Ekain Fernandez

Fluidized Bed Membrane Reactors for Ultra Pure H2 Production—A Step forward towards Commercialization

In this research the performance of a fluidized bed membrane reactor for high temperature water gas shift and its long term stability was investigated to provide a proof-of-concept of the new system at lab scale. A demonstration unit with a capacity of 1 Nm3/h of ultra-pure H2 was designed, built and operated over 900 h of continuous work. Firstly, the performance of the membranes were investigated at different inlet gas compositions and at different temperatures and H2 partial pressure differences. The membranes showed very high H2 fluxes (3.89 × 10−6 mol·m−2·Pa−1·s−1 at 400 °C and 1 atm pressure difference) with a H2/N2 ideal perm-selectivity (up to 21,000 when integrating five membranes in the module) beyond the DOE 2015 targets. Monitoring the performance of the membranes and the reactor confirmed a very stable performance of the unit for continuous high temperature water gas shift under bubbling fluidization conditions. Several experiments were carried out at different temperatures, pressures and various inlet compositions to determine the optimum operating window for the reactor. The obtained results showed high hydrogen recovery factors, and very low CO concentrations at the permeate side (in average <10 ppm), so that the produced hydrogen can be directly fed to a low temperature PEM fuel cell.

Morphology and N2 Permeance of Sputtered Pd-Ag Ultra-Thin Film Membranes

The influence of the temperature during the growth of Pd-Ag films by PVD magnetron sputtering onto polished silicon wafers was studied in order to avoid the effect of the support roughness on the layer growth. The surfaces of the Pd-Ag membrane films were analyzed by atomic force microscopy (AFM), and the results indicate an increase of the grain size from 120 to 250–270 nm and film surface roughness from 4–5 to 10–12 nm when increasing the temperature from around 360–510 K. After selecting the conditions for obtaining the smallest grain size onto silicon wafer, thin Pd-Ag (0.5–2 µm thick) films were deposited onto different types of porous supports to study the influence of the porous support, layer thickness and target power on the selective layer microstructure and membrane properties. The Pd-Ag layers deposited onto ZrO2 3-nm top layer supports (smallest pore size among all tested) present high N2 permeance in the order of 10−6 mol·m−2·s−1·Pa−1 at room temperature.

Metallic porous supports and ceramic interface layer development for H2 separation membranes

Abstract Hydrogen separation membranes are typically composed of three components: the porous support (ceramic or metallic, as studied in the present work), the porous ceramic interface layer and the hydrogen selective dense layer (usually Pd or a Pd based alloy). The development of a good support and an appropriate ceramic interface layer is a key issue in the high performance membrane manufacturing process. Metallic supports specifically developed for this application have yet to be developed; those used have different features and are manufactured for applications such as filtering devices. There is a clear need to develop porous supports for hydrogen separation membranes that have good surface quality (roughness and pore size) to allow the deposition of a thin selective layer (typically of Pd). In addition, the development of the ceramic layer is of importance, to allow the deposition of a Pd continuous layer of minimum thickness to increase hydrogen permeation and decrease manufacturing costs by minimising use of expensive Pd. The development and characterisation of a thin Pd–Ag membrane deposited by PVD on a composite metallic–ceramic porous support is reported. The surface properties of AISI 316L and nickel supports were improved and the interdiffusion of Pd and Ag was avoided by deposition of an yttria stabilised zirconia (YSZ) layer by dip coating of nanosized YSZ powders.