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
Influence of the power supply on the energy efficiency of an alkaline water electrolyser
(Elsevier, 2009) Ursúa Rubio, Alfredo; Marroyo Palomo, Luis; Gubía Villabona, Eugenio; Gandía Pascual, Luis; Diéguez Elizondo, Pedro; Sanchis Gúrpide, Pablo; Ingeniería Eléctrica y Electrónica; Ingeniaritza Elektrikoa eta Elektronikoa; Ingeniería Mecánica, Energética y de Materiales; Mekanika, Energetika eta Materialen Ingeniaritza; Química Aplicada; Kimika Aplikatua; Gobierno de Navarra / Nafarroako Gobernua
Electric energy consumption represents the greatest part of the cost of the hydrogen produced by water electrolysis. An effort is being carried out to reduce this electric consumption and improve the global efficiency of commercial electrolysers. Whereas relevant progresses are being achieved in cell stack configurations and electrodes performance, there are practically no studies on the effect of the electric power supply topology on the electrolyser energy efficiency. This paper presents an analysis on the energy consumption and efficiency of a 1 N m3 h1 commercial alkaline water electrolyser and their dependence on the power supply topology. The different topologies of power supplies are first summarised, analysed and classified into two groups: thyristor-based (ThPS) and transistor-based power supplies (TrPS). An Electrolyser Power Supply Emulator (EPSE) is then designed, developed and satisfactorily validated by means of simulation and experimental tests. With the EPSE, the electrolyser is characterised both obtaining its I–V curves for different temperatures and measuring the useful hydrogen production. The electrolyser is then supplied by means of two different emulated electric profiles that are characteristic of typical ThPS and TrPS. Results show that the cell stack energy consumption is up to 495 W h N m3 lower when it is supplied by the TrPS, which means 10% greater in terms of efficiency.
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
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
Conversion of a commercial spark ignition engine to run on hydrogen: performance comparison using hydrogen and gasoline
(Elsevier, 2010) Sopena Serna, Carlos; Diéguez Elizondo, Pedro; Sáinz Casas, David; Urroz Unzueta, José Carlos; Guelbenzu, E.; Gandía Pascual, Luis; Ingeniería; Ingeniaritza
The modifications performed to convert the spark ignition gasoline-fueled internal combustion engine of a Volkswagen Polo 1.4 to run with hydrogen are described. The car is representative of small vehicles widely used for both city and interurban traffic. Main changes included the inlet manifold, gas injectors, oil radiator and the electronic management unit. Injection and ignition advance timing maps were developed for lean mixtures with values of the air to hydrogen equivalence ratio (λ) between 1.6 and 3. The established engine control parameters allowed the safe operation of the hydrogen-fueled engine (H2ICE) free of knock, backfire and pre-ignition as well with reasonably low NOx emissions. The H2ICE reached best brake torque of 63 Nm at 3800 rpm and maximum brake power of 32 kW at 5000 rpm. In general, the brake thermal efficiency of the H2ICE is greater than that of gasoline-fueled engine except for the H2ICE working at very lean conditions (λ = 2.5) and high speeds (above 4000 rpm). A significant effect of the spark advance on the NOx emissions has been found, specially for relatively rich mixtures (λ < 2). Small changes of spark advance with respect to the optimum value for maximum brake torque give rise to an increase of pollutant emissions. It has been estimated that the hydrogen-fueled Volkswagen Polo could reach a maximum speed of 140 km/h with the adapted engine. Moreover, there is enough reserve of power for the vehicle moving on typical urban routes and routes with slopes up to 10%.
Open Access
Effect of oxygen addition, reaction temperature and thermal treatments on syngas production from biogas combined reforming using Rh/alumina catalysts
(Elsevier, 2019) Navarro Puyuelo, Andrea; Reyero Zaragoza, Inés; Moral Larrasoaña, Ainara; Bimbela Serrano, Fernando; Bañares, Miguel A.; Gandía Pascual, Luis; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Dry reforming and partial oxidation of biogas were studied using 0.5 wt.% Rh/Al2O3 catalysts, both inhouse prepared and commercial. The effects of O2 addition on syngas yield and biogas conversion were studied at 700 C using different O2/CH4 ratios in the gas feeding stream: 0 (dry reforming), 0.12, 0.25, 0.45 and 0.50. The highest CH4 conversion, H2 yield and H2/CO molar ratio were obtained with an O2/CH4 ratio of 0.45, even though simultaneous valorization of both CH4 and CO2 could be best attained when the O2/CH4 ratio was 0.12. Increased biogas conversions and syngas yields were obtained by increasing reaction temperatures between 650 and 750 C. A detrimental influence on catalytic activity could be observed when the catalyst was subjected to calcination. Increasing the hold time of the thermal conditioning of the catalyst under inert flow altered Rh dispersion, though had no significant impact on catalyst performance in the dry reforming of methane at 700 C and 150 N L CH4/(gcat h). Characterization of spent samples after reaction by Raman spectroscopy revealed the presence of carbonaceous deposits of different nature, especially on the commercial(named as Rh com) and calcined (Rh calc) catalysts, though oxygen addition in the biogas feed significantly reduced the amount of these deposits. The Rh catalysts that had not been calcined after impregnation (Rh prep) did not present any noticeable characteristic peaks in the G and D bands. In particular, scanning transmission electron microscopy (STEM) images of the spent Rh prep sample revealed the presence of very highly dispersed Rh nanoparticles after reaction, of particle sizes of about 1 nm, and no noticeable C deposits. Combined oxy-CO2 reforming of biogas using highly dispersed and low metal-loading Rh/Al2O3 catalysts with low O2 dosage in the reactor feed can be used to effectively transform biogas into syngas.
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
Hydrogen production from water electrolysis: current status and future trends
(IEEE, 2012) Ursúa Rubio, Alfredo; Gandía Pascual, Luis; Sanchis Gúrpide, Pablo; Ingeniería Eléctrica y Electrónica; Ingeniaritza Elektrikoa eta Elektronikoa; Química Aplicada; Kimika Aplikatua
This paper reviews water electrolysis technologies for hydrogen production and also surveys the state of the art of water electrolysis integration with renewable energies. First, attention is paid to the thermodynamic and electrochemical processes to better understand how electrolysis cells work and how they can be combined to build big electrolysis modules. The electrolysis process and the characteristics, advantages, drawbacks, and challenges of the three main existing electrolysis technologies, namely alkaline, polymer electrolyte membrane, and solid oxide electrolyte, are then discussed. Current manufacturers and the main features of commercially available electrolyzers are extensively reviewed. Finally, the possible configurations allowing the integration of water electrolysis units with renewable energy sources in both autonomous and grid-connected systems are presented and some relevant demonstration projects are commented.
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.