Physicochemical characteristics of calcined MnFe 2 O 4 solid nanospheres and their catalytic activity to oxidize para-nitrophenol with peroxymonosulfate and n-C 7 asphaltenes with air
Fecha de publicación: 01/03/2021

Manganese ferrite solid nanospheres (MSNs) were prepared by a solvothermal method and calcined at various temperatures up to 500 °C. Their surface area, morphology, particle size, weight change during calcination, surface coordination number of metal ions, oxidation state, crystal structure, crystallite size, and magnetic properties were studied. The MSNs were used as catalysts to activate potassium peroxymonosulfate (PMS) for the oxidative degradation of para-nitrophenol (PNP) from water and for the oxidation of n-C₇ asphaltenes in flowing air at atmospheric (0.084 MPa) and high pressure (6 MPa). Mn was in oxidation states (II) and (III) at calcination temperature of 200 °C, and the crystalline structure corresponded to jacobsite. Mn was in oxidation states (III) and (IV) at 350 °C and in oxidation states (II), (III), and (IV) at 500 °C, and the crystalline structure was maghemite at both temperatures. MSN catalysts generated hydroxyl (HO·) and sulfate (SO₄^·-) radicals in the PMS activation and generated HO· radicals in the n-C₇ asphaltene oxidation. In both reactions, the best catalyst was MSN calcined at 350 °C (MSN350), because it has the highest concentration of Mn(III) in octahedral B sites, which are directly exposed to the catalyst surface, and the largest total and lattice oxygen contents, favoring oxygen mobility for Mn redox cycles. The MSN350 sample reduces the decomposition temperature of n-C₇ asphaltenes from 430 to 210 °C at 0.084 MPa and from 370 to 200 °C at 6.0 MPa. In addition, it reduces the effective activation energy by approximately 77.6% in the second combustion (SC) region, where high-temperature oxidation reactions take place.

Extra-Heavy Crude Oil Viscosity Reduction Using and Reusing Magnetic Copper Ferrite Nanospheres
Fecha de publicación: 15/01/2021

The main objective of this study is the synthesis, use, and reuse of magnetic copper ferrite nanospheres (CFNS) for extra-heavy oil viscosity reduction. The CFNS were synthesized using a solvothermal method resulting in mean particle size of 150 nm. Interactions of CFNS with the crude oil were evaluated through asphaltene adsorption isotherms, as well as static and dynamic rheology measurements for two cycles at 25 °C. Adsorption and desorption experiments corroborated that most of the asphaltenes adsorbed can be removed for nanoparticle reuse. During the rheology tests, nanoparticles were evaluated in the first cycle at different concentrations from 300 to 1500 mg/L, leading to the highest degree of viscosity reduction of 18% at 500 mg/L. SiO₂ nanoparticles were evaluated for comparison issues, obtaining similar results regarding the viscosity reduction. After measurements, the CFNS were removed with a magnet, washed with toluene, and further dried for the second cycle of viscosity reduction. Rheology tests were performed for a second time at a fixed concentration of 500 mg/L, and slight differences were observed regarding the first cycle. Finally, changes in the extra-heavy oil microstructure upon CFNS addition were observed according to the significant decrease in elastic and viscous moduli