Open Access
Gold supported on CuOₓ/CeO₂ catalyst for the purification of hydrogen by the CO preferential oxidation reaction (PROX)
(Elsevier, 2014) Arzamendi Manterola, Gurutze; Gandía Pascual, Luis; Química Aplicada; Kimika Aplikatua
Hydrogen produced from the conversion of hydrocarbons or alcohols contains variable amounts of CO that should be removed for some applications such as feeding low-temperature polymer electrolyte membrane fuel cells (PEMFCs). The CO preferential oxidation reaction (PROX) is particularly well-suited for hydrogen purification for portable and on-board applications. In this work, the synthesis and characterization by XRF, BET, XRD, Raman spectroscopy and H2-TPR of a gold catalyst supported on a coppercerium mixed oxide (AuCeCu) for the PROX reaction are presented. The comparison of this catalyst with the copper–cerium mixed oxide (CeCu) revealed that the experimental procedure used for the deposition of gold gave rise to the loss of reducible material by copper lixiviation. However, the AuCeCu solid was more active for CO oxidation at low temperature. A kinetic study has been carried over the AuCeCu catalyst for the PROX reaction and compared with that of the CeCu catalyst. The main difference between the models affected the contribution of the CO adsorption term. This fact may be related to the surface electronic activity produced by the interaction of the cationic species in the AuCeCu solid, able to create more active sites for the CO adsorption and activation in the presence of gold.
Open Access
Oak wood extracts applied to the grapevine. An alternative to obtain quality Garnacha wines
(Elsevier, 2018) Jiménez Moreno, Nerea; Moler Cuiral, José Antonio; Urmeneta Martín-Calero, Henar; Suberviola Ripa, Julián; Cibriain Sabalza, Félix; Gandía Pascual, Luis; Ancín Azpilicueta, Carmen; Química Aplicada; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Estadística e Investigación Operativa; Estatistika eta Ikerketa Operatiboa
Open Access
Rutas y retos para la valorización de biogás
(Universidad Libre (Colombia), 2017) Navarro Puyuelo, Andrea; Reyero Zaragoza, Inés; Moral Larrasoaña, Ainara; Bimbela Serrano, Fernando; Gandía Pascual, Luis; Química Aplicada; Kimika Aplikatua
Las tecnologías de digestión anaerobia para procesar corrientes residuales (fracción orgánica de residuos de vertedero, lodos de estaciones depuradoras de aguas residuales, purines, etc.) han originado un incremento de la producción de biogás. El biogás está compuesto principalmente por metano y dióxido de carbono, aunque contiene otros componentes minoritarios e impurezas que obligan a efectuar tratamientos para su purificación y acondicionamiento. Existen diversas alternativas para el aprovechamiento y la valorización de este gas, como son: su utilización directa en la generación de energía calorífica y/o eléctrica, su conversión a biometano, y la producción de gas de síntesis (H2+CO), que posteriormente permite producir combustibles líquidos y/o compuestos químicos de interés como el metanol. En este trabajo se presenta una revisión general de las alternativas de valorización de biogás, con énfasis en los procesos de reformado catalítico, tales como el reformado seco o con vapor de agua y procesos de reformado combinado incluyendo la oxidación parcial.
Open Access
Characterization of combustion anomalies in a hydrogen-fueled 1.4 L commercial spark-ignition engine by means of in-cylinder pressure, block-engine vibration, and acoustic measurements
(Elsevier, 2018) Diéguez Elizondo, Pedro; Urroz Unzueta, José Carlos; Sáinz Casas, David; Machín Mindán, Jorge; Arana Burgui, Miguel; Gandía Pascual, Luis; Institute for Advanced Materials and Mathematics - INAMAT2
Abnormal combustion phenomena are among the main hurdles for the introduction of hydrogen in the transportation sector through the use of internal combustion engines (ICEs). For that reason the challenge is to guarantee operation free from combustion anomalies at conditions close to the ones giving the best engine output (maximum brake torque and power). To this end, an early and accurate detection of abnormal combustion events is decisive in order to allow the electronic control unit deciding suitable correcting actions. In this work, an automotive size 4-cylinder 1.4 L naturally aspirated port-fuel injection spark ignition Volkswagen engine adapted to run on hydrogen has been investigated. Three distinct methods (in-cylinder pressure, block-engine vibration and acoustic measurements) have been employed to detect abnormal combustion phenomena provoked through the enrichment of the hydrogen-air mixture fed to the cylinders under a wide range of engine speeds (1000–5000 rpm). It has been found that the high-frequency components of the in-cylinder pressure and block engine acceleration signals obtained after a Fourier transform analysis can be used for very sensitive detection of knocking combustion cycles. In the case of the ambient noise measurements, a spectral analysis in terms of third octave bands of the signal recorded by a microphone allowed an accurate characterization. Combustion anomalies could be detected through more intense octave bands at frequencies between 250 Hz and 4 kHz in the case of backfire and between 8 kHz and 20 kHz for knock. Computational fluid dynamics simulations performed indicated that some characteristics of the engine used such as the cylinder valves dimensions and the hydrogen flow rate delivered by the injectors play important roles conditioning the likelihood of suffering backfire events.
Open Access
Conversion of a gasoline engine-generator set to a bi-fuel (hydrogen/gasoline) electronic fuel-injected power unit
(Elsevier, 2011) Sáinz Casas, David; Diéguez Elizondo, Pedro; Urroz Unzueta, José Carlos; Sopena Serna, Carlos; Guelbenzu, E.; Pérez Ezcurdia, Amaya; Benito Amurrio, Marta; Marcelino Sádaba, Sara; Arzamendi Manterola, Gurutze; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
The modifications performed to convert a gasoline carbureted engine-generator set to a bi-fuel (hydrogen/gasoline) electronic fuel-injected power unit are described. Main changes affected the gasoline and gas injectors, the injector seats on the existing inlet manifold, camshaft and crankshaft wheels with their corresponding Hall sensors, throttle position and oil temperature sensors as well as the electronic management unit. When working on gasoline, the engine-generator set was able to provide up to 8 kW of continuous electric power (10 kW peak power), whereas working on hydrogen it provided up to 5 kW of electric power at an engine speed of 3000 rpm. The air-to-fuel equivalence ratio (λ) was adjusted to stoichiometric (λ = 1) for gasoline. In contrast, when using hydrogen the engine worked ultra-lean (λ = 3) in the absence of connected electric load and richer as the load increased. Comparisons of the fuel consumptions and pollutant emissions running on gasoline and hydrogen were performed at the same engine speed and electric loads between 1 and 5 kW. The specific fuel consumption was much lower with the engine running on hydrogen than on gasoline. At 5 kW of load up to 26% of thermal efficiency was reached with hydrogen whereas only 20% was achieved with the engine running on gasoline. Regarding the NOx emissions, they were low, of the order of 30 ppm for loads below 4 kW for the engine-generator set working on hydrogen. The bi-fuel engine is very reliable and the required modifications can be performed without excessive difficulties thus allowing taking advantage of the well-established existing fabrication processes of internal combustion engines looking to speed up the implementation of the energetic uses of hydrogen.
Open Access
Conversion of a commercial gasoline vehicle to run bi-fuel (hydrogen-gasoline)
(Elsevier, 2012) Sáinz Casas, David; Diéguez Elizondo, Pedro; Sopena Serna, Carlos; Urroz Unzueta, José Carlos; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
Bi-fuel internal combustion engine vehicles allowing the operation with gasoline or diesel and hydrogen have great potential for speeding up the introduction of hydrogen in the transport sector. This would also contribute to alleviate the problem of urban air pollution. In this work, the modifications carried out to convert a Volkswagen Polo 1.4 into a bi-fuel (hydrogen-gasoline) car are described. Changes included the incorporation of a storage system based on compressed hydrogen, a machined intake manifold with a low-pressure accumulator where the hydrogen injectors were assembled, a new electronic control unit managing operation on hydrogen and an electrical junction box to control the change from a fuel to another. Change of fuel is very simple and does not require stopping the car. Road tests with hydrogen fuel gave a maximum speed of 125 km/h and an estimated consumption of 1 kg of hydrogen per 100 km at an average speed of 90 km/h. Vehicle conversion to bi-fuel operation is technically feasible and cheap.
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
Kinetic analysis and CFD simulations of the photocatalytic production of hydrogen in silicone microreactors from water-ethanol mixtures
(Elsevier, 2017) Castedo, Alejandra; Uriz Doray, Irantzu; Soler, Lluís; Gandía Pascual, Luis; Llorca Piqué, Jordi; Kimika Aplikatua; Institute for Advanced Materials and Mathematics - INAMAT2; Química Aplicada
Silicone microreactors containing microchannels of 500 μm width in a single or triple stack configuration have been manufactured, coated with an Au/TiO2 photocatalyst and tested for the photocatalytic production of hydrogen from water-ethanol gaseous mixtures under UV irradiation. Computational fluid dynamics (CFD) simulations have revealed that the design of the distributing headers allowed for a homogeneous distribution of the gaseous stream within the channels of the microreactors. A rate equation for the photocatalytic reaction has been developed from the experimental results obtained with the single stack operated under different ethanol partial pressures, light irradiation intensities and contact times. The hydrogen photoproduction rate has been expressed in terms of a Langmuir-Hinshelwood-type equation that accurately describes the process considering that hydrogen is produced through the dehydrogenation of ethanol to acetaldehyde. This equation incorporates an apparent rate constant (kapp) that has been found to be proportional to the intrinsic kinetic rate constant (k), and that depends on the light intensity (I) as follows: kapp = k·I0.65. A three-dimensional isothermal CFD model has been developed in which the previously obtained kinetic equation has been implemented. The model adequately describes the production of hydrogen of both the single and triple stacks. Moreover, the specific hydrogen productions (i.e. per gram of catalyst) are very close for both stacks thus suggesting that the scaling-up of the process could be accomplished by simply numbering-up. However, small deviations between the experimental and predicted hydrogen production suggest that a fraction of the radiation is absorbed by the microreactor components which should be taken into account for scaling-up purposes.
Open Access
Experimental study of the performance and emission characteristics of an adapted commercial four-cylinder spark ignition engine running on hydrogen-methane mixtures
(Elsevier, 2014) Diéguez Elizondo, Pedro; Urroz Unzueta, José Carlos; Marcelino Sádaba, Sara; Pérez Ezcurdia, Amaya; Benito Amurrio, Marta; Sáinz Casas, David; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
The use of hydrogen/methane mixtures with low methane contents as fuels for internal combustion engines (ICEs) may help to speed up the development of the hydrogen energy market and contribute to the decarbonization of the transportation sector. In this work, a commercial 1.4 L four-cylinder Volkswagen spark-ignition engine previously adapted to operate on pure hydrogen has been fueled with hydrogen/methane mixtures with 5–20 vol.% methane (29.6–66.7 wt.%). An experimental program has been executed by varying the fuel composition, air-to-fuel ratio (λ), spark advance and engine speed. A discussion of the results regarding the engine performance (brake torque, brake mean effective pressure, thermal efficiency) and emissions (nitrogen oxides, CO and unburned hydrocarbons) is presented. The results reveal that λ is the most influential variable on the engine behavior due to its marked effect on the combustion temperature. As far as relatively high values of λ have to be used to prevent knock, the effect on the engine performance is negative. In contrast, the specific emissions of nitrogen oxides decrease due to a reduced formation of thermal NOx. A clear positive effect of reducing the spark advance on the specific NOx emissions has been observed as well. As concerns CO and unburned hydrocarbons (HCs), their specific emissions increase with the methane content of the fuel mixture, as expected. However, they also increase as λ increases in spite of the lower fuel concentration due to a proportionally higher reduction of the power. Finally, the effect of the increase of the engine speed is positive on the CO and HCs emissions but negative on that of NOx due to improved mixing and higher temperature associated to intensified turbulence in the cylinders.
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