Metodología para la caracterización de aceites usados en aviación basada en técnicas espectroscópicas

Esta tesis se enmarca en el programa de doctorado realizado por convenio entre la Facultad de Ingeniería de la UNIMET (Caracas) y el Departamento de Proyectos de Ingeniería de la Universidad Politécnica de Valencia. La investigación que se ha planteado consiste en el desarrollo de una metodología predictiva del cumplimiento de requisitos funcionales de los aceites empleados en aviación, con el objetivo de sustituir los actuales análisis fisicoquímicos de los aceites en servicio (que permiten determinar la degradación u oxidación de los aceites mencionados) por modelos estadísticos que parten de la información obtenida por espectroscopia de infrarrojo (FTIR). Se han realizado análisis por FTIR de 4 tipos de aceite (aceites minerales usados, aceites minerales envejecidos en laboratorio, aceites sintéticos usados y aceites sintéticos envejecidos en laboratorio) y aplicado modelos de regresión multivariante para poder predecir la acidez (uno de los principales indicadores de desgaste) de los aceites. De esta forma es posible realizar de manera más rápida y más económica (sin consumo de reactivos) los ensayos que necesitan las aeronaves privadas en Venezuela (y las correspondientes regulaciones de los diferentes países) para mantener el certificado de aeronavegabilidad. El analizar aceites envejecidos en condiciones controladas de laboratorio tiene como interés conocer cómo afecta el tiempo y la temperatura a cada tipo de aceite de manera que pueda garantizarse el perfil FTIR de los aceites usados en condiciones reales. En los modelos elaborados para mejorar la capacidad de predicción de la acidez de los aceites, se ha trabajado especialmente la localización de los rangos del espectro en los que aparecen los principales compuestos de degradaciónLeal De Rivas, BC. (2014). Metodología para la caracterización de aceites usados en aviación basada en técnicas espectroscópicas [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/48468TESI

Evaluación de procesos de desgaste en turbinas aeronáuticas mediante espectrometría por disco rotativo(rde) y por contador de partículas láser(lnf)

En esta ponencia se realiza una revisión de diferentes metodologías para la evaluación de procesos de desgaste en turbinas aéreas derivadas. Mediante el análisis de las características del lubricante utilizado, a través de espectrometría de micropartículas y de la evaluación por contadores de partículas de tamaño superior a los 20 micrómetros, se pretende determinar procesos de desgaste y correlaciones entre diversos parámetros de funcionamiento de la turbina. Para ello se presentan las principales metodologías de análisis de aceite en uso, indicando la información que suministran, los ámbitos en los que su aplicación es pertinente, y se muestran los resultados de diferentes casos de aplicación correspondientes tanto a aeronaves de ala fija como de ala rotativa

Catalytic removal of chlorinated compounds over ordered mesoporous cobalt oxides synthesised by hard-templating

This work evaluates the catalytic behaviour of a series of mesoporous bulk cobalt oxide prepared by hard-templating using SBA-15, SBA-16 and SBA-3. In addition, a bulk catalyst obtained by silica aquagel confined precipitation is also examined. The oxidation of 1,2-dichloroethane has been selected as a model reaction for determining their suitability for the efficient removal of chlorinated pollutants in gaseous waste streams. The catalytic behaviour is found to depend on the abundance of surface adsorbed oxygen species and a good low-temperature reducibility. These key physico-chemical properties are optimised for nanocasted Co3O4 prepared by using SBA-15 as hard template. This sample is characterised by a relatively high surface area, a nanorod-like morphology and a high quality 2D ordered mesoporous structure. At 375–400 °C this sample attains an efficient oxidation of the chlorinated feed to CO2 and HCl/Cl2 while keeping a reasonable stability with time.Ministry of Economy and Competitiveness (CTQ2016-80253-R) Basque Government (Grant 2011/065, IT657-13

Bulk Co3O4 for Methane Oxidation: Effect of the Synthesis Route on Physico-Chemical Properties and Catalytic Performance

The synthesis of bulk pure Co3O4 catalysts by different routes has been examined in order to obtain highly active catalysts for lean methane combustion. Thus, eight synthesis methodologies, which were selected based on their relatively low complexity and easiness for scale-up, were evaluated. The investigated procedures were direct calcination of two different cobalt precursors (cobalt nitrate and cobalt hydroxycarbonate), basic grinding route, two basic precipitation routes with ammonium carbonate and sodium carbonate, precipitation-oxidation, solution combustion synthesis and sol-gel complexation. A commercial Co3O4 was also used as a reference. Among the several examined methodologies, direct calcination of cobalt hydroxycarbonate (HC sample), basic grinding (GB sample) and basic precipitation employing sodium carbonate as the precipitating agent (CC sample) produced bulk catalysts with fairly good textural and structural properties, and remarkable redox properties, which were found to be crucial for their good performance in the oxidation of methane. All catalysts attained full conversion and 100% selectivity towards CO2 formation at a temperature of 600 °C while operating at 60,000 h−1. Among these, the CC catalyst was the only one that achieved a specific reaction rate higher than that of the reference commercial Co3O4 catalyst.This research was funded by the Spanish Ministry of Science and Innovation (PID2019-107105RB-I00 AEI/FEDER, UE), Basque Government (IT1297-19) and the University of The Basque Country UPV/EHU (PIF15/335 and DOCREC21/23)

Co3O4 hollow nanotubes for the catalytic oxidation of C2-chlorinated VOCs

Structured Co3O4 catalysts with a hollow nanotube morphology were prepared by several synthesis routes based on the Kirkendall effect. The resulting samples were kinetically evaluated in the gas-phase oxidation of vinyl chloride and 1,2-dichloroethane, two model C2-chlorinated volatile organic compounds; and exhaustively characterised by means of BET measurements, X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry and temperature-programmed techniques (adsorption of ammonia and chlorinated VOC, O2-TPD, H2-TPR and TPO). The performance of the prepared nanotubes was essentially controlled by the presence of active oxygen species at the surface, which in turn depended on the Co2+/Co3+ molar ratio, and the adsorption capacity of the catalyst for the chlorocarbon. Both pollutants were efficiently converted to deep oxidation products at relatively low temperatures. In addition, the optimal catalyst exhibited an appreciable stability when operating during 120 h.Ministry of Science and Innovation (PID2019-107105RB-I00 AEI/FEDER, UE and PDC2022-133897-I00) // Basque Government (IT1509-22) // University of the Basque Country UPV/EHU (PIF18/185

On the Effect of the Synthesis Route of the Support in Co3O4/CeO2 Catalysts for the Complete Oxidation of Methane

Six ceria supports synthesized by various synthesis methodologies were used to deposit cobalt oxide. The catalysts were thoroughly characterized, and their catalytic activity for complete methane oxidation was studied. The supports synthesized by direct calcination and precipitation with ammonia exhibited the best textural and structural properties as well as the highest degree of oxidation. The remaining supports presented poorer textural properties to be employed as catalytic supports. The cobalt deposited over the first two supports presented a good dispersion at the external surface, which induced a significant redox effect that increased the number of Co3+ ions on their surface. Consequently, the presence of highly active lattice oxygen species on the surface of these catalysts was favored. Additionally, the optimal active catalyst (Co-DC) revealed a significant resistance to water vapor inhibition, owing to the high hydrophobicity of the ceria support.Spanish Ministry of Science and Innovation (PID2019-107105RB-I00 AEI/FEDER, UE and PDC2022-133897-I00), Basque Government (IT1509-22), University of the Basque Country UPV/EHU (DOCREC21/23

Comparative Study of Strategies for Enhancing the Performance of Co3O4/Al2O3 Catalysts for Lean Methane Combustion

Spinel-type cobalt oxide is a highly active catalyst for oxidation reactions owing to its remarkable redox properties, although it generally exhibits poor mechanical, textural and structural properties. Supporting this material on a porous alumina can significantly improve these characteristics. However, the strong cobalt–alumina interaction leads to the formation of inactive cobalt aluminate, which limits the activity of the resulting catalysts. In this work, three different strategies for enhancing the performance of alumina-supported catalysts are examined: (i) surface protection of the alumina with magnesia prior to the deposition of the cobalt precursor, with the objective of minimizing the cobalt–alumina interaction; (ii) coprecipitation of cobalt along with nickel, with the aim of improving the redox properties of the deposited cobalt and (iii) surface protection of alumina with ceria, to provide both a barrier effect, minimizing the cobalt–alumina interaction, and a redox promoting effect on the deposited cobalt. Among the examined strategies, the addition of ceria (20 wt % Ce) prior to the deposition of cobalt resulted in being highly efficient. This sample was characterized by a notable abundance of both Co3+ and oxygen lattice species, derived from the partial inhibition of cobalt aluminate formation and the insertion of Ce4+ cations into the spinel lattice.This research was funded by the Ministry of Economy and Competitiveness (CTQ2016-80253-R AEI/FEDER, UE), Basque Government (IT1297-19) and the University of The Basque Country UPV/EHU (PIF15/335

Beneficial effects of nickel promoter on the efficiency of alumina-supported Co3O4 catalysts for lean methane oxidation

In this work bimetallic Ni catalysts supported over Co-Al2O3 and monometallic Co-Al2O3 and Ni-Al2O3 catalysts were examined for the complete oxidation of methane. With a 30 % total metallic loading, the samples were synthesized by a sequential precipitation route. All samples were characterized by nitrogen physisorption, X-ray fluorescence, X-ray diffraction, Raman spectroscopy, scanning electron microscopy, scanning-transmission electron microscopy, X-Ray photoelectron spectroscopy, and temperature-programmed reduction with hydrogen and methane. Their catalytic performance was investigated in the temperature range of 200-600 degrees C with a space velocity of 60.000 h-1. The bimetallic catalysts showed a better behavior in the oxidation reaction than the monometallic counterparts, mainly due to the good dispersion of Ni on the surface of the Co-Al2O3 samples. This has enabled the insertion of Ni2+ ions into the cobalt spinel lattice, which in turn provoked an increase in the amount of Co3+ species, and a subsequent enhanced mobility of oxygen species in the spinel. In this sense, the 5Ni/25Co catalyst showed the best performance, thus reducing the value of the T50 by 25 degrees C with respect to the monometallic catalysts.This research was funded by the Spanish Ministry of Science and Innovation (PID2019-107105RB-I00 AEI/FEDER, UE), Basque Government (IT1509-22) and the University of The Basque Country UPV/EHU (DOCREC21/23). The authors wish to thank the technical and human support provided by SGIker (UPV/EHU). In addition, authors acknowledge the use of instrumentation as well as the technical advice provided by the National Facility ELECMI ICTS, node ‘Advanced Microscopy Laboratory’ at University of Zaragoza

Effect of Residual Na+ on the Combustion of Methane over Co3O4 Bulk Catalysts Prepared by Precipitation

The effect of the presence of residual sodium (0.4 %wt) over a Co3O4 bulk catalyst for methane combustion was studied. Two samples, with and without residual sodium, were synthesized by precipitation and thoroughly characterised by X-ray diffraction (XRD), N-2 physisorption, Wavelength Dispersive X-ray Fluorescence (WDXRF), temperature-programmed reduction with hydrogen followed by temperature-programmed reduction with oxygen (H-2-TPR/O-2-TPO), temperature-programmed reaction with methane (CH4 -TPRe), ultraviolet-visible-near-infrared diffuse reflectance spectroscopy (UV-vis-NIR DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). It was found that during calcination, a fraction of the sodium atoms initially deposited on the surface diffused and migrated into the spinel lattice, inducing a distortion that improved its textural and structural properties. However, surface sodium had an overall negative impact on the catalytic activity. It led to a reduction of surface Co3+ ions in favour of Co2+, thus ultimately decreasing the Co3+/Co2+ molar ratio (from 1.96 to 1.20) and decreasing the amount and mobility of active lattice oxygen species. As a result, the catalyst with residual sodium (T-90 = 545 degrees C) was notably less active than its clean counterpart (T-90 = 500 degrees C). All of this outlined the significance of a proper washing when synthesizing Co3O4 catalyst using a sodium salt as the precipitating agent.This research was funded by the Ministry of Economy and Competitiveness grant number [CTQ2016-80253-R] and the University of the Basque Country UPV/EHU (PIF15/335)