Browsing by Author "Medrano, J.A."
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Item The membrane-assisted chemical looping reforming concept for efficient H2 production with inherent CO2 capture: Experimental demonstration and model validation: Experimental demonstration and model validation(2018-04-01) Medrano, J.A.; Potdar, I.; Melendez, J.; Spallina, V.; Pacheco Tanaka, David A.; van Sint Annaland, M.; Gallucci, F.; Tecnalia Research & Innovation; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOSIn this work a novel reactor concept referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR) has been demonstrated at lab scale under different operating conditions for a total working time of about 100 h. This reactor combines the advantages of Chemical Looping, such as CO2 capture and good thermal integration, with membrane technology for a better process integration and direct product separation in a single unit, which in its turn leads to increased efficiencies and important benefits compared to conventional technologies for H2 production. The effect of different operating conditions (i.e. temperature, steam-to-carbon ratio or oxygen feed in the reactor) has been evaluated in a continuous chemical looping reactor, and methane conversions above 90% have been measured with (ultra-pure) hydrogen recovery from the membranes. For all the cases a maximum recovery factor of around 30% has been measured, which could be increased by operating the concept at higher pressures and with more membranes. The optimum conditions have been found at temperatures around 600 °C for a steam-to-carbon ratio of 3 and diluted air in the air reactor (5% O2). The complete demonstration has been carried out feeding up to 1 L/min of CH4 (corresponding to 0.6 kW of thermal input) while up to 1.15 L/min of H2 was recovered. Simultaneously, a phenomenological model has been developed and validated with the experimental results. In general, good agreement is observed, with overall deviations below 10% in terms of methane conversion, H2 recovery and separation factor. The model allows better understanding of the behavior of the MA-CLR concept and the optimization and design of scaled-up versions of the concept.Item Pd-based membranes performance under hydrocarbon exposure for propane dehydrogenation processes: Experimental and modeling: Experimental and modeling(2022-03-08) Brencio, C.; Fontein, F.W.A.; Medrano, J.A.; Di Felice, L.; Arratibel, A.; Gallucci, F.; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOSIn this work, a novel Pd–Ag double-skinned (DS-) membrane is used for the first time in conditions typical of propane dehydrogenation (PDH). This membrane presents a protective layer on top of the H2-selective one, which acts as shield against chemical deactivation and mechanical erosion under reaction conditions. While the protective layer is already been proven as an efficient barrier against membrane erosion in fluidized beds, there is no validation yet under PDH reaction. The DS- membrane performance is compared with a conventional (C-) Pd–Ag membrane under alkane/alkene exposure, at 400–500 °C and 3 bar, to investigate whether the incorporation of the protective layer would be suited for H2 separation in PDH systems, and if coking rate would be affected. The novel membrane shows a H2 permeance of 2.28 × 10−6 mol∙m−2 s−1∙Pa−1 at 500 ᵒC and 4 bar of pressure difference, overcoming the performance of the conventional PdAg one (1.56x∙10−6 mol m−2 s−1∙Pa−1). Both membranes present a stable H2 flux under alkane exposure, while deactivation occurs under exposure to alkenes. A model able to describe the H2 flux through Pd-based membranes is presented to fit the experimental data and predict membrane performance. The model includes mass transfer limitations in the retentate and a corrective inhibition factor to account for the competitive adsorption of hydrocarbon species in the H2 selective layer. The experimental results obtained under alkene exposure deviates from model predictions; this can be attributed to carbon deposition on the surface of the selective layer, as further detected on the DS-membrane by Scanning Electron Microscopy (SEM)/Energy Dispersive X-Ray Analysis (EDX), which is the main factor for membrane deactivation.Item Upgrading biogas with novel composite carbon molecular sieve (CCMS) membranes: Experimental and techno-economic assessment: Experimental and techno-economic assessment(2020-08-15) Medrano, J.A.; Llosa-Tanco, M.A.; Cechetto, V.; Pacheco-Tanaka, D.A.; Gallucci, F.; TECNOLOGÍA DE MEMBRANAS E INTENSIFICACIÓN DE PROCESOSThe use of biogas as feedstock for hydrogen production was widely proposed in the literature in the last years as a strategy to reduce anthropogenic carbon emissions. However, its lower heating value compared to natural gas hampers the revamping of existing reforming plants. The use of composite carbon molecular sieve membranes for biogas upgrading (CO2 removal from biogas) was investigated experimentally in this work. In particular, ideal perm-selectivities and permeabilities above the Robeson plot for CO2/CH4 mixtures have been obtained. These membranes show better performances compared to polymeric membranes, which are nowadays commercialized for CO2 separation in natural gas streams. Compared to polymeric membranes, carbon membranes do not show deactivation by plasticization when exposed to CO2, and thus can find industrial application. This work was extended with a techno-economic analysis where carbon membranes are installed in a steam methane reforming plant. Results have been first validated with data from literature and show that the use of biogas increases the costs of hydrogen production to a value of 0.25 €/Nm3 compared to the benchmark technology (0.21 €/Nm3). On the other hand, the use of biogas leads to a decrease in carbon emissions up to 95%, thus the use of biogas for hydrogen production is foreseen as a very interesting alternative to conventional technologies in view of the reduction in the carbon footprint in the novel technologies that are to be installed in the near future.