Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Nanocomposites de Poliuretanos Elastoméricos y Nanotubos de Carbono Multipared

218p. -- Tesis con mención "Doctor europeus" realizada en el periodo de Octubre 2005-Mayo 2010, en el Grupo "Materiales+Tecnologías" (GMT).

Modular integration and on-chip sensing approaches for tunable fluid control polymer microdevices

228 p.

Measurement of polycyclic aromatic hydrocarbons in ambient air by fluorescence spectroscopic techniques

250 p. + anexos

Reutilización de escoria negra de acería como soporte en biofiltros para la eliminación de H2S del biogás.

[EN]Due to the limitations associated with fossil fuels it is necessary to promote energy sources that are renewable as well as eco-friendly, such as biogas generated in anaerobic digesters. The biogas, composed principally of methane and CO2, is the result of the biodegradation of organic matter under anaerobic conditions. Its use as fuel is limited by the presence of minority compounds such as hydrogen sulphide (H2S); therefore, its pre-treatment is necessary. Currently there are various technologies for the removal of H2S from a gas stream, but most of them are based on physic-chemical treatments which have a number of drawbacks as reactive consumption, generation of secondary flows, etc. Biofiltration has been used as an efficient and low cost alternative to conventional purification processes, and excellent results for the degradation of H2S have been obtained. However process can be limited due to the progressive ageing of the support material, along with the loss of nutrients and other specific characteristics necessary for the good development of biomass. The purpose of this project is to develop a mixed support consisting of a mixture of an organic material and an inorganic support for its application in the removal of the H2S from biogas. This support material helps to optimize the characteristics of the bed and extend its lifespan. The development of such material will contribute to the implementation of biofiltration for treating biogas from anaerobic digesters for its use as biofuel. The inorganic material used is electric arc furnace (EAF) black slag, a by-product generated in large quantities in the production of steel in the Basque Country. Although traditionally the slag has been used in civil engineering, its physicochemical characteristics make it suitable for reuse as a filter medium in biofiltration. The main conclusion drawn from the experimental results is that EAF black slag is a suitable co-packing material in organic biofilters treating H2S-polluted gaseous streams. High pollutant removal rates have been achieved during the whole experimental period. The removal capacity recorded in biofilters with less inorganic material was higher than in those with higher slag portion. Nevertheless, all the biofilters have shown a satisfactory response even at high inlet loads (48 g·m-3·h-1), where the RE has not decreased over 82%.

Skate elektriko baten gauzatzea, hautabideak eta diseinua.

[EU]Lan honetan hutsetik hasita skate motorizatu baten diseinu bat egin da, Industria Teknologian Ingeniaritzako Graduan eskuratutako jakintzak erabiliz. Skatea gazteengan oso erabilia den garraiobide bat da aisia dela-eta, eta sinpletasuna eta ekonomia kontuan hartuta, aisia eta ingurugiroarekiko konpromisoa nahasten dira diseinu honekin. Lanak bide argi bat dauka: hasieran merkatuaren egoera aztertzen da, gero diseinu posible batzuk proposatu ahal izateko, eta hortik aukera bat jorratu ahal izateko. Hortaz, prozesua hasieratik hasita, egitura hau izango du lanak: Hasteko, skate motorizatuen merkatuko egoera zein den aztertzen da, ondoren eta helburuak zeintzuk diren kontutan izanda, diseinu posible batzuk proposatu ahal izateko, alternatiben analisien atalean ageri direnak. Proposamen horiek aztertu egiten dira, alde on eta txarrak desberdinduz eta horietako soluzio bat aukeratuz. Aukeratutako diseinuaren CAD modelo bat eraikitzen da, ondoren egoera fisikoa matematikoki modelizatzeko eta beharrezko kalkuluak egin ahal izateko, metodologia atalean eta eranskinetan ageri direnak, hala nola, azelerazio jakin bat lortzeko behar den potentzia, transmisioan beharrezkoak diren kalkuluak kokatu beharreko elementuak zeintzuk diren erabaki ahal izateko, etab. Bide honetan, jorraturiko diseinuaz gain beste diseinu optimizatu eta konplexuago bat proposatzen da, ikerketa bidea zabalik duena, enpresa mundura gehiago zuzendua. Azkenik, lana burutzeko bete behar izan diren ataza bakoitzaren deskribapena eta iraupena, aurrekontua eta gastu aitorpena, arriskuen analisia eta proiektu honetatik atera ditugun ondorioak ematen dira.

A-SCALA: an age-structured statistical catch-at-length analysis for assessing tuna stocks in the eastern tropical Pacific Ocean

English: We describe an age-structured statistical catch-at-length analysis (A-SCALA) based on the MULTIFAN-CL model of Fournier et al. (1998). The analysis is applied independently to both the yellowfin and the bigeye tuna populations of the eastern Pacific Ocean (EPO). We model the populations from 1975 to 1999, based on quarterly time steps. Only a single stock for each species is assumed for each analysis, but multiple fisheries that are spatially separate are modeled to allow for spatial differences in catchability and selectivity. The analysis allows for error in the effort-fishing mortality relationship, temporal trends in catchability, temporal variation in recruitment, relationships between the environment and recruitment and between the environment and catchability, and differences in selectivity and catchability among fisheries. The model is fit to total catch data and proportional catch-at-length data conditioned on effort. The A-SCALA method is a statistical approach, and therefore recognizes that the data collected from the fishery do not perfectly represent the population. Also, there is uncertainty in our knowledge about the dynamics of the system and uncertainty about how the observed data relate to the real population. The use of likelihood functions allow us to model the uncertainty in the data collected from the population, and the inclusion of estimable process error allows us to model the uncertainties in the dynamics of the system. The statistical approach allows for the calculation of confidence intervals and the testing of hypotheses. We use a Bayesian version of the maximum likelihood framework that includes distributional constraints on temporal variation in recruitment, the effort-fishing mortality relationship, and catchability. Curvature penalties for selectivity parameters and penalties on extreme fishing mortality rates are also included in the objective function. The mode of the joint posterior distribution is used as an estimate of the model parameters. Confidence intervals are calculated using the normal approximation method. It should be noted that the estimation method includes constraints and priors and therefore the confidence intervals are different from traditionally calculated confidence intervals. Management reference points are calculated, and forward projections are carried out to provide advice for making management decisions for the yellowfin and bigeye populations. Spanish: Describimos un análisis estadístico de captura a talla estructurado por edad, A-SCALA (del inglés age-structured statistical catch-at-length analysis), basado en el modelo MULTIFAN- CL de Fournier et al. (1998). Se aplica el análisis independientemente a las poblaciones de atunes aleta amarilla y patudo del Océano Pacífico oriental (OPO). Modelamos las poblaciones de 1975 a 1999, en pasos trimestrales. Se supone solamente una sola población para cada especie para cada análisis, pero se modelan pesquerías múltiples espacialmente separadas para tomar en cuenta diferencias espaciales en la capturabilidad y selectividad. El análisis toma en cuenta error en la relación esfuerzo-mortalidad por pesca, tendencias temporales en la capturabilidad, variación temporal en el reclutamiento, relaciones entre el medio ambiente y el reclutamiento y entre el medio ambiente y la capturabilidad, y diferencias en selectividad y capturabilidad entre pesquerías. Se ajusta el modelo a datos de captura total y a datos de captura a talla proporcional condicionados sobre esfuerzo. El método A-SCALA es un enfoque estadístico, y reconoce por lo tanto que los datos obtenidos de la pesca no representan la población perfectamente. Además, hay incertidumbre en nuestros conocimientos de la dinámica del sistema e incertidumbre sobre la relación entre los datos observados y la población real. El uso de funciones de verosimilitud nos permite modelar la incertidumbre en los datos obtenidos de la población, y la inclusión de un error de proceso estimable nos permite modelar las incertidumbres en la dinámica del sistema. El enfoque estadístico permite calcular intervalos de confianza y comprobar hipótesis. Usamos una versión bayesiana del marco de verosimilitud máxima que incluye constreñimientos distribucionales sobre la variación temporal en el reclutamiento, la relación esfuerzo-mortalidad por pesca, y la capturabilidad. Se incluyen también en la función objetivo penalidades por curvatura para los parámetros de selectividad y penalidades por tasas extremas de mortalidad por pesca. Se usa la moda de la distribución posterior conjunta como estimación de los parámetros del modelo. Se calculan los intervalos de confianza usando el método de aproximación normal. Cabe destacar que el método de estimación incluye constreñimientos y distribuciones previas y por lo tanto los intervalos de confianza son diferentes de los intervalos de confianza calculados de forma tradicional. Se calculan puntos de referencia para el ordenamiento, y se realizan proyecciones a futuro para asesorar la toma de decisiones para el ordenamiento de las poblaciones de aleta amarilla y patudo.

Development of the heterogeneous catalysts for the production of levulinic acid from furfuryl alcohol

207 p.

Análisis de accidente grave de un establecimiento afectado por la directiva 2012/18/UE.

[Es]Los establecimientos industriales a los que la directiva 2012/18/UE es de aplicación deben establecer las acciones necesarias para controlar y planificar los riesgos inherentes a los accidentes graves que pueden ser causados por sustancias peligrosas. Esta directiva obliga a los establecimientos afectados clasificados como nivel superior a elaborar un informe de seguridad en el que se realicen análisis de riesgos de los posibles accidentes graves con el fin de calcular los posibles daños que pudieran producirse. Para ello se siguen una serie de metodologías que incluyen desde el análisis de las posibles hipótesis de accidente grave hasta el cálculo de sus consecuencias para personas, bienes materiales y medio ambiente. El informe técnico trata de analizar las consecuencias de un accidente real provocado por una nube tóxica de dióxido de nitrógeno (NO2) y se comparan sus resultados con los datos reales del accidente. Asimismo se utilizan una serie de supuestos para analizar las consecuencias de un escenario de riesgo en la misma instalación que debiera estar incluido en el informe de seguridad.

Influencia del vehículo eléctrico en la red eléctrica, en función del comportamiento social.

[ES]En la actualidad, el modelo de transporte apenas ha avanzado en el intento de frenar el Cambio Climático o en el cuidado del medio ambiente. Además, el gran negocio que existe detrás del petróleo hace que este tipo de transporte sea poco sostenible. Es por eso que se está desarrollando, a nivel nacional e internacional, una solución a dicho problema que es el uso del vehiculó eléctrico (VE). La introducción masiva del VE permitirá el uso extensivo de fuentes de energía no contaminantes e intermitentes, como son las energías renovables. Sin embargo, los VEs están lejos de ser una tecnología probada. Existen aún muchos problemas en torno a él que deben ser resueltos, entre ellos se encuentra el desarrollo de las baterías, su modelo de negocio y coste o la influencia de la conexión del VE sobre la red eléctrica. Este último problema, estará muy influenciado por el comportamiento social del futuro conductor, lo cual es el eje central del proyecto.

Estrategias en la localización de espacios para actividades productivas y económicas con un enfoque integrador: economía, sostenibilidad y planeamiento .

536 p.

Air Quality and Europeans' Subjective Well-being

[EN]Happiness economics deals with self-reported subjective well-being, or life satisfaction, and its relationship to a wide variety of other variables. On the study of these other factors, this line of research has helped demonstrate that higher levels of environmental quality increase people’s subjective well-being. This paper focuses on analyzing the relationship between subjective well-being and air quality. On the one hand, the life satisfaction approach to environmental valuation is cautiously described, and on the other hand, the method is implemented in an empirical analysis that seeks to assess how an increase in the level of air pollution at a regional level affects individual-level subjective well-being in Europe. We use a dataset that merges the third wave of the European Social Survey (ESS) with a dataset that includes regional air pollution (including CO, PM10, NO2, SO2 and Benzene) and other regional variables. We find a robust negative impact for CO, a positive impact for SO2, and no conclusive evidence of any effect on subjective well-being for the remaining three pollutants.

Edificación sostenible. Aplicaciones desde la perspectiva del marketing

[ES]El sector de la construcción genera una serie de impactos sobre el bienestar de las personas y el medio ambiente, derivados básicamente del consumo de recursos, emisiones de gases contaminantes y demolición de los edificios. A lo largo del trabajo se aportan ideas y soluciones potenciales para que las empresas apuesten por un modelo de construcción sostenible. Para ello se analiza el entorno de las empresas vinculadas al sector de la construcción, que permite estudiar los factores que afectan a las organizaciones. Además se desglosan las actividades de una sociedad enfocada hacia la edificación sostenible, para finalmente exponer conclusiones de como se le puede añadir valor a una vivienda desde una perspectiva ecológica, durante todo el proceso de extracción y trasformación de materias primas, diseño, producción, comercialización y servicio postventa. Finalmente, para contrastar lo analizado a lo largo del trabajo y tener la perspectiva sobre el tema de una empresa referente en la construcción, se ha realizado una entrevista a D. Javier Pérez Uribarri, Partner Senior Architect de IDOM, y a D. Blas Beristain de la Rica, M. Arquitecto de IDOM y Responsable del Área de Edificación Sostenible.

El papel del medioambiente en el desarrollo sostenible

En el primer apartado me he centrado en los problemas ambientales más conocidos hoy en día, explicando las razones por las que ocurren estos problemas y las posibles soluciones. Una vez explicados estos problemas he mencionado la ausencia de la variable medioambiental en el mercado, las razones por las que no está y la necesidad de integrarla en él. A partir de ahí me he centrado más en el mundo de la empresa y el medio ambiente, las razones por las que algunas empresas tienden a integrar o no en sus decisiones el posible deterioro al medio ambiente y una vez han decidido integrar esa variable los diferentes instrumentos que pueden utilizar para el buen cuidado del medio ambiente.

La Pobreza Energética: una primera aproximación

[ES] El objetivo de este trabajo es definir adecuadamente el concepto de pobreza energética y explicar cuáles son los enfoques o metodologías que actualmente existen para medirla. También se analiza cuál es la situación actual de la pobreza energética en España así como la relación que existe entre la pobreza energética y el desempleo. Además, se muestran cuáles son las principales consecuencias que genera la pobreza energética sobre la salud, el medio ambiente y la degradación de los edificios. Por último se hace un análisis de las diferentes políticas e iniciativas en términos de pobreza energética que se han tomado en algunos países de la Unión Europea y en España.