Desarrollo, Producción e Innovación en la Investigación científica
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Item Vanadium and titanium oxide supported on mesoporous CMK-3 as new catalysts for oxidative desulfurization.(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 MaríaVanadium supported-CMK-3 catalysts with vanadium loading of 1–7 wt.% were studied in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. The activity was compared with titanium supported-CMK-3. Structural and textural characterization of the catalysts was performed by means of N2 adsorption, XRD, UV–vis–DRS, Raman spectroscopy, XPS, TEM and TPR. The dispersion and the nature of the vanadium species depend on the V loading, so does the catalyst activity. Vanadium supported-CMK-3 with 7 wt.% of vanadium loading 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 short time in mild conditions. Carbon ordered mesoporous CMK-3 with high surface area and high pore volume promotes a very good anchorage of metallic oxides in the carbons framework reaching high active sites distribution and more stable nanoclusters. The reusability of the catalyst indicates that V-CMK-3 is a potential catalyst for the ODS of dibenzothiopheneItem Novel preparation of CMK-3 nanostructured material modified with titania applied in hydrogen uptake and storage.(Univesidsad Tecnológica Nacional., 2016) Juárez , Juliana María; Ledesma , Brenda Cecilia; Gómez Costa, Marcos Bruno; Beltramone, Andrea Raquel; Anunziata , Oscar Alfredo; Anunziata , Oscar Alfredo; Ledesma , Brenda CeciliaThis work deals with the development of a novel procedure to synthesize titania-modified nano structured carbon employing Ti-SBA-15 as hard template. The new mesoporous carbon displays high specific surface area of 1044 m2/g and large pore volume of 0.7 cm3/g. XRD pattern of Ti-CMK-3 indicates that the ordered structure of this material is similar to the CMK-3. XRD, XPS and UVeVis-DRS analysis indicated that Ti is highly dispersed as anatase phase in Ti-CMK-3. The synthesized Ti-CMK-3 exhibited significantly enhanced H2 storage properties (2.6 wt%, equivalent to 13 mmol/g) compared with CMK-3 without Ti (2.2 wt%, 11 mmol/g) at 77 K and 10 bar.Item Novel and simple one-pot method for the synthesis of Ti02 modified-CMK-3 applied in oxidative desulfurization of refractory organosulfur compounds.(Univesidsad Tecnológica Nacional., 2016) Rivoira , Lorena Paola; Ledesma , Brenda Cecilia; Juárez , Juliana María; Beltramone , Andrea Raquel; Juárez , Juliana María; Ledesma , Brenda CeciliaTi-CMK-3 carbon mesoporous was prepared using a novel synthesis method. This new method avoids the hard template synthesis used commonly. The precursors of silicon, carbon and titanium are incorporated together with the other components during the only step of the synthesis. The method developed here, allows reducing time and energy consumption by 60% and thus, the cost of the overall process of synthesis. Structural and textural characterization of the titanium modified-mesoporous carbon was performed by N2 adsorption, XRD, UV–Vis DRS, XPS, Raman spectroscopy and TEM. The characterization results indicated that the textural and structural properties of the material synthesized by the short time method are comparable with the properties of the material prepared by the hard template method. Ti modified-mesoporous carbon was synthesized by dif- ferent methods in order to prepare catalysts to be tested in the oxidative desulfurization (ODS) of sulfur com- pounds. The catalyst prepared by the one-pot method is capable to oxidize high amount of sulfur (2000 ppm) in only 30 min of reaction time at 60–80 °C. The good performance and stability of the catalyst prepared using a novel synthesis method was attributed to well dispersed anatase nanospecies over the high area mesoporous carbon. Main advantage of the present study is the reduction of time and cost in the synthesis of the new material and the applicability for ODS reactions.Item Noble-bimetallic supported CMK-3 as a novel catalyst for hydrogenation of tetralin in the presence of sulfur and nitrogen.(Univesidsad Tecnológica Nacional., 2016) Vallés , Verónica Alejandra; Ledesma , Brenda Cecilia; Juárez , Juliana María; Gómez Costa, Marcos Bruno; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Juárez , Juliana María; Ledesma , Brenda CeciliaCarbon ordered mesoporous CMK-3 with high surface area and high pore volume promotes a very good dispersion of Pt or Ir monometallic and Pt-Ir-bimetallic crystallites in the carbon framework. High active and stable nanospecies are responsible for the good activity and selectivity found in the hydrogenation of tetralin to decalin in the presence of N as indole and S as dibenzothiophene under mild conditions in a Batch reactor. The catalysts prepared were extensively characterized by XRD, N2 adsorption isotherms, XPS, TEM, ICP, CO Chemisorption and TPR. The analysis showed that the carbon mesoporous structure was maintained after metal incorporation, and very high dispersed metal-supported catalyst was obtained. The activity was compared using the turnover number, Pt-Ir-CMK-3 being the most active cat alyst in the presence of the inhibitors. The bimetallic catalyst showed more resistance to inhibition than monometallic catalysts. The reusability of Pt-Ir-CMK-3 suggests that it is a potential catalyst for hydrotreating reactions.Item Novel preparation of titania-modified CMK-3 nanostructured material as support for Ir catalyst applied in hydrodenitrogenation of indole.(Univesidsad Tecnológica Nacional., 2017) Ledesma , Brenda Cecilia; Juárez , Juliana María; Vallés , Verónica Alejandra; Anunziata , Oscar Alfredo; Beltramone, Andrea RaquelAbstract Iridium catalyst was prepared using a novel tita nium oxide-CMK-3 support synthesized as a replica of Ti SBA-15. The catalyst was applied in the hydrodenitrogena tion of indole. The activity was compared with an iridium catalyst supported over a grafted titanium-CMK-3. Struc tural and textural characterization of the catalysts was per formed by means of N2 adsorption, XRD, UV–Vis–DRS, Raman spectroscopy, XPS, TEM and H2 Chemisorption. Ir Ti-CMK-3 was the most active catalyst for the hydro denitrogenation reaction at mild conditions. Titanium oxide contained in carbon ordered mesoporous CMK-3 promotes a very good anchorage of iridium metallic clusters in the carbon framework reaching high active site distribution and more stable nanoclusters.Item Vanadium and titanium oxide supported on mesoporous CMK-3 as new catalysts for oxidative desulfurization.(Univesidsad Tecnológica Nacional., 2017) Rivoira , Juliana María; Juárez , Juliana María; Falcón, Horacio; Gómez Costa, Marcos Bruno; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Juárez , Juliana MaríaDiesel emissions contribute to environmental issues associated to sulfur oxides released during the combustion process of fuels. Ultra-low-sulfur-diesel (ULSD) is diesel with substantially lowered sulfur content. Many countries have established regulations to restrict the S content in petroleum products to be 15 ppm and zero emission is even expected1 . Alternatively, oxidative desulfurization (ODS) provides selective removal of those refractory sulfur compounds at proper temperatures and pressure and is capable to eliminate most refractory sulfur compounds in HDS. This is the process wherein dibenzothiophene derivatives are converted to their corresponding sulfone, which could be easily separated from the oil. Therefore, ODS has a great potential to become a complementary process to traditional HDS in the production of deeply desulfurized diesel fuels. In view of the recent studies, Ti and V oxides have demonstrated to improve S-compounds oxidation2,3. In this work we evaluate vanadium and titanium-based catalysts supported over a mesoporous carbon with large surface area (CMK-3) in the ODS of dibenzothiophene as a model sulfur compound.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.Item Synthesis and characterization of a nanoporous carbon CMK-3 modified with iron for the ODS of DBT.(Univesidsad Tecnológica Nacional., 2017) Juárez , Juliana María; Rivoira , Lorena Paola; Gómez Costa, Marcos Bruno; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Rivoira , Lorena PaolaA nanostructured Carbon CMK-3 modified with Fe by using different sources of Fe, were used in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. Ordered mesoporous carbon CMK-3 was synthesized via a two-step impregnation of the SBA-15 silica mesonanopores with a solution of sucrose using an incipient wetness method. The sucrose–silica composite was heated at 1173 K for 4 h under nitrogen flow. The silica template was dissolved in 5 wt.% hydrofluoric acid in order to remove the silica. The template-free carbon product thus obtained was filtered, washed with deionized water and ethanol and dried. Fe-CMK-3 was prepared by wetness impregnation using FeCl3.6H2O and FeNO3.9H2O as different sources of Fe. A solution of FeCl3.6H2O/ FeNO3.9H2O in ethanol was mixed with the carbon solution at room temperature. The solution was placed in a rotary evaporator to remove excess of ethanol at about 333 K and 60 rpm. Afterwards, the sample was dried at 373 K for 18 h and was thermally treated in a dynamic inert (N2) atmosphere. The percentage of Fe has been 2 wt.% with respect to carbon in the final FeCl3-CMK-3 and FeNO3-CMK 3 material. Porous carbon CMK-3 and the samples modified with Fe were characterized by XRD, FTIR, XPS, BET, TEM and SEM. These studies indicated that it was possible to obtain a CMK-3 replica successfully from SBA-15, using sucrose as a carbon precursor. Wide angle XRD pattern of the sample modified with FeCl3.6H2O implies the formation of the magnetite phase in the silica channels. The surface areas were 1320 m2/g for the CMK-3 and 1240 m2/g and 609 m2/g for FeCl3- CMK-3 and FeNO3-CMK-3, respectively. While the nanomaterial area is significantly smaller with the incorporation of the metal, CMK-3`s characteristic structure is maintained after the metal is within the host, in agreement with the XRD studies. The catalytic activity was improved when the nanoporous carbon was modified with Fe. The sample modified with FeCl3.6H2O 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 short time in mild conditions.Item Novel preparation of titania-modified CMK-3 nanostructured material as support for Ir catalyst applied in hydrodenitrogenation of indole.(Univesidsad Tecnológica Nacional., 2018) Ledesma , Brenda Cecilia; Juárez , Juliana María; Vallés , Verónica Alejandra; Anunziata , Oscar Alfredo; Beltramone , Andrea Raquel; Anunziata , Oscar Alfredo; Vallés , Verónica Alejandra; Juárez , Juliana MaríaIridium catalyst was prepared using a novel titanium oxide-CMK-3 support synthesized as a replica of Ti-SBA-15. The catalyst was applied in the hydrodenitrogenation of indole. The activity was compared with an iridium catalyst supported over a grafted titanium CMK-3. Structural and textural characterization of the catalysts was performed by means of N2 adsorption, XRD, UV–Vis–DRS, Raman spectroscopy, XPS, TEM and H2 Chemisorption. Ir-Ti-CMK-3 was the most active catalyst for the hydrodenitrogenation reaction at mild conditions. Titanium oxide contained in carbon ordered mesoporous CMK-3 promotes a very good anchorage of iridium metallic clusters in the carbon framework reaching high active site distribution and more stable nanoclustersItem Novel and simple one-pot method for the synthesis of titanium modified-CMK-3 applied in desulfurization of refractory oeganosulfur compounds.(Univesidsad Tecnológica Nacional., 2018) Rivoira , Lorena Paola; Ledesma , Brenda Cecilia; Juárez , Juliana María; Beltramone, Andrea Rauqel; Juárez , Juliana María; Ledesma , Brenda CeciliaTi-CMK-3 carbon mesoporous was prepared using a novel synthesis method. This new method avoids the hard template synthesis used commonly. The method developed here, allows reducing time, energy consumption and cost. Our primary aim in this work is to evaluate the ODS activity of the Ti-modified mesoporous carbon CMK-3, synthesized by the short time method, in order to achieve total removal of sulfur compounds from diesel fuel. The catalytic oxidation of the sulfur compound with hydrogen peroxide was carried out in a glass batch reactor, equipped with a magnetic stirrer, a thermometer and a condenser. In a typical run, the solid catalyst (60 mg) was suspended under stirring (750 rpm) in 20 mL of a solution of 500 ppm of S as DBT (or other) in acetonitrile. Then, appropriate amount of 30% aqueous H2O2 was added at constant temperature. The experiments were performed in a three-phase liquid-liquid-solid (L (oil) –L (solvent) –S (catalyst)) system, acetonitrile was used as solvent and dodecane as oil phase. Solution samples were recovered at various times. The products were analyzed by GC HP 5890 Series II with a HP-5 column and connected to FID and PFPD detectors, after filtration and eventually decantation step. The products were confirmed using a Shimadzu GCMS. Structural and textural characterization of the titanium modified-mesoporous carbon was performed by N2 adsorption, XRD, UV-Vis-DRS, XPS, Raman spectroscopy and TEM. The characterization results indicated that the textural and structural properties of the material synthesized by the short time method are comparable with the properties of the material prepared by the hard template method. Ti modified-mesoporous carbon was synthesized by different methods in order to prepare catalysts to be tested in the oxidative desulfurization (ODS) of sulfur compounds. The good performance and stability of the catalyst prepared using a novel synthesis method was attributed to well dispersed anatase nanospecies over the high area mesoporous carbon. Main advantage of the present study is the reduction of time and cost in the synthesis of the new material and the applicability for ODS reactions.
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