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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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  • PublicationOpen 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 Publikoa
    Methanolysis 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.
  • PublicationOpen 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 Publikoa
    The 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.
  • PublicationOpen Access
    Outstanding performance of rehydrated Mg-Al hydrotalcites as heterogeneous methanolysis catalysts for the synthesis of biodiesel
    (Elsevier, 2018) Navajas León, Alberto; Campo Aranguren, Idoia; Moral Larrasoaña, Ainara; Echave, Javier; Sanz Iturralde, Oihane; Montes, Mario; Odriozola, José Antonio; Arzamendi Manterola, María Cruz; Gandía Pascual, Luis; Química Aplicada; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2
    There is still a need for active, selective and stable heterogeneous catalysts for the synthesis of biodiesel. In this work, magnesium-aluminium hydrotalcites with Mg/Al molar ratios within the 1.5–5 range were synthesized by coprecipitation and used as transesterification catalysts for the synthesis of biodiesel. The mixed oxides obtained after calcination recovered the hydrotalcite structure in the form of meixnerite after rehydration in boiling water. The solids were characterized by XRD, TGA, N2 adsorption-desorption, and SEM. Basic properties were assessed by means of Hammett indicators and CO2-TPD. Rehydrated materials with the highest Mg/Al ratios showed some distinctive features: low surface area, well defined flake-like crystals, high basicity and strong basic sites with H_ values above 11. They were also the most active catalysts allowing to achieve 51–75% sunflower oil methanolysis conversion after 8 h of reaction under mild conditions (60 °C, 1 atm), methanol/oil molar ratio of 12 using between 2 and 6 wt% of catalyst. The conversion increased up to 96% (92% fatty acid methyl esters yield) using 2 wt% catalyst and methanol/oil molar ratio of 48. Catalyst leaching was not a serious problem with these solids that could be reutilized maintaining very good activities. A general accordance between solids basic properties and their catalytic performance has been observed. These results are among the best reported in the literature for heterogeneous methanolysis catalysts and have been attributed to the high basicity of the rehydrated solids and the presence of strong and accessible basic sites probably consisting in interlayer hydroxide anions at the edges of the crystals.