In this study, a micro-structured catalytic hollow fiber membrane reactor (CHFMR) has been prepared, characterized and evaluated for performing steam methane reforming (SMR) reaction, using Rh/CeO2 as the catalyst and a palladium membrane for separating hydrogen from the reaction. Preliminary studies on a catalytic hollow fiber (CHF), a porous membrane reactor configuration without the palladium membrane, revealed that stable methane conversions reaching equilibrium values can be achieved, using approximately 36 mg of 2 wt.%Rh/CeO2 catalyst incorporated inside the micro-channels of alumina hollow fibre substrates (around 7 cm long in the reaction zone). This proves the advantages of efficiently utilizing catalysts in such a way, such as significantly reduced external mass transfer resistance when compared with conventional packed bed reactors. It is interesting to observe catalyst deactivation in CHF when the quantity of catalyst incorporated is less than 36 mg, although the Rh/CeO2 catalyst supposes to be quite resistant against carbon formation. The "shift" phenomenon expected in CHFMR was not observed by using 100 mg of 2 wt.%Rh/CeO2 catalyst, mainly due to the less desired catalyst packing at the presence of the dense Pd separating layer. Problems of this type were solved by using 100 mg of 4 wt.% Rh/CeO2 as the catalyst in CHFMR, resulting in methane conversion surpassing the equilibrium conversions and no detectable deactivation of the catalyst. As a result, the improved methodology of incorporating catalyst into the micro-channels of CHFMR is the key to a more efficient membrane reactor design of this type, for both the SMR in this study and the other catalytic reforming reactions.
Dual-phase molten salt-ceramic membranes show high permselectivity for CO2 when molten carbonate is supported in a porous oxygen-ion and/or electron conductor. In this arrangement, the support likely contributes to permeation. Thus, if one is to understand and ultimately design membranes, it is also important to perform experiments with an inert support where permeation relies upon the molten carbonate properties alone. Here, a nominally inert material (Al2O3) was used in order to restrict permeation to molten carbonate. Model Al2O3 dual-phase membranes were fabricated using laser drilling to provide an order of magnitude difference in molten salt-gas interfacial area between feed and permeate sides. Molten carbonate thickness in the model membranes was also varied, independent of the molten salt-gas interfacial area. For all thicknesses studied, CO2 permeation rates showed a significant temperature dependence from 500 to 750 °C, suggesting an activated process was rate-limiting, likely a permeate-side molten salt-gas interfacial process, i.e. desorption of CO2. We applied these findings in asymmetric hollow-fibre supports, a geometry with inherent modularity and scalability, by developing a new carbonate infiltration method to control molten carbonate distribution within the hollow fibre. Compared to a conventionally prepared dual-phase hollow-fibre membrane with an uncontrolled distribution of carbonates, permeation rates were increased by up to 4 times when the molten salt was confined to the packed-pore network, i.e. without infiltrating the hollow-fibre micro-channels. X-ray micro-CT investigations supported the idea that the resulting increase in interfacial area for desorption of CO2 was the key structural difference contributing to increased permeation rates. For CO2 separation, where large volumes of gas must be processed, such increases in permeation rates will reduce the demand for membrane materials, although one must note the higher permeation rates achievable with oxygen-ion and/or electron conducting supports.
Application of composite Pd based membranes represents a promising alternative for hydrogen purification. Here we propose the application of asymmetric alumina hollow fibres as a support for Pd deposition. Hollow fibres were sintered at different temperatures (1300 and 1400 o C). Characterisations of the substrate showed that it presents the desired morphological structure, with finger-voids extending to almost 90% of the fibre, high porosity and suitable mechanical strength. Hydrogen permeations through the composite membrane formed by the deposition of one palladium (Pd) layer on the alumina hollow fibre sintered at 1300 o C was on average 100% greater than using the hollow fibre sintered at 1400 o C. For 2 Pd layers, this difference decreased to 22%, showing that the substrate influence is more evident in thinner Pd membranes. The obtained H2 flux was equal to 0.80 μmol m -2 s -1 (at 450 o C and 180 kPa) and it is one of highest flux reported in the literature.
Microstructured alumina hollow fibers, which contain a plurality of radial microchannels with significant openings on the inner surface, have been fabricated in this study and used to develop an efficient catalytic hollow fiber reactor. Apart from low mass-transfer resistance, a unique structure of this type facilitates the incorporation of Ni-based catalysts, which can be with or without the aged secondary support, SBA-15. In contrast to a fixed bed reactor, the catalytic hollow fiber reactor shows similar methane conversion, with a gas hourly space velocity that is approximately 6.5 times higher, a significantly greater CO2 selectivity, and better productivity rates. These results demonstrate the advantages of dispersing the catalyst inside the microstructured hollow fiber as well as the potential to reduce the required quantity of catalyst.
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