Facultad Regional Córdoba
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Item Eliminación de azufre mediante desulfuración oxidativa con Ti-SBA-16. Parte I. Síntesis y caracterización.(Univesidsad Tecnológica Nacional., 2015) Rivoira , Lorena Paola; Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Ponte , María Virginia; Martínez , María Laura; Beltramone , Andrea Raquel; Martínez , María Laura; Ponte , María Virginia; Ledesma , Brenda Cecilia; Ledesma , Lorena Paola; Vallés , Verónica AlejandraSe desarrollaron catalizadores tipo SBA-16 modificados con Ti como TiO2 y como heteroatomo y se probaron en la desulfuración oxidativa (ODS) del dibenzotiofeno predominante en el combustible líquido. Se utilizó TiO2 puro como referencia para comparar la actividad catalitica. Los catalizadores fueron caracterizados mediante análisis químico, XRD, EDX y TEM. El estado de coordinación tetraédrico del titanio (en la muestra de Ti-SBA-16) u octaédrico (en la muestra de TiO2/SBA-16) en la matriz de sílice se determinó por XPS, UV-vis DRS, FTIR, Raman y XANES. La actividad catalítica se muestra en la Parte 2 de este trabajo.Item Tetralin Hydrogenation over Ir-Pt/SBA-15. Optimization by experimental desing.(Univesidsad Tecnológica Nacional., 2015) Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Rivoira , Lorena Paola; Cussa , jorgelina; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Cussa , jorgelina; Rivoira , Lorena Paola; Ledesma , Brenda CeciliaBimetallic catalysts have received considerable attention for hydrotreating (HDT) because they show high activity. The features of the catalysts here studied are going to be correlated with their catalytic performance in the hydrogenation of tetralin at mild conditions. The final goal is to find the optimal proportion of each metal in order to be more active and the best reaction conditions (temperature and amount of catalyst). The statistical experiments design is the process of planning an experiment to obtain appropriate data that can be analyzed by statistical methods, to produce concrete and valid conclusions. One of the main advantages in the response curve is to visualize the response for all levels of the experimental factors Experiment design response surface methodology (RSM) is used in this work to model and to optimize the process. Platinum and Iridium nanoparticles were incorporated into SBA-15 support by the wet co impregnation method. Ir content was set as 1wt. % and Pt was varied from 0 to 1wt. %. The catalysts were characterized by XRD, BET, XPS, TEM, ICP and TPR. XRD profiles are characteristic of the two-dimensional p6mm hexagonal mesostructure with d100 spacing of 10.16 nm; where the d100 spacing upon Ir and Pt incorporation were quite similar to pristine SBA-15. The TEM images and XPS demonstrate that the metal particles were mainly present inside the porous and XPS and TPR corroborated the reduced state of the metals. The catalytic activity was measured in a 4563Parr reactor at 15 atm of hydrogen and 360 rpm. Feed consisted in 50 mL of tetralin in Dodecane, the amount of tetralin is set according to the ratio of catalyst mass/mass reagent corresponding to each reaction. The application of this methodology allows a better understanding of the influence of the different factors: content of metal on catalyst (A), relationship: mass of catalyst/reagent mass (B) and reaction temperature (C), on two responses: conversion at 3 h and at 5 h of reaction time. These factors were carefully selected taking account the influence of the parameters in the reaction. The design was analyzed by Statgraphics and Statistica Soft. We found that, the variable Catalyst has the best influence over the Conversion at the 95.0% confidence level, according to the Pareto.Item Hydrodenitrogenation of over Ir supporteD Ti-SBA-15 modified with F AND AI.(Univesidsad Tecnológica Nacional., 2015) Ledesma , Brenda Cecilia; Vallés , Verónica Alejandra; Rivoira , Lorena Paola; Balangero, Gerardo Simón; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Rivoira , Lorena Paola; Vallés , Verónica AlejandraThe hydrodenitrogenation of Indole has been studied over a series of Ti-modified SBA 15 supports and their respective Ir-catalysts. Ti-SBA-15 was synthesized using sol-gel method and Ti was added during the synthesis using TEOT as Ti source. Ti was incorporated into the framework replacing the Si atoms in the mesoporous structure. Ir/Ti-SBA-15 with and without F and/or Al were prepared to improve the catalytic activity. F and Al have been incorporated by wetness impregnation method. The effect of the incorporation of F and Al in the mesoporous structure was tested in the hydrodenitrogenation reaction of indole. The catalysts were extensively characterized by X-ray diffraction (XRD), N2 adsorption isotherms, TEM, FTIR and UV-vis-DRS and Raman spectroscopy. The low angle X-ray analysis showed for all the materials intensive reflection, characteristic of SBA-15 structure. The mesoporous structure was maintained after F and Al incorporation. The results showed that Ti incorporation reduces significantly the cluster size and improves considerably the Ir cluster dispersion. The catalytic activity of Ir/Ti-SBA-15 modified with F and Al, with higher acidity, avoided the irreversible adsorption of indole. The catalytic activity was studied in a 4563 Parr reactor, at 250°C, 15 atm of pressure of hydrogen and 360 rpm. The catalysts synthesized had good activity measured in hydrodenitrogenation of indole at mild conditions. The preliminary results show these materials as promising catalysts for HDN reactions.Item 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 LauraOver 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)Item Experimental Desing Optimization of the tetralin Hydrogenation over Pt-Ir/SBA-15.(Univesidsad Tecnológica Nacional., 2015) Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Rivoira , Lorena Paola; Cussa , jorgelina; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Cussa , jorgelina; Rivoira , Lorena Paola; Ledesma , Brenda Ceciliahe oil refining industry has a difficult challenge to meet the increasingly stringent regula tions on environmental issues. Contaminants such as sulfur, nitrogen, fused ring aromatic compounds or metals are the principal to remove to achieve "green" fuels. The hydrotreating (HDT) is one of the processes most used in the refinery to remove these contaminants. To optimize the gas oil hydrotreater, it is crucial to understand the aromatic hydrogenation reac tion chemistry occurring in the gas oil hydrotreater. To find alternative processes, it is neces sary to develop new and more active catalysts to replace the current ones. Bimetallic Pt–Pd catalysts have received considerable attention, because they show high actvity in a variety of catalytic applications [1,2]. From a fundamental point of view, exploring bimetallic catalysts also allows better understanding of mechanisms and variables involved in the catalytic reac tions. The features of the catalysts here studied are going to be correlated with their catalytic performance in the hydrogenation of tetralin. The final goal is to find the optimal proportion of each metal in order to be more active and the best reaction conditions. The statistical expe riments design is the process of planning an experiment to obtain appropriate data that can be analyzed by statistical methods, to produce concrete and valid conclusions [3]. One of the main advantages in the response curve is to visualize the response for all levels of the experi mental factors Experiment design response surface methodology (RSM) is used in this work to model and to optimize the process.Item 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 AlejandraOver 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).Item Hydrogenation of tetralin in presence of nitrogen using a noble-bimetallic couple over a Ti-modified SBA-15.(Univesidsad Tecnológica Nacional., 2017) Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Rivoira , Lorena Paola; Cussa , jorgelina; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Cussa , jorgelina; Rivoira , Lorena Paola; Ledesma , Brenda CeciliaThe increased attention paid to catalytic hydrogenation in the oil refining industry is due in part to legislation regarding the maximum contents of sulfur, aromatic compounds, and alkenes in traffic fuels. Aromatics in diesel increase the particle emissions in exhaust gases and they have the further effect of lowering the fuel quality. Many factors such as the catalysts, process parameters, feedstock source and quality, reactivities of sulfur compounds, inhibition effects of H2S, nitrogen compounds and aromatics present in the feed, etc. can have significant influences on the degree of hydrogenation of diesel feeds1,2. Recently, studies have been reviewed and the investigations have also been extended to noble metals3 . In our previous investigations with bimetallic catalysts4 , we had very good results preparing the catalysts by co impregnation of the relevant metals on the SBA-15 mesoporous matrix. These studies showed high activity, selectivity and stability as well also greater resistance to poisons compared to monometallic catalysts. In this contribution titanium is incorporated in tetrahedral position replacing silicon in the mesoporous framework. We expect that Ti incorporation improve the dispersion of the bimetallic clusters. In the present work three compounds tetralin, indole and quinoline were used as models for the compounds in diesel. The model compounds were hydrogenated both separately and as mixtures in order to study the inhibition effect.Item ODS of dibenzothiophene over V-SBA-15 mesoporous material.(Univesidsad Tecnológica Nacional., 2016) Rivoira , Lorena Paola; Martínez , María Laura; Falcón, Horacio; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Martínez , María LauraOxidative desulfurization (ODS) is considered a new alternative method for deep sulfur elimination from light oils. This can be due to its attractive properties, including lower temperature and pressure conditions and lower operating cost than conventional hydrodesulfurization 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. The oxidation of DBTs with organic hydroperoxides or H2O2 was studied over various catalytic heterogeneous systems, such as supported oxide metals or titanium silicalites1-9. Vanadosilicates were used as catalysts for the desulfurization of light oil10-12. The oxidation of (DBTs) was also performed using WOx/ZrO2 catalyst13, supported Pd, Cr2O3, unsupported manganese oxides and a commercial Co Mo/Al2O3 with hydrogen peroxide as oxidant14. In general, when tetravalent cations like Ti4+, Zr4+, V4+, Sn4+, etc. are incorporated to the framework of SBA 15, the electroneutrality is maintained but some redox properties are incorporated to the support surface15,16 . In this work we evaluate vanadium modified mesoporous SBA-15 in the ODS of dibenzothiophene as a model sulfur compoundItem Optimización de la síntesis del material mesoestructurado SBA-3 mediante diseño experimental.(Univesidsad Tecnológica Nacional., 2016) Ponte, María Virginia; Rivoira , Lorena Paola; Cussa , Jorgelina; Martínez , María Laura; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Anunziata , Oscar Alfredo; Martínez , María Laura; Cussa , jorgelina; Rivoira , Lorena PaolaEl material SBA-3 está constituido por una estructura de sílice mesoporosa de ordenamiento de poros regular hexagonal, diámetro de poro >3nm; presenta alta área superficial y alto volumen de poro. Se utilizó la metodología de Superficie de Respuesta para el modelado y optimización de las condiciones de síntesis de SBA-3. Se analizaron como factores del Diseño la influencia de la relación molar entre el surfactante (CTAB) y la fuente de silicio (TEOS), el tiempo de envejecimiento, la temperatura y el pH de la síntesis utilizando HCl. La respuesta analizada fue la intensidad de difracción de rayos X para el plano [100]. Las superficies de respuestas se obtuvieron con el diseño Box–Behnken, buscando la combinación de los parámetros que dieran como resultado la mejor estructura en el material sintetizado. Mediante la aplicación de metodología estadística, los mayores valores de la función objetivo (intensidad de DRX para el plano [100]) se obtuvieron utilizando valores de la relación molar CTAB/TEOS de 0,07-0,16; HCl/TEOS de 8-11; temperatura de síntesis de 35-45 (ºC) y tiempos de envejecimiento de 12-24hr.Item Óxidos de vanadio y titanio soportados sobre CMK-3 como un nuevo catalizador para la desulfuración oxidativa de DBT.(Univesidsad Tecnológica Nacional., 2016) Rivoira , Lorena Paola; Juárez , Juliana María; Falcón, Horacio; Gómez Costa, Marcos Bruno; Anunziata , Oscar Alfredo; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Juárez , Juliana MaríaEn el presente trabajo se estudiaron catalizadores de vanadio soportados sobre el carbón mesoporosos CMK 3 con diferentes contenidos de Vanadio (1-7 % p/p) en la desulfurización oxidativa de dibenzotiofeno (DBT) como modelo de compuestos sulfurados. La actividad catalítica se comparó con catalizadores de Titanio soportados en CMK-3. Las propiedades estructurales y texturales de los catalizadores se analizaron mediante estudios de adsorción de N2, XRD, UV-Vis-DRS y TEM. Tanto la dispersión como la actividad catalítica dependen fuertemente del contenido de vanadio. La muestra que contiene el 7% p/p de Vanadio es el catalizador con mejor actividad catalítica para la reacción de ODS de DBT utilizando peróxido de hidrógeno ((H2O2) como oxidante y acetonitrilo como solvente. El 100% de la eliminación de DBT se alcanzó a corto plazo en condiciones suaves. El carbon mesoporoso CMK-3 con una alta área superficial y gran volumen de poros promueve el anclaje del metal en la red de carbono, lo que permite alcanzar una alta distribución de sitios activos y nanoclusters más estables. La reutilización del catalizador indica que V-CMK-3 es un catalizador potencial para los ODS de dibenzotiofeno.