Facultad Regional Córdoba

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    Sulfur elimination by ODSwith titanium-modified SBA-16.
    (Univesidsad Tecnológica Nacional., 2015) Rivoira , Lorena Paola; Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Martínez , María Laura; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel
    Over the past, oxidative desulfurization (ODS) has drawn considerable interest as a new alter-native method for deep sulfur elimination from light oils. This can be attributed to its attractive properties, including lower temperature and pressure conditions and lower operating cost than conventional hydrodesulfurization (HDS) process. Oxidation of organosulfur compounds results in the formation of sulfoxides/sulfones, highly polar and hence easily removed by both extraction into polar solvents or by adsorption. Due to their low reactivity, dibenzothiophene derivatives (DBTs) are the most refractory species to be eliminated from oils. Hence, the ODS process through which DBTs are converted to their corresponding sulfones involves great interest at present. In this work, we describe the preparation and characterization of new mesoporous catalytic materials based on Ti-containing SBA-16. We study here, the effect of the preparation method of titania-modified SBA-16 (characteristics of the active Ti and/or TiO2 species) and the effect of the different operation conditions in ODS of DBT under mild conditions in order to find the best performance. TiO2-modified mesoporous SBA-16 and titanium-substituted mesoporous SBA-16 were developed and tested in the oxidative desulfurization (ODS) of dibenzothiophene prevailing in liquid fuel. We assessed the impact exerted on performance of different reaction variables, including (nature and amount of the active catalytic species, phase system, molar ratio of oxidant H2O2 and DBT, reaction temperature, nature of the substrate and reuse of catalysts). We achieved 90% of S removal from a 0.2 wt.% dibenzothiophene solution at 60°C in less than 1 h of reaction. The best catalytic results are obtained with high exposed surface of nanometric TiO2 species of TiO2/SBA-16 sample. The activated catalyst is very active in ODS reaction and can be reused four times with no loss in activity
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    Vanadium oxide supported on mesoporous SBA-15 modified with AI and Ga as a highly active catalyst in the ODS of DBT.
    (Univesidsad Tecnológica Nacional., 2017) Rivoira , Lorena Paola; Martínez , María Laura; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo
    Vanadium pentoxide supported on mesoporous SBA-15 catalysts with different vanadium loadings were studied in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. The catalytic activity was improved when SBA-15 framework was modified with Al and Ga as heteroatom substituting Si. Structural and textural characterization of the catalysts were performed by means of XRD, N2 adsorption, UV–Vis–DRS, XPS, NMR, TEM, Raman, TPR and Py-FTIR. UV–Vis– DRS and Raman demonstrated that highly dispersed vanadium pentoxide crystallites are responsible for the high activity in the sulfur removal. The high dispersion depends on the vanadium loading and on the nature of the support. The more acidic support allowed better dispersion of the vanadium species. The Ga modified support with an intermediate V/Si ratio of 1/30 was the most active catalyst for ODS of DBT, using hydrogen peroxide (H2O2) as oxidant and acetonitrile as solvent. 100% of DBT elimination was attained at a
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    Iron-modified mesoporous materials as catalysts for ODS of sulfur compounds.
    (Univesidsad Tecnológica Nacional, 2018) Rivoira , Lorena Paola; Juárez , Juliana María; Martínez , María Laura; Beltramone , Andrea Raquel; Juárez , Juliana María
    Mandatory environmental regulations have been legislated all over the world so the top permitted content of sulfur in diesel is 15 ppm. ODS is the oxidation of sulfur compounds present in diesel to form sulfoxides and sulfones. These substances are highly polar and hence easily removed by extraction with solvent. Oxidant agent commonly used are peroxides such as hydrogen peroxide and tert-butylhydroperoxide (Di Giusepe et al., 2009). Since Diesel is a non-polar liquid while H2O2 is a polar liquid, a polar solvent is needed. The formed polar products can be easily removed from the operation unit by liquid liquid extraction. Mesoporous materials have been tried showing potential catalytic applications. Transition metals are commonly used as catalyst in ODS such as Mo, Mn, Sn, Fe, Zn, V and Ti (Cedeño-Caero et al., 2011). In this work, we propose the application of different supports as SBA-15, MCM-48, CMK-1 and CMK-3 for the preparation of Fe-catalysts.