Browsing by Author "Martínez, María Laura"
Now showing 1 - 20 of 33
- Results Per Page
- Sort Options
Item Catalytic oxidation of sulfur compounds over Ce-SBA-15 and Ce-Zr-SBA-15(2021) Rivoira, Lorena Paola; Vallés, Verónica Alejandra; Martínez, María Laura; Yanika, Sa-ngasaeng; Siriporn, JongpatiwutThe catalytic oXidation of different sulfur compounds, commonly present in liquid fuel, was studied over a series of ceria and ceria-zirconium based oXidation mesoporous catalysts. SBA-15 was synthesized using sol-gel method and Ce and Ce-Zr were added by two different procedures: i) directly during the synthesis and ii) via post- synthesis method. The catalysts were characterized by XRD, N2 adsorption isotherms, XPS, DRUV-Vis, TEM, SEM and Py-FTIR. Low angle XRD, N2 isotherms and TEM confirmed that the structure was not changed after metal incorporation. Wide angle XRD, UV–vis-DRS, XPS and TEM determined that the catalysts prepared by direct synthesis presented higher dispersion of Ce oXides, smaller particle size and isolated Zr4+ species. FTIR of adsorbed/desorbed pyridine indicated that zirconium as promoter increases the Lewis acidity of the catalysts, especially during direct synthesis. Ce-Zr-SBA-15 catalyst prepared by direct synthesis was very active in the oXidation of dibenzothiophene, 4,6-dimethyl dibenzothiophene and benzothiophene using hydrogen peroXide (H2O2) as oXidant agent and acetonitrile as polar solvent. The effect of acidity in the catalyst, hydrogen peroXide concentration and temperature was studied. The deactivation test demonstrated that the catalyst is stable and adequate for the industrial process.Item Desulfuración oxidativa utilizando material mesoporoso Ti-SBA-16(2014) Rivoira, Lorena Paola; Vallés, Verónica; Ledesma, Brenda; Martínez, María Laura; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelLa oxidación de compuestos organosulfurados conduce a la formación de los sulfóxidos/sulfonas correspondientes, lo que permite que sean fácilmente removidos mediante extracción en solventes polares o por adsorción. El proceso de ODS es llevado a cabo bajo condiciones muy suaves, comparado con el proceso convencional de HDS. El objetivo del presente trabajo es estudiar el efecto del método de preparación de SBA-16 modificada con titanio en el rendimiento de la ODS del DBT con H2O2 y acetonitrilo como solvente en condiciones suaves de reacción. Se estudiaron dos materiales TiO2-SBA-16 obtenido por impregnación húmeda y Ti-SBA-16 obtenido mediante síntesis directa. con una relación de Si/Ti=20. Para la actividad catalítica se lleva a cabo la reacción de oxidación a 70°C y presión atmosférica se utilizó un reactor batch. Se utilizó H2O2 como agente oxidante y acetonitrilo como solvente.Item Eliminación de azufre mediante desulfuración oxidativa con SBA-16 modificada con titanio(2014) Rivoira, Lorena Paola; Vallés, Verónica; Ledesma, Brenda; Martínez, María Laura; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelLa oxidación de compuestos organosulfurados conduce a la formación de los sulfóxidos/sulfonas correspondientes, los cuales son mucho más polares, lo que permite que sean fácilmente removidos mediante extracción en solventes polares o por adsorción. El proceso de ODS es llevado a cabo bajo condiciones muy suaves (presión atmosférica y 60-90ºC), comparado con el proceso convencional de HDS, donde comúnmente son usadas presiones mayores a los 30 bar y temperaturas desde los 300 a los 380ºC. Resultados recientes muestran que tamices moleculares que contienen Ti exhiben buena reactividad catalítica en la oxidación de sulfuro, mercaptano, tiofeno y derivados (1). El objetivo del presente trabajo es estudiar el efecto del método de preparación de SBA-16 modificada con titanio (características de las especies activas de Ti y/o TiO2) en el rendimiento de la ODS del DBT con H2O2 y acetonitrilo como solvente en condiciones suaves de reacción.Item Esterification of succinic acid using sulfated zirconia supported on SBA-15(2021) Aguzin, Federico L.; Martínez, María Laura; Beltramone, Andrea Raquel; Padró, Cristina L.; Okulik, NoraCatalytic esterification of succinic acid with ethanol to obtain diethyl succinate (DES), a nontoxic plasticizer, is reported. Three sulfated zirconias supported on SBA-15 [SZ-SBA-15(X)] with Si/Zr molar ratios (X) of 10, 20, and 30 were syn- thesized and characterized. N2 adsorption/desorption isotherms and X-ray dif- fraction patterns evidenced preservation of the ordered mesoporous structure of the catalysts after incorporation of Zr. Yields of DES greater than 85 % were obtained at the final reaction time by using SZ-SBA-15(10) and SZ-SBA-15(20) catalysts, which were higher than those achieved with Amberlyst 36. Reuse of the SZ-SBA-15(20) catalyst showed that, even though the structure of the support was preserved, decreases in sulfur concentration and in the DES yield occurred.Item Estudio de la influencia de la temperatura de síntesis y la concentración de surfactante en la síntesis de SBA-3(2014) Ponte, María Virginia; Martínez, María Laura; Gómez Costa, Marcos Bruno; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelEn este trabajo se presentan resultados de preparación y caracterización de SBA-3, estudiando la variación de la temperatura de síntesis, así como la de la relación molar CTAB/TEOS. Condiciones de síntesis suaves (303 K) y adecuadas relaciones de surfactante/precursor de silicio conducen a un material mesoporoso con un ordenamiento regular hexagonal, característico de SBA-3 con elevada regularidad estructural.Item EXperimental design optimization of the ODS of DBT using vanadium oXide supported on mesoporous Ga-SBA-15(2020) Rivoira, Lorena Paola; Cussa, Jorgelina; Martínez, María Laura; Beltramone, Andrea RaquelEXperiment design-response surface methodology is applied in this work to model and optimize the o Xidation of dibenzothiophene (DBT) using VOX-Ga-SBA-15 catalyst. The analyzed variables are the influence of the nature of the catalyst (V and Ga loading), the s ubstrate/catalyst mass ratio (g DBT/g of catalyst) and the o Xidant/substrate molar ratio (H2O2/DBT). The response analyzed is conversion of DBT at 15 min of reaction time. A set of re- sponse surfaces were obtained applying the BoX-Behnken Design. Based on statistical methodology it was pos- sible to find the best arrangement between the amounts of the gallium heteroatom and the vanadium active species. The higher levels of the objective function were obtained employing the catalyst with 4 wt.% of gallium and 6 wt.% of vanadium; the optimal ratio between g DBT/g of catalyst was 4 and the molar ratio between H2O2/DBT was 5. Gallium incorporation as heteroatom in tetrahedral position allowed the better anchorage ofthe active species of vanadium, generating a very well dispersed catalyst. The optimized catalyst minimized the mass transfer limitation and moreover, was active after several recycles. The best catalyst was likewise very active for the oXidation of the most refractory sulfur compounds as benzothiophene and 4,6-dimetyldi- benzothiopene.Item HDT of the model diesel feed over Ir-modified Zr-SBA-15 catalysts(2018) Vallés, Verónica Alejandra; Yanika, Sa-ngasaeng; Martínez, María Laura; Siriporn, Jongpatiwut; Beltramone, Andrea RaquelIridium catalyst using different zirconium modified-SBA-15 supports were tested in the HDT of tetralin and typical sulfur and nitrogen compounds present in diesel feed. The zirconium modified-SBA-15 supports were synthesized by sol-gel method using two sources of zirconium, zirconyl chloride and zirconium (IV) propoXide. Regarding XRD, N2 adsorption isotherms and TEM, we obtained better textural and structural properties using the alkoXide, especially when lactic acid was added in order to decrease the hydrolysis rate of zirconium propoXide. In addition, XPS and DRUV-Vis demonstrated that zirconium was incorporated mainly as tetrahedral Zr4+ species NH3-TPD showed that higher acidity is observed when tetrahedral Zr4+ species are present. Iridium dispersion was determined by TEM and H2-chemisorption and reducibility by XPS and TPR. Among the catalysts prepared, the catalyst synthesized using zirconium propoXide and lactic acid presented the highest dispersion, lowest cluster size and lowest reduction temperature. Consequently, this was the most active catalyst for the hydrogenation of tetralin, the HDN of indole and quinoline and the HDS of dibenzothiophene (DBT) and 4,6- dimethyldibenzothiophene (4,6-DMDBT). The presence of Zr+4 had a remarkable effect on the dispersion and reducibility capacity of the iridium actives species. In addition, the presence of moderate acidity in this material gives the best catalyst for HDN and HDS in the studied conditions. The inhibition effect of the sulfur and nitrogen compounds over tetralin hydrogenation was studied using individual feeds and a miXture feed. We observe that 4,6-DMDBT and quinoline were the most refractory compounds and they showed the highest inhibition effect. Tetralin hydrogenation was stronger inhibited when using the miXture feed compared with the individual feeds. This can be explained in terms of the competition between the different compounds that retard the rate of hydrogenation of tetralin. However, a high conversion of tetralin was achieved even when 300 ppm of S or N wasItem Hidrogenación de tetralin utilizando un catalizador bifuncional de iridio/platino-SBA-15(2014) Vallés, Verónica; Ledesma, Brenda; Rivoira, Lorena Paola; Cussa, Jorgelina; Martínez, María Laura; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelLos catalizadores bimetálicos de Pt–Pd han recibido considerable atención debido a que demuestran tener una alta actividad en una amplia variedad de aplicaciones catalíticas (1). Con alta actividad, selectividad y estabilidad, comparada con catalizadores monometálicos de Pt y Pd. Por ejemplo, catalizadores bimetálicos Pt-Pd muestran tener mayor resistencia frente a envenenamientos en comparación con catalizadores de Pt (2-4). Las características estudiadas del catalizador serán correlacionadas con su performance catalítica en la hidrogenación del tetralin. El objetivo final es encontrar la proporción óptima de cada uno de los metales de forma de lograr la mayor actividad en dicho proceso.Item Hydrodenitrogenation of indol using iridium catalyst supported on titanium nanotubes(2022) Ledesma, Brenda Cecilia; Martínez, María Laura; Gómez Costa, Marcos Bruno; Beltramone, Andrea RaquelThe HDN of indole was studied over iridium modified titanate nanotube catalyst. Titaniun nanotube was prepared by the alkaline hydrothermal method. Iridium was added by wetness impregnation. The activity was compared with Ir-TiO2 and commercial NiMo/Al2O3 catalysts. The catalysts prepared were characterized by X-ray diffraction (XRD), N2 adsorption isotherms, UV–Vis-DRS, XPS, TEM, Py- FTIR and H2-Chemisorption. XRD, N2 isotherms and UV–vis-DRS confirmed the nanotube structure. The analysis showed that the mesoporous structure was maintained after Ir incorporation. The results showed that titanate nanotube as support significantly reduce the size of iridium crystallites and improves its dispersion considerably. Iridium titanate nanotube presented abundant and strong Bronsted acidity compared with TiO2 iridium catalyst. Ir-TNT was the most active catalyst for indole HDN, in mild conditions in a Batch reactor. The Bronsted acidity in synergic effect with Lewis acidity and hydrogenolysis capacity of iridium species were the responsible for the good activity.The HDN of indole was studied over iridium modified titanate nanotube catalyst. Titaniun nanotube was prepared by the alkaline hydrothermal method. Iridium was added by wetness impregnation. The activity was compared with Ir-TiO2 and commercial NiMo/Al2O3 catalysts. The catalysts prepared were characterized by X-ray diffraction (XRD), N2 adsorption isotherms, UV–Vis-DRS, XPS, TEM, Py- FTIR and H2-Chemisorption. XRD, N2 isotherms and UV–vis-DRS confirmed the nanotube structure. The analysis showed that the mesoporous structure was maintained after Ir incorporation. The results showed that titanate nanotube as support significantly reduce the size of iridium crystallites and improves its dispersion considerably. Iridium titanate nanotube presented abundant and strong Bronsted acidity compared with TiO2 iridium catalyst. Ir-TNT was the most active catalyst for indole HDN, in mild conditions in a Batch reactor. The Bronsted acidity in synergic effect with Lewis acidity and hydrogenolysis capacity of iridium species were the responsible for the good activity.Item Hydrodeoxygenation of guaiacol over pt/ga-mesoporous catalysts(2020) Beltramone, Andrea R.; Martínez, María Laura; Rivoira, LorenaLa hidrodesoxigenación (HDO) de guayacol, utilizado como molécula modelo, ha sido estudiada en un reactor batch sobre catalizadores de platino soportado sobre SBA-15 a 12 atm de presión y diferentes temperaturas, utilizando dodecano como solvente de reacción. El catalizador fue modificado con galio, incorporándolo como heteroátomo en la red mesoporosa de silíceos, mediante síntesis directa con el objetivo de modificar la naturaleza del soporte, pretendiendo mejorar la actividad catalítica del material. La acidez moderada que genera la incorporación de galio mejora la distribución de las especies activas de platino. En base a los resultados obtenidos el catalizador más activo en la HDO de guaiacol a 12 atm y 200°C fue Pt-Ga-SBA-15, con un 95% de conversión de reactivo en menos de 1 h de reacción.Item Hydrogenation of tetralin over Ir catalysts supported on titania-modified SBA-16(2014) Ledesma, Brenda; Vallés, Verónica; Rivoira, Lorena Paola; Martínez, María Laura; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelAbstract A series of Ti modified SBA-16 supports and their respective Ir-catalysts were prepared and character- ized to study the effect of support preparation method on the dispersion of iridium and on the characteristics of Ir surface species. Two methods of incorporation of titania were tested: the sol–gel method in order to obtain Ti as heteroatom and incipient wetness impregnation to obtain Ti as TiO2 (anatase phase). The results show that supports with different Ti species and dispersion can be obtained. The final catalyst was characterized at different preparation stages by XRD, elemental analysis and BET. The presence of Ti as Ti4? in the nanostructure of SBA and as TiO2 (anatase phase) was analyzed by UV–Vis–DRS and Raman spectroscopy. The iridium oxidation sate upon Ti-con- taining SBA-16 was studied by XPS, EDX, TEM and XRD, arriving at the good proportion of Ir0. H2 chemi- sorption and TEM characterization for Ti-SBA-16 indi- cated that Ir particle size was lower than anatase/SBA-16. The catalyst that we synthesized had good activity mea- sured in tetralin hydrogenation in presence of quinoline at mild conditions. The experimental data were quantitatively represented by a modified Langmuir–Hinshelwood-type rate equation. The preliminary results show these materials as promising catalysts for HDS/HDN reactions.Item Hydrogenation of tetralin over Ir-containing mesoporous catalysts(2012) Vallés, Verónica; Balangero, Gerardo Simón; Martínez, María Laura; Gómez Costa, Marcos Bruno; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelThe yield in fluid catalytic cracking (FCC) depends on the extent of aromatic hydrogenation in the gas oil hydrotreater. To optimize the gas oil hydrotreater, it is crucial to understand the aromatic hydrogenation reaction chemistry occurring in the gas oil hydrotreater. Gas oils, which consist of hydrocarbons in the boiling point range of 290−570 °C, contain several aromatic compounds (including three rings, two rings, and one ring). Light cycle oil (LCO), which contains large concentrations of aromatics, has a poor cetane value and, hence, by itself, is a very poor-quality diesel. Because the current regulations [on cetane and polynuclear aromatic (PNA) hydrocarbons] are not stringent, LCO is currently blended with diesel. However, it is anticipated (based on existing regulations in Europe and California) that diesel quality in the near future will be more stringently regulated in terms of cetane and aromatics. To find alternative processes, it is necessary to develop new and more active catalysts to replace the current ones. Optimal design and operation of such hydrogenation processes can be achieved through the use of reliable simulation tools; however, such tools require detailed knowledge of kinetic pathways and rates.1−3 Kinetic experiments on hydrogenation are typically performed in the gas phase under atmospheric pressure on group VIII metal catalysts. Previously, Beltramone et al.4,5 reported a detailed study and a quantitative network analysis of polynuclear aromatics aromatization at industrial conditions, and Korre and Klein6 reported an exhaustive study in a batch reactor at high pressure. Otherwise, the sulfur and nitrogen compounds found in synthetic feedstocks and heavy petroleum fractions can strongly inhibit hydroprocessing reactions through competitive adsorp- tion. The presence of these species even at low concentrations can limit the observed catalytic activity and necessitate the use Article Current processes for dearomatization use catalysts combin- ing the acidity of a support and the hydrogenation and hydrogenolysis/ring-opening activity of an incorporated metal. Hydrogenation/hydrocracking is most often practiced on cyclic molecules over primarily acidic zeolite, alumina, or silica- alumina-supported noble and other group VIII metal catalysts. Different processes have used catalysts such as NiMo, CoMo, NiW, Pt, and Pd on various supports.7−17 The dominance of the acid function can lead to cracking, and thus, a primary focus is the optimization of the acid function. In fact, it was shown recently that significant enhancements in hydrogenation can be made by focusing on the metal function. The metal function is usually provided by Pt and/or Pd, but it has been shown that Ir, Ru, and Rh also have exceptional activities and selectivities for the target reaction of hydrogenation and, depending on the reaction conditions, selective ring-opening.18−20 Some alumina- supported transition-metal catalysts have much higher hydro- denitrogenation (HDN) and hydrodesulfurization (HDS) activities than the conventional NiMo system.21−25 For example, Rh, Ir, Ru, and Pt supported on silica or alumina are known to effectively catalyze nitrogen removal from methylamine, quinoline, or pyridine also in the reduced state.26 Noble-metal sulfides, either unsupported as bulk compounds27 or supported on active carbon,28 have been studied extensively in hydrorefining. It has been shown that transition-metal sulfides of the second and third rows such as those containing Ru, Rh, Os, and Ir are especially active during HDS reactions.27 Similarly, sulfides of Ir, Os, and Re were found to be most active in the HDN of quinoline,28 and sulfides of Ir and Pt were found to be most active in the HDN of pyridine.29 However, catalytic properties of metal deposited on alumina or other supports have been studied less frequently, and moreover, the primary attention to date has been devoted only to Ru.30 It was shown by Cinibulk and Vit́31 that the HDN of higher pressures and temperatures to obtain desired conversions. Therefore, the need for more active catalysts is crucial in this process. The development of highly active and selective hydrotreating catalysts is one of the most pressing problems facing the petroleum induItem Indole HDN using iridium nanoparticles supported on titanium nanotubes(2022) Ledesma, Brenda Cecilia; Martínez, María Laura; Gómez Costa, Marcos Bruno; Beltramone, Andrea RaquelThe HDN of indole was studied over iridium modified titanate nanotube catalyst. Titanium nanotube was prepared by the alkaline hydrothermal method. Iridium was added by wetness impregnation. The activity was compared with Ir–TiO2 and commercial NiMo/Al2O3 catalysts. The catalysts prepared were characterized by X-ray diffraction (XRD), N2 adsorption isotherms, UV–Vis-DRS, FTIR, XPS, TEM, Py-FTIR and H2-Chemisorption. XRD, N2 isotherms and UV–vis-DRS con- firmed the nanotube structure. The analysis showed that the mesoporous structure was maintained after Ir incorporation. The results showed that titanate nanotube as support significantly reduce the size of iridium crystallites and improves its dispersion considerably. Iridium titanate nanotube presented abundant and strong Brönsted acidity compared with TiO2 iridium catalyst. According a kinetic study, Ir–TNT was the most active catalyst for indole HDN, in mild conditions in a Batch reactor. The Brönsted acidity in synergic effect with Lewis acidity and hydrogenolysis capacity of iridium species were the responsible for the good activity.Item Influencia del proceso de síntesis de materiales mesoporosos ácidos en la obtención de hmf a partir de fructosa(2020) Mayer, Sergio; Falcon, Horacio; Ribotta, Pablo; Perez, Susana; Campos Martin, Jose Miguel; Garcia Fierro, Jose Luis; Martínez, María Laura; Beltramone, Andrea R.Motivados por el agotamiento irreversible de los recursos fósiles, en la actualidad se realizan esfuer-zos en obtener moléculas orgánicas de valor agregado a partir de biomasa. El 5-hidroximetilfurfural (HMF) es, junto al furfural, uno de los productos químicos de fuentes renovables de mayor interés por su potencial empleo en la obtención de bioplásticos, biocombustibles, lubricantes y adhesivos basados en furanos. Aquí presentamos dos catalizadores sintetizados por dos vías de síntesis diferentes, ambos con la incorporación de especies oxidadas de Zr, los cuales fueron caracterizados por XRD de bajo y alto ángulo, XPS y TPD-NH3. Los análisis demuestran la obtención de mesoporosos con arreglo de poros homogéneo, la incorporación de especies de Zr en red y extra-red y la generación de una acidez superficial moderada. Se discuten las propiedades obtenidas en relación a la reacción de deshidratación de fructosa a HMF, su conversión y rendimiento. El material Zr-SBA-15, que incorpora Zr in situ, de-muestra tener la mayor actividad catalítica, convirtiendo un 61,7 % de la fructosa y generando HMF con un rendimiento del 51,9 % en 2 h de reacción a 150 °C en un arreglo catalizador – solución acuosa de fructosa al 30 % – metil-isobutil-cetona (MIKB):2-butanol 7:3 P/P.Item Influencia del proceso de síntesis de materiales mesoporosos ácidos en la obtención de HMF a partir de fructosa(2019) Beltramone, Andrea R.; Mayer, Sergio; Falcón, Horacio; Ribotta, Pablo; Pérez, Susana; Campos Martin, José Miguel; Garcia Fierro, josé Luis; Martínez, María LauraMotivados por el agotamiento irreversible de los recursos fósiles, en la actualidad se realizan esfuer-zos en obtener moléculas orgánicas de valor agregado a partir de biomasa. El 5-hidroximetilfurfural (HMF) es, junto al furfural, uno de los productos químicos de fuentes renovables de mayor interés por su potencial empleo en la obtención de bioplásticos, biocombustibles, lubricantes y adhesivos basados en furanos. Aquí presentamos dos catalizadores sintetizados por dos vías de síntesis diferentes, ambos con la incorporación de especies oxidadas de Zr, los cuales fueron caracterizados por XRD de bajo y alto ángulo, XPS y TPD-NH3. Los análisis demuestran la obtención de mesoporosos con arreglo de poros homogéneo, la incorporación de especies de Zr en red y extra-red y la generación de una acidez superficial moderada. Se discuten las propiedades obtenidas en relación a la reacción de deshidratación de fructosa a HMF, su conversión y rendimiento. El material Zr-SBA-15, que incorpora Zr in situ, de-muestra tener la mayor actividad catalítica, convirtiendo un 61,7 % de la fructosa y generando HMF con un rendimiento del 51,9 % en 2 h de reacción a 150 °C en un arreglo catalizador – solución acuosa de fructosa al 30 % – metil-isobutil-cetona (MIKB):2-butanol 7:3 P/P.Item Inhibition of the hydrogenation of tetralin by nitrogen and sulfur compounds over Ir/SBA-16(2011) Balangero, Gerardo Simón; Martínez, María Laura; Gómez Costa, Marcos Bruno; Anunziata, Oscar Alfredo; Beltramone, Andrea RaquelIn this work we study the catalytic properties of 5 wt.% Ir-containing SBA-16 catalysts (with and without aluminum as heteroatom), in the hydrogenation of tetralin to decalin, in the presence of 100 ppm of N as quinoline, indole and carbazole, and 100 ppm of S as dibenzothiophene and 4,6-dimethyl- dibenzothiophene at 250 ◦C and 15 atm of pressure of hydrogen, using a Parr reactor. Ir/SBA-16 and Ir/Al-SBA-16 were prepared by wetness impregnation using Iridium Acetylacetonate as source of Ir. The Ir/SBA-16 catalyst synthesized by us had high activity measured in tetralin hydrogenation at mild con- ditions. The experimental data was quantitatively represented by a modified Langmuir–Hinshelwood type rate equation, using the apparent adsorption constants calculated from the inhibition results for the individual compounds. The catalyst showed a good resistance to sulfur and nitrogen compounds. The inhibiting effect increased in the order: DBT < quinoline < 4,6-dimethyl-DBT < indole < carbazole. The inhibiting effect of the nitrogen/sulfur compounds was strong, but the activity was still higher than with commercial NiMo/alumina catalyst. We present in this contribution a successfully developed, high loaded and well dispersed Ir/SBA-16 catalysts, that have been shown to maintain a useful catalytic activity, even in the presence of relatively high amounts of sulfur compounds (up to 100 ppm, sulfur basis). Consequently, economically successful processes have evolved, based on this class of catalysts.Item Iridium-supported SBA-15 modified with Ga and Al as a highly active catalyst in the hydrodenitrogenation of quinoline(2020) Ledesma, Brenda Cecilia; Martínez, María Laura; Beltramone, Andrea RaquelIr-supported SBA-15 was studied in the hydrodenitrogenation (HDN) of quinoline as a model nitrogen com- pound. The activity was improved when Si-SBA-15 support was modified with Ga and Al. Characterization of the catalysts was performed by XRD, N2 adsorption, XPS, H2 chemisorption, TEM, TPR, NMR and Py-FTIR. Dispersion and nature of the iridium species are dependent parameters on the support characteristics. Better activity for the elimination of the nitrogen atom was observed with Ir-Ga-SBA-15 as compared to Ir-Al-SBA-15 at 250 and 300 °C. However, the TON value for Ir-Al-SBA-15 was higher than Ir-Ga-SBA-15 at 300 °C, indicating the influence of the stronger Bronsted acidity in the elimination of the nitrogen atom at higher temperature. The enhanced activity was attributed to the particularly good dispersion of the iridium catalytic centers and to the synergic effect of Bronsted and Lewis acid sites, derived from Ga or Al incorporation. Ga-SBA-15 with 1 wt.% of iridium loading was the most active catalyst for HDN of quinoline. 95% of nitrogen elimination was attained at short time in mild conditions. The reusability of the catalyst presents it as potential catalyst for HDN process.Item Iron-modified mesoporous materials as catalysts for ODS of sulfur compounds(2020) Rivoira, Lorena Paola; Juárez, Juliana María; Martínez, María Laura; Beltramone, Andrea RaquelFe-modified mesoporous catalysts were used in the ODS of DBTs using H2O2 as oXidant and acetonitrile as solvent. SBA-15, MCM-48, CMK-3 and CMK-1 were used as supports. Iron was incorporated using iron nitrate by wetness impregnation. The catalysts were characterized by XRD, N2 isotherms, TEM, XPS and ICP. We developed catalysts with high specific surface area, pore volume and narrow mesopore size distribution and highly dis- persed Fe- species. The catalysts were tested in the o Xidative desulfurization of different sulfur compounds as benzothiophene, dibenzothiopene and 4,6-dimethyl dibenzothiopene. The catalyst prepared using CMK-3 as support was the most active for the ODS reaction. The good activity was related with the high dispersion of the iron oXides, mainly in the magnetite phase. Temperature, hydrogen peroXide and sulfur initial concentration were studied using Fe-CMK-3 in the oXidation of DBT. The optimal operation conditions were determined. Fe- CMK-3 is an active and stable catalyst to be applied in the industrial process of ODS.Item Mesopore carbón starch with acid properties: synthesis and characterization(2020) Martínez, María Laura; Anunziata, Oscar A.We have shown that a promising material with acidic properties can be successfully prepared from starch mesoporous carbon (SMC), functionalized with sulfated zirconia. The process of assembling P123, starch, zirconia, and silicon synthesized Zr-modified ordered mesoporous carbon. SMC and Zr-SMC were characterized by BET for their texture properties and, using Scanning Electron Microscopy (SEM), their morphology. Acidic properties were acquired by programmed thermodesorption of ammonia (NH3 TPD). These studies show that the Zr-SMCs material is mainly composed of mesopores with an average pore size of approximately 3.5 nm, high surface area and pore volume, and has medium to strong acidity properties.Item Multiple-wall carbon nanotubes obtained with mesoporous material decorated with ceria-zirconia(2020) Rodríguez, Miguel Angel; Anunziata, Oscar Alfredo; Beltramone, Andrea Raquel; Martínez, María LauraIn this work, Ceria-Zirconia on ordered Santa Barbara mesoporous silica (Ce-Zr-SBA-15), has been used directly as a catalyst for the synthesis of carbon nanotubes (CNTs) through Chemical Vapor Deposition (CVD). In addition to cerium oxide, it contains zirconium oxide nano crystallites, which act as catalysts for carbon nanostructures. The catalytic performance of this material was evaluated for the decomposition of ethanol at 900 °C, with N2 flow. The carbon decomposed from absolute ethanol diffuses through the surface of the nanostructured catalytic material and precipitates in the form of MWCNT structures, which could be identified by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), showing average diameters of 30–35 nm.