Open 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, Oihane; Montes, Mario; Odriozola, José A.; Arzamendi Manterola, Gurutze; 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.
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
Application of eco-design and life cycle assessment standards for environmental impact reduction of an industrial product
(MDPI, 2017) Navajas León, Alberto; Uriarte Elizaga, Leire; Gandía Pascual, Luis; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Química Aplicada
Eco-design is included within the framework of the standard for “Environmental management systems—Guidelines for incorporating Eco-design” (ISO 14006:2011). Eco-design process, as defined in standard, has six steps: (i) Specify product functions; (ii) Environmental assessment of products; (iii) Strategies of improvement; (iv) Environmental objectives; (v) Product specification; and (vi) Technical solutions. Step (ii), determination of the stage or process of the product life cycle that has the highest environmental impact; this is perhaps the most controversial step because the standard does not specify which tool should be used. This lack of specification has generated some distrust with regard to eco-design, hindering its development. In order to make a trustworthy eco-design, Life Cycle Assessment (LCA) should be applied as a tool for environmental impact quantification. The main objective of this work is to apply standardised eco-design methodology for the reduction of the environmental impact of an industrial product in Spain using LCA as a tool for the environmental product assessment. LCA standardised process (ISO 14040,14044:2006) is included in the eco-design process. A glass container intended for cough syrup delivery has been selected as an industrial product to be eco-designed. Following the methodology described, the overall normalised impact decreased 35.1% when a PET container substituted a glass container. Environmental impacts have been reduced following standardised eco-design and LCA methodologies, serving as an example to industry and administration regarding how to eco-design with the confidence of obtaining reliable results
Open Access
Life cycle assessment of natural gas fuelled power plants based on chemical looping combustion technology
(Elsevier, 2019-07-30) Navajas León, Alberto; Mendiara, Teresa; Goñi, Víctor; Jiménez, Adrián; Gandía Pascual, Luis; Abad, Alberto; García Labiano, Francisco; Diego, Luis F. de; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Among the different Carbon Capture and Storage (CCS) technologies being developed in the last decades, Chemical Looping Combustion (CLC) stands out since it allows inherent CO2 capture. In the CLC process, there is a solid oxygen carrier circulating between two reactors in a cycle that allows providing the oxygen needed for combustion. In one of the reactors, named as fuel reactor, the fuel is introduced and combusted while the oxygen carrier reduction takes place. In the second reactor, named air reactor, the oxygen carrier is reoxidized in air. Different materials based on copper, nickel and iron oxides have been proposed as oxygen carriers for the CLC process. This work presents an environmental evaluation of the CLC process for natural gas based on Life Cycle Assessment (LCA). Five different oxygen carrier materials already tested in pilot plants were considered and the results compared to the conventional natural gas combustion in a gas turbine in a combined cycle without and with CO2 capture using postcombustion capture with amines. In view of the results, lower impact of the CLC process compared to the base case is expected without and with CO2 capture. The influence of several variables on the results was considered, such as temperature in the air reactor, lifetime of the oxygen carrier and possibility of recuperation of the depleted oxygen carrier. The nickel-based oxygen carriers were identified as the most adequate to be used in natural gas combustion. However, due to their toxicity, several analyses were also performed in order to identify improvements in the known oxygen carriers that can qualify them to replace nickel-based materials.
Open Access
Three-dimensional printing of acrylonitrile butadiene styrene microreactors for photocatalytic applications
(American Chemical Society, 2020) Cabrera Barrios, Aarón; Pellejero, Ismael; Oroz Mateo, Tamara; Salazar, Cristina; Navajas León, Alberto; Fernandez Acevedo, Claudio; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua, PC003-004; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
Miniaturization is a key aspect for many technological applications and the use of microreactors is an excellent solution for the intensification of chemical processes for a variety of applications. However, standard microfabrication requires large facilities and intricate fabrication protocols, and consequently it is not easily available, generally resulting in high production costs. Herein, we present a very cheap, fast and easy microreactor design for photocatalytic applications based on direct fused filament 3D printing as a facilitating and widespread technology. The microreactor consists of three bodies directly printed in ABS (Acrylonitrile Butadiene Styrene): a main body with a serpentine microchannel pattern where the photocatalyst is placed, a top holder with a transparent polymer window, and a base to clamp the parts. Several microreactor units were coated with TiO2 doped with Cu (2.4 wt.%) nanoparticles synthesized by FSP (Flame Spray Pyrolysis) and tested for the photocatalytic degradation of two water pollutants showing excellent performance.