Facultad Regional Córdoba

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    ODS of dibenzothiopene with 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; Anunziata , Oscar Alfredo; Martínez , María Laura
    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 attrac tive properties, including lower temperature and pressure conditions and lower operating cost [1-3] than conventional hydrodesulfurization (HDS) process. Oxidation of organosulfur com pounds 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, diben zothiophene 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 [4-6]. We recently reported a good performance of this sup port in hydrotreating processes [7]. In this work, we describe the preparation and characteriza tion 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 tempe rature, nature of the substrate and reuse of catalysts)
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    Sulfur elimination by oxidative desulfurization with titanium-modified SBA-16L.
    (Univesidsad Tecnológica Nacional., 2016) Rivoira , Lorena Paola; Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Martínez , María Laura; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Martínez , María Laura; Ledesma , Brenda Cecilia; Vallés , Verónica Alejandra
    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 attrac tive properties, including lower temperature and pressure conditions and lower operating cost [1-3] than conventional hydrodesulfurization (HDS) process. Oxidation of organosulfur com pounds 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, diben zothiophene 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 [4-6]. We recently reported a good performance of this sup port in hydrotreating processes [7]. In this work, we describe the preparation and characteriza tion 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 tempe rature, nature of the substrate and reuse of catalysts).
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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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    VOx-SBA-15 modified with AI and Ga in ODS of DBT.
    (Univesidsad Tecnológica Nacional., 2018) Rivoira , Lorena Paola; Martínez , María Laura; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Martínez , María Laura
    In order to adapt current processes to the strict regulatory requirements, several technologies have been developed for deep desulfurization of diesel fuel. The major portion of sulfur compounds in light cycle oils (LCO) are dibenzothiophene (DBT) and alkyl-dibenzothiophenes, which are not easily removable by hydrotreating. Vanadium oxides supported on mesoporous SBA-15 catalysts with different vanadium loadings were studied in the oxidative desulfurization (ODS) of dibenzothiophene. 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 VO4-3 species are responsible for the high activity in the sulfur removal. The Ga modified support with an intermediate V/Si ratio was the most active catalyst, using hydrogen peroxide as oxidant and acetonitrile as solvent. 100% of DBT elimination was attained at a short time in mild conditions. Gallium and aluminum incorporation modified successfully the nature of the SBA-15 surface by generating Bronsted and Lewis acidity. The interaction between the acid sites with the vanadium active sites improved the activity of the catalysts. The more acidic support allowed better dispersion of the vanadium species due to stronger interaction metal-support. The reusability of the catalysts indicates that vanadium oxide supported on mesoporous SBA-15 modified with Ga and Al are potential catalysts for the ODS of dibenzothiophene.