Person: Arzamendi Manterola, María Cruz
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Arzamendi Manterola
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María Cruz
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Química Aplicada
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0000-0002-6276-8029
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313
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Publication Open Access Pseudo-homogeneous and heterogeneous kinetic models of the NaOH-catalyzed methanolysis reaction for biodiesel production(MDPI, 2021) Zabala, Silvia; Reyero Zaragoza, Inés; Campo Aranguren, Idoia; Arzamendi Manterola, María Cruz; Gandía Pascual, Luis; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaMethanolysis of vegetable oils in the presence of homogeneous catalysts remains the most important process for producing biodiesel. However, there is still a lack of accurate description of the reaction kinetics. This is in part due to the complexity of the reacting system in which a large number of interconnected reactions take place simultaneously. In this work, attention is focused on the biphasic character of the reaction medium, formed by two immiscible liquid phases. The behavior of the phases is investigated regarding their physicochemical properties, mainly density and mutual solubility of the components, as well as composition. In addition, two kinetic models with different level of complexity regarding the biphasic character of the reaction medium have been developed. It has been found that a heterogeneous model considering the presence of the two phases and the distribution of the several compounds between them is indispensable to get a good description of the process in terms of oil conversion and products yields. The model captures the effects of the main variables of an isothermal batch methanolysis process: methanol/oil molar ratio, reaction time and catalyst concentration. Nevertheless, some adjustment is still required as concerns modelling of the saponification reactions and catalyst deactivation.Publication Open Access Reaction monitoring by ultrasounds in a pseudohomogeneous medium: triglyceride ethanolysis for biodiesel production(MDPI, 2022) Reyero Zaragoza, Inés; Gandía Pascual, Luis; Arzamendi Manterola, María Cruz; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaThe sound propagation speed measurement us is used for monitoring triglyceride ethanol-ysis in a broad range of reaction conditions (mainly, temperature: 23–50◦C; ethanol/oil: from 6 to 24 mol/mol). Experimentally, us slightly increased with the reaction time in all cases as a result of the contribution of its dynamic mixture components. Nomoto’s expression for homogeneous mixtures offered suitable us estimation but with values notably higher than the experimental ones due to the resistance to sound propagation offered by the ethanol/oil interphase (non-homogeneous medium). Our strategy was based on both the comparison of the experimental us values and the theoretical ones correlated by means of triglyceride conversion and on the estimation of the sound speed of oil/ethanol that could emulate the resistance offered by the interphase. The evolution of the reactions was predicted quite well for all the experiments carried out with very different reaction rates. Nev-ertheless, at the beginning of the reaction, the estimated conversion (outside of industrial interests) showed important deviations. The presence of the intermediate reaction products, diglycerides, and monoglycerides could be responsible for those deviations.Publication Open Access Gaseous fueling of an adapted commercial automotive spark-ignition engine: simplified thermodynamic modeling and experimental study running on hydrogen, methane, carbon monoxide and their mixtures(Elsevier, 2023) Urroz Unzueta, José Carlos; Diéguez Elizondo, Pedro; Arzamendi Manterola, María Cruz; Arana Burgui, Miguel; Gandía Pascual, Luis; Ingeniería; Ingeniaritza; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Zientziak; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaIn the present work, methane, carbon monoxide, hydrogen and the binary mixtures 20 % CH4–80 % H2, 80 % CH4–20 % H2, 25 % CO–75 % H2 (by volume) were considered as fuels of a naturally aspirated port-fuel injection four-cylinder Volkswagen 1.4 L spark-ignition (SI) engine. The interest in these fuels lies in the fact that they can be obtained from renewable resources such as the fermentation or gasification of residual biomasses as well as the electrolysis of water with electricity of renewable origin in the case of hydrogen. In addition, they can be used upon relatively easy modifications of the engines, including the retrofitting of existing internal combustion engines. It has been found that the engine gives similar performance regardless the gaseous fuel nature if the air–fuel equivalence ratio (λ) is the same. Maximum brake torque and mean effective pressure values within 45–89 N⋅m and 4.0–8.0 bar, respectively, have been obtained at values of λ between 1 and 2 at full load, engine speed of 2000 rpm and optimum spark-advance. In contrast, the nature of the gaseous fuel had great influence upon the range of λ values at which a fuel (either pure or blend) could be used. Methane and methane-rich mixtures with hydrogen or carbon monoxide allowed operating the engine at close to stoichiometric conditions (i.e. 1 < λ < 1.5) yielding the highest brake torque and mean effective pressure values. On the contrary, hydrogen and hydrogen-rich mixtures with methane or carbon monoxide could be employed only in the very fuel-lean region (i.e. 1.5 < λ < 2). The behavior of carbon monoxide was intermediate between that of methane and hydrogen. The present study extends and complements previous works in which the aforementioned fuels were compared only under stoichiometric conditions in air (λ = 1). In addition, a simple zero-dimensional thermodynamic combustion model has been developed that allows describing qualitatively the trends set by the several fuels. Although the model is useful to understand the influence of the fuels properties on the engine performance, its predictive capability is limited by the simplifications made.Publication Open Access From fundamental materials chemistry to sensing applications: unravelling the water adsorption mechanism of a luminescent optical fibre sensor membrane(Elsevier, 2024) Cruz Quesada, Guillermo; Rosales Reina, Beatriz; López Torres, Diego; Reinoso, Santiago; López Ramón, María Victoria; Arzamendi Manterola, María Cruz; Elosúa Aguado, César; Espinal Viguri, Maialen; Garrido Segovia, Julián José; Ciencias; Ingeniería Eléctrica, Electrónica y de Comunicación; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC; Zientziak; Ingeniaritza Elektrikoa, Elektronikoaren eta Telekomunikazio Ingeniaritzaren; Universidad Pública de Navarra / Nafarroako Unibertsitate PublikoaThis work provides insight into the correlation between the luminescent response of a water-vapour optical fibre sensor and the textural properties of its lanthanide-doped silica coating. To this end, a library of 16 silica xerogels derived from combinations between 2 lanthanide dopants (EuIII, TbIII) and 8 antenna ligands was synthesised and characterised by photoluminescence spectroscopy and N2 and CO2 adsorption-desorption isotherms, among others. Based on the best luminescent response and most-suited porous texture, the material doped with TbIII and 2,2′-(4-(2-Ethoxyethoxy)pyridine-2,6-diyl)bis(4,5-dihydrooxazole) was selected to construct the probe. A film of this material was affixed to a commercial silica fibre by dip-coating and the resulting sensor was tested in a climatic chamber with relative humidity ranging from 20 to 90% to obtain normalised time-response and calibration curves at three temperatures. The response was linear up to certain water-vapour concentrations, beyond which abruptly changed to polynomial, acting against the sensor resolution. The adsorption mechanism was elucidated by comparing the isosteric enthalpies of adsorption calculated from the sensor calibration curves to those determined from the monolith water-vapour isotherms, revealing that capillary condensation in the membrane mesopores was the key phenomenon leading to the response deviating from linearity.Publication Open Access Acid-catalyzed etherification of glycerol with tert-butanol: reaction monitoring through a complete identification of the produced alkyl ethers(MDPI, 2023) Cornejo Ibergallartu, Alfonso; Reyero Zaragoza, Inés; Campo Aranguren, Idoia; Arzamendi Manterola, María Cruz; Gandía Pascual, Luis; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2Higher tert-Butyl glycerol ethers (tBGEs) are interesting glycerol derivatives that can be produced from tert-butyl alcohol (TBA) and glycerol using an acid catalyst. Glycerol tert-butylation is a complex reaction that leads to the formation of five tBGEs (two monoethers, two diethers, and one triether). In order to gain insight into the reaction progress, the present work reports on the monitoring of glycerol etherification with TBA and p-toluensulfonic acid (PTSA) as homogeneous catalysts. Two analytical techniques were used: gas chromatography (GC), which constitutes the benchmark method, and( 1)H nuclear magnetic resonance (H-1 NMR), whose use for this purpose has not been reported to date. A method for the quantitative analysis of tBGEs and glycerol based on H-1 NMR is presented that greatly reduced the analysis time and relative error compared with GC-based methods. The combined use of both techniques allowed for a complete quantitative and qualitative description of the glycerol tert-butylation progress. The set of experimental results collected showed the influence of the catalyst concentration and TBA/glycerol ratio on the etherification reaction and evidenced the intrinsic difficulties of this process to achieve high selectivities and yields to the triether.