A problem that has become apparently growing in the deployment of renewable energy systems is the power grids inability to accept the forecasted growth in renewable energy generation integration. To support forecasted growth in renewable generation integration, it is now recognised that Energy Storage Technologies (EST) must be utilised. Recent advances in Hydrogen Energy Storage Technologies (HEST) have unlocked their potential for use with constrained renewable generation. HEST combines Hydrogen production, storage and end use technologies with renewable generation in either a directly connected configuration, or indirectly via existing power networks. A levelised cost (LC) model has been developed within this thesis to identify the financial competitiveness of the different HEST application scenarios when used with grid constrained renewable energy. Five HEST scenarios have been investigated to demonstrate the most financially competitive configuration and the benefit that the by-product oxygen from renewable electrolysis can have on financial competitiveness. Furthermore, to address the lack in commercial software tools available to size an energy system incorporating HEST with limited data, a deterministic modelling approach has been developed to enable the initial automatic sizing of a hybrid renewable hydrogen energy system (HRHES) for a specified consumer demand. Within this approach, a worst-case scenario from the financial competitiveness analysis has been used to demonstrate that initial sizing of a HRHES can be achieved with only two input data, namely – the available renewable resource and the load profile. The effect of the electrolyser thermal transients at start-up on the overall quantity of hydrogen produced (and accordingly the energy stored), when operated in conjunction with an intermittent renewable generation source, has also been modelled. Finally, a mass-transfer simulation model has been developed to investigate the suitability of constrained renewable generation in creating hydrogen for a hydrogen refuelling station.

Recently, the increasing level of atmospheric CO₂ has been widely noticed due to its association with global warming, provoking a growth in environmental concerns toward the continued use of fossil fuels. To mitigate the concentration of atmospheric CO₂, various strategies have been implemented. Among options to turn waste CO₂ into useful fuels and chemicals, carbon capture and utilisation along with renewable hydrogen production as the source materials for methanol production is more preferable. In the 1960s, the highly active and economic Cu/ZnO/Al₂O₃ catalyst was developed for CO₂ hydrogenation reaction to methanol, since then, metal nanoparticles and nanocomposites have been extensively investigated and applied. Especially, bimetallic catalysts have emerged as an important class of catalysts due to their unique properties and superior catalytic performances compared to their monometallic counterparts. This thesis presents the evolution of the catalyst development for CO₂ hydrogenation to methanol: Firstly, we introduced the CuZn-based catalysts with Zn content increased in the bimetallic CuZn system via a heterojunction synthesis approach. Secondly, we increased the active CuZn sites via introducing ultra-thin layered double hydroxide as the catalyst precursor for methanol production from CO₂ and H₂. Thirdly, a new class of Rh-In bimetallic catalysts were studied, which shows high methanol yield and selectivity under thermodynamically unfavourable methanol synthesis conditions owing to the strong synergies of Rh-In bimetallic system. Fourthly, for the renewable methanol production from H₂ and CO₂, the hydrogen source must come from the green production routes. Therefore, an in-depth study of a nanocomposite system, CdS-carbon nanotubes-MoS₂, for photocatalytic hydrogen production from water has been demonstrated. Finally, the conclusion of this thesis is given and an outlook is presented for the future development in this research area.

Biomass-fuelled proton exchange membrane fuel cells (PEMFCs) offer asolution for replacing fossil fuel for hydrogen production. Through using thebiomass-derived hydrogen as fuel, PEMFCs may become an efficient andsustainable energy system for small and medium-sized enterprises. The aim ofthis thesis is to evaluate the performance and potential applications of biomassfuelledPEMFC systems which are designed to convert biomass to electricity andheat. Biomass-fuelled PEMFC systems are simulated by Aspen plus based ondata collected from experiments and literature.The impact of the quality of the hydrogen-rich gas, anode stoichiometry, CH4content in the biogas and CH4 conversion rate on the performance of the PEMFCis investigated. Also, pinch technology is used to optimize the heat exchangernetwork to improve the power generation and thermal efficiency.For liquid and solid biomass, anaerobic digestion (AD) and gasification (GF),respectively, are relatively viable and developed conversion technologies. ForAD-PEMFC, a steam reformer is also needed to convert biogas to hydrogen-richgas. For 100 kWe generation, the GF-PEMFC system yields a good technicalperformance with 20 % electrical efficiency and 57 % thermal efficiency,whereas the AD-PEMFC system only has 9 % electrical efficiency and 13 %thermal efficiency. This low efficiency is due to the low efficiency of theanaerobic digester (AD) and the high internal heat consumption of the AD andthe steam reformer (SR). For the environmental aspects, the GF-PEMFC systemhas a high CO2 emissions offset factor and the AD-PEMFC system has anefficient land-use.The applications of the biomass-fuelled PEMFC systems are investigated on adairy farm and an olive oil plant. For the dairy farm, manure is used as feedstockto generate biogas through anaerobic digestion. A PEMFC qualified for 40 %electrical efficiency may generate 360 MWh electricity and 680 MWh heat peryear to make a dairy farm with 300 milked cows self-sufficient in a sustainableway. A PEMFC-CHP system designed for an olive oil plant generating annual 50000 m3 solid olive mill waste (SOMW) and 9 000 m3 olive mill waste water(OMW) is simulated based on experimental data from the Biogas2PEM-FCproject1. After the optimization of the heat exchanger network, the PEMFC-CHP  system can generate 194 kW electricity which corresponds to 62 % of the totalelectricity demand of the olive oil plant.The economic performance of the PEMFC and biogas-fuelled PEMFC areassessed roughly including capital, operation &amp; maintenance (O&amp;M) costs of thebiogas plant and the PEMFC-CHP, the cost of heat and electricity, and the valueof the digestate as fertilizer. / <p>QC 20151109</p>

[ES] La presente tesis doctoral se enmarca en el ámbito de la producción de hidrógeno renovable, y en el estudio metodologías de intensificación de procesos para la producción de hidrógeno mediante reactores de membrana y reactores que operan a alta presión. Para la producción de hidrógeno renovable, se estudió en detalle el proceso de reformado autotérmico (ATR) de bioetanol. Se diseñó y construyó un sistema de reacción de escala de laboratorio, que se operó bajo condiciones reales de operación industrial. En una primera etapa, se realizó la evaluación de distintos catalizadores comerciales para el ATR de etanol. Tras la selección del tipo de catalizador con mejor rendimiento, se probaron distintas variaciones sobre el mismo, añadiendo dopantes a la fase activa y al soporte. Los catalizadores con mejores resultados se probaron durante más de 100 h manteniendo su rendimiento. Una vez seleccionados la composición primara de los catalizadores, se hicieron pruebas para el escalado y optimización de los catalizadores fabricados mediante un proceso industrial. Se estudiaron los efectos de las condiciones de operació, siendo el parámetro de mayor relevancia la relación O/C. El mejor de los catalizadores desarrollados aumentó el rendimiento y disminuyó la producción de hidrocarburos en estas condiciones, alcanzándose un rendimiento de hasta 3.1 mol H2 / mol etanol. Este catalizador se probó durante 200 horas, manteniendo su estabilidad en todo el periodo, validando su aplicación en un reformador de etanol para la producción de hidrógeno. En otro apartado, se estudió la utilización de membranas de transporte de oxígeno como elemento distribuidor de oxígeno para el sistema de reacción de ATR, permitiendo alimentar al reactor oxígeno de alta pureza producido in-situ. Se probaron membranas capilares de BSCF. En el sistema de reacción de ATR, las membranas mostraron una permeación acorde a los valores habituales para este material. Se estudió el comportamiento de las membranas de BSCF en una atmósfera con vapor, en la que la permeación alcanzada disminuyó en presencia de vapor. La utilización de estas membranas en la reacción de ATR requeriría de un escalado correcto, pues el flujo de oxígeno aportado por la membrana sería bajo respecto a las necesidades de oxígeno de la reacción de ATR. Seguidamente, se probaron los efectos de la aplicación de capas protectoras porosas sobre los capilares de BSCF, para mejorar su estabilidad química en ambientes de rección. Mediante la técnica de dip-coating se aplicaron capas porosas de BSCF, CTO-CMO (Ce0.8Tb0.2O2--δ- MnCo2O4) y CTO. La aplicación de estas capas aumentó la permeación por la mejora en el área superficial de intercambio y de las reacciones superficiales, alcanzándose 3 - 3.6 NmL·min-1·cm-2 para las membranas recubiertas, frente a 2.4 NmL·min-1·cm-2 para la membrana sin recubrimiento. Estas mismas membranas se probaron en un reactor de membrana, en reacción con CH4. Las capas aporataron efectos catalíticos y protectores respecto a la membrana sin tratamiento superficial. Las capas de CTO y CTO-CMO aumentaron la permeación de oxígeno y la conversión de CH4, que alcanzó valores del 100%, y además, resultaron estables en las condiciones de reacción, mientras que las membranas con capa de BSCF y sin recubrimiento tuvieron conversiones más bajas y su estructura quedó degradada por la atmósfera de la reacción. Finalmente, se llevó a cabo el diseño y construcción de un sistema de reacción de alta presión para el estudio de procesos de producción de hidrógeno a alta presión a presiones de hasta 300 barg. En esta unidad, se podrán llevar a cabo reacciones de producción de hidrógeno a partir de biomasa en agua supercrítica. Adicionalmente, se diseñó un reactor de membrana que permitirá el trabajo con membranas de permeación de gases en condiciones de alta severidad, con potencial aplicación en la producción de hidrógeno a partir de reacciones de reformado con una alta eficiencia. / [CA] La present tesi doctoral s'emmarca en l'àmbit de la producció d'hidrogen renovable, i en l'estudi metodologies d'intensificació de processos per a la producció d'hidrogen mitjançant reactors de membrana i reactors que operen a alta pressió. Per a la producció d'hidrogen renovable, es va estudiar detalladament el procés de reformat autotérmico (ATR) de bioetanol. Es va dissenyar i va construir un sistema de reacció d'escala de laboratori, que es va operar sota condicions reals d'operació industrial. En una primera etapa, es va realitzar l'avaluació de diferents catalitzadors comercials per al ATR d'etanol. Després de la selecció de la mena de catalitzador amb millor rendiment, es van provar diferents variacions sobre aquest, afegint dopants a la fase activa i al suport. Els catalitzadors amb millors resultats es van provar durant més de 100 h mantenint el seu rendiment. Una vegada seleccionats la composició prevalguera dels catalitzadors, es van fer proves per a l'escalat i optimització dels catalitzadors fabricats mitjançant un procés industrial. Es van estudiar els efectes de les condicions de operació, sent el paràmetre de major rellevància la relació O/C. El millor dels catalitzadors desenvolupats va augmentar el rendiment i va disminuir la producció d'hidrocarburs en aquestes condicions, aconseguint-se un rendiment de fins a 3.1 mol H2 / mol etanol. Aquest catalitzador es va provar durant 200 hores, mantenint la seua estabilitat en tot el període, validant la seua aplicació en un reformador d'etanol per a la producció d'hidrogen. En un altre apartat, es va estudiar la utilització de membranes de transport d'oxigen com a element distribuïdor d'oxigen per al sistema de reacció de ATR, permetent alimentar al reactor oxigen d'alta puresa produït in-situ. Es van provar membranes capil·lars de BSCF. En el sistema de reacció de ATR, les membranes van mostrar una permeación concorde als valors habituals per a aquest material. Es va estudiar el comportament de les membranes de BSCF en una atmosfera amb vapor, en la qual la permeación aconseguida va disminuir en presència de vapor. La utilització d'aquestes membranes en la reacció de ATR requeriria d'un escalat correcte, perquè el flux d'oxigen aportat per la membrana seria baix respecte a les necessitats d'oxigen de la reacció de ATR. Seguidament, es van provar els efectes de l'aplicació de capes protectores poroses sobre els capil·lars de BSCF, per a millorar la seua estabilitat química en ambients de recció. Mitjançant la tècnica de dip-coating es van aplicar capes poroses de BSCF, CTO-CMO i CTO. L'aplicació d'aquestes capes va augmentar la permeación per la millora en l'àrea superficial d'intercanvi i de les reaccions superficials, aconseguint-se 3 - 3.6 NmL·min-1·cm-2 per a les membranes recobertes, enfront de 2.4 NmL·min-1·cm-2 per a la membrana sense recobriment. Aquestes mateixes membranes es van provar en un reactor de membrana, en reacció amb CH4. Les capes aporataron efectes catalítics i protectors respecte a la membrana sense tractament superficial. Les capes de CTO i CTO-CMO van augmentar la permeación d'oxigen i la conversió de CH4, que va aconseguir valors del 100%, i a més, van resultar estables en les condicions de reacció, mentre que les membranes amb capa de BSCF i sense recobriment van tindre conversions més baixes i la seua estructura va quedar degradada per l'atmosfera de la reacció. Finalment, es va dur a terme el disseny i construcció d'un sistema de reacció d'alta pressió per a l'estudi de processos de producció d'hidrogen a alta pressió a pressions de fins a 300 barg. En aquesta unitat, es podran dur a terme reaccions de producció d'hidrogen a partir de biomassa en aigua supercrítica. Addicionalment, es va dissenyar un reactor de membrana que permetrà el treball amb membranes de permeación de gasos en condicions d'alta severitat, amb potencial aplicació en la producció d'hidrogen a partir de reaccions de reformat amb una alta eficiència. / [EN] This doctoral thesis is framed in the field of renewable hydrogen production, and in the study of process intensification methodologies for the production of hydrogen through membrane reactors and reactors that operate at high pressure. For the production of renewable hydrogen, the bioethanol autothermal reforming (ATR) process was studied in detail. He designed and built a laboratory scale reaction system, which was operated under real industrial operating conditions. In a first stage, the evaluation of different commercial catalysts for ethanol ATR was carried out. After selecting the type of catalyst with the best performance, different variations were tested on it, adding dopants to the active phase and to the support. The catalysts with the best results were tested for more than 100 h maintaining their performance. Once the primary composition of the catalysts had been selected, tests were carried out for the scaling and optimization of the catalysts manufactured by means of an industrial process. The effects of operating conditions were studied, the most relevant parameter being the O / C ratio. The best of the developed catalysts increased the yield and decreased the production of hydrocarbons under these conditions, reaching a yield of up to 3.1 mol H2 / mol ethanol. This catalyst was tested for 200 hours, maintaining its stability throughout the period, validating its application in an ethanol reformer for the production of hydrogen. In another section, the use of oxygen transport membranes as an oxygen distributor element for the ATR reaction system was studied, allowing the reactor to be fed high-purity oxygen produced in-situ. Capillary membranes from BSCF were tested. In the ATR reaction system, the membranes showed a permeation according to the usual values for this material. The behavior of the BSCF membranes was studied in an atmosphere with steam, in which the permeation achieved decreased in the presence of steam. The use of these membranes in the ATR reaction would require correct scaling, since the flow of oxygen provided by the membrane would be low compared to the oxygen needs of the ATR reaction. Next, the effects of the application of porous protective layers on the BSCF capillaries were tested, to improve their chemical stability in rection environments. By means of the dip-coating technique, porous layers of BSCF, CTO-CMO and CTO were applied. The application of these layers increased the permeation due to the improvement in the surface area of exchange and of the surface reactions, reaching 3 - 3.6 NmL · min-1 · cm-2 for the coated membranes, compared to 2.4 NmL · min-1 · cm-2 for the uncoated membrane. These same membranes were tested in a membrane reactor, in reaction with CH4. The layers supported catalytic and protective effects with respect to the membrane without surface treatment. The CTO and CTO-CMO layers increased oxygen permeation and CH4 conversion, which reached values of 100%, and were also stable under the reaction conditions, while the membranes with BSCF layer and without coating had conversions. lower and its structure was degraded by the atmosphere of the reaction. Finally, the design and construction of a high pressure reaction system was carried out for the study of high pressure hydrogen production processes at pressures up to 300 barg. In this unit, hydrogen production reactions can be carried out from biomass in supercritical water. Additionally, a membrane reactor was designed that will allow work with gas permeation membranes under conditions of high severity, with potential application in the production of hydrogen from reforming reactions with high efficiency. / Represa Bullido, Á. (2022). Desarrollo de sistemas catalíticos e intensificación de procesos para la producción de hidrógeno comprimido y productos de interés [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/183153

Orientador: José Luz Silveira / Resumo: A inserção de fontes alternativas e confiáveis de energia na sociedade brasileira vem ganhando destaque e crescente importância, contudo, ainda é um grande desafio, visto que a sociedade ainda é majoritariamente dependente de combustíveis fósseis. Os impactos ambientais causados por eles são prejudiciais à vida humana e ao meio ambiente, além de confirmar a urgência da aplicação de tais tecnologias em diferentes cenários da sociedade. O hidrogênio, como vetor energético, vem ganhando destaque e aplicações dentro dos mais variados setores da sociedade, principalmente no setor de transporte como combustível. Dado ao exposto, esse trabalho tem como objetivo analisar a produção de hidrogênio renovável para uso como combustível veicular. A metodologia para a análise técnica consistiu em obter o consumo de energia elétrica para produção do hidrogênio, para assim com base nos recursos solares, eólicos e de biogás de São Paulo (SP), realizar o balanço energético e desta forma dimensionar o sistema híbrido. Baseado nos resultados técnicos, a metodologia econômica permitiu analisar a viabilidade financeira de implementar o sistema híbrido dimensionado permitindo determinar o nível de investimento, o custo da energia elétrica gerada, o custo do hidrogênio gerado e o período de retorno do investimento. A análise ambiental fundamentou-se em determinar a eficiência ecológica considerando os sistemas geradores de eletricidade para o processo de eletrólise da água. Os resultados obtidos most... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The insertion of alternative and reliable sources of energy in Brazilian society has been gaining prominence and growing importance, however, it is still a great challenge, since society is still mostly dependent on fossil fuels. The environmental impacts caused by them are harmful to human life and the environment, in addition to confirming the urgency of the application of such technologies in different scenarios of society. Hydrogen, as an energy vector, has been gaining prominence and applications within the most varied sectors of society, mainly in the transport sector as a fuel. Given the above, this work aims to analyze the production of renewable hydrogen for use as a vehicle fuel. The methodology for the technical analysis consisted of obtaining the consumption of electric energy for the production of hydrogen, so that, based on the solar, wind and biogas resources of São Paulo (SP), carry out the energy balance and thus dimension the hybrid system. Based on the technical results, the economic methodology made it possible to analyze the financial feasibility of implementing the scaled hybrid system allowing to determine the level of investment, the cost of the electricity generated, the cost of the hydrogen generated and the period of return on investment. The environmental analysis was based on determining the ecological efficiency considering the electricity generating systems for the water electrolysis process. The results obtained show that the proposed hybrid sy... (Complete abstract click electronic access below) / Mestre