Open Access
Catalytic performance of bulk and Al₂O₃-supported molybdenum oxide for the production of biodiesel from oil with high free fatty acids content
(MDPI, 2020) Navajas León, Alberto; Reyero Zaragoza, Inés; Jiménez Barrera, Elena; Romero Sarria, Francisca; Llorca Piqué, Jordi; Gandía Pascual, Luis; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
Non-edible vegetable oils are characterized by high contents of free fatty acids (FFAs) that prevent from using the conventional basic catalysts for the production of biodiesel. In this work, solid acid catalysts are used for the simultaneous esterification and transesterification with methanol of the FFAs and triglycerides contained in sunflower oil acidified with oleic acid. Molybdenum oxide (MoO₃), which has been seldom considered as a catalyst for the production of biodiesel, was used in bulk and alumina-supported forms. Results showed that bulk MoO3 is very active for both transesterification and esterification reactions, but it suffered from severe molybdenum leaching in the reaction medium. When supported on Al₂O₃, the MoO₃ performance improved in terms of active phase utilization and stability though molybdenum leaching remained significant. The improvement of catalytic performance was ascribed to the establishment of MoO₃Al₂O₃ interactions that favored the anchorage of molybdenum to the support and the formation of new strong acidic centers, although this effect was offset by a decrease of specific surface area. It is concluded that the development of stable catalysts based on MoO₃ offers an attractive route for the valorization of oils with high FFAs content.
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, Gurutze; 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.

Reyero Zaragoza, Inés

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