC-MS, which indicated the opening of the pyridine ring.

The results highlight that cobalt ferrite-based catalysts employed in oxidative denitrogenation are capable of degrading and mineralizing quinoline under mild conditions, as confirmed by TOC analyses. The surface properties of the coatings significantly increased the catalytic efficiency, emphasizing their potential as environmentally friendly and efficient candidates for the removal of nitrogen compounds from fossil fuels.

Keywords: Oxidative denitrogenation; cobalt ferrite; coated catalysts; quinoline removal; fossil fuels
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