• Energy Research

Membrane reactor processes are being increasingly proposed as an attractive solution for pure hydrogen production due to the possibility to integrate production and separation inside a single reactor vessel. High hydrogen purity can be obtained through dense metallic membranes, especially palladium and its alloys, which are highly selective to hydrogen. The use of thin membranes seems to be a good industrial solution in order to increase the hydrogen flux while reducing the cost of materials. Typically, the diffusion through the membrane layer is the rate-limiting step and the hydrogen permeation through the membrane can be described by the Sieverts’ law but, when the membrane becomes thinner, the diffusion through the membrane bulk becomes less determinant and other mass transfer limitations might limit the permeation rate. Another way to increase the hydrogen flux at a given feed pressure, is to increase the driving force of the process by feeding a sweep gas in the permeate side. This effect can however be significantly reduced if mass transfer limitations in the permeate side exist. The aim of this work is to study the mass transfer limitation that occurs in the permeate side in presence of sweep gas. A complete model for the hydrogen permeation through Pd–Ag membranes has been developed, adding the effects of concentration polarization in retentate and permeate side and the presence of the porous support using the dusty gas model equation, which combines Knudsen diffusion, viscous flow and binary diffusion. By studying the influence of the sweep gas it has been observed that the reduction of the driving force is due to the stagnant sweep gas in the support pores while the concentration polarization in the permeate is negligible.

Poultry slaughterhouse wastewater (PSW) contains high organic matter and nutrients requiring thus a special treatment before its final disposal. In this work, acid precipitation (H2SO4) followed by microalgae "Chlorella vulgaris" cultivation both in batch and continuous processes was studied as an alternative method for PSW treatment. By reducing the pH value of PSW from 6 to 7 to 4, about 80% of the total chemical oxygen demand (CODT) was removed as sludge. In the supernatant, the COD residual was efficiently removed (83%) by microalgae in the batch process, using an internal-loop concentric tube photobioreactor (4.5 L). Moreover, in continuous process, after 89 h, the COD value resulted lower than 200 mg L-1 and 1.2 g L-1 of microalgae in the output line. The proposed PSW treatment method is promising from economic and environmental viewpoints, since the microalgal biomass can be valued in a biorefinery context.

In this paper, we report the performance of supported Pd–Ru membranes for possible applications to hydrogen purification and/or production. For this purpose, we fabricated three ultra-thin α-alumina-supported membranes by combined plating techniques: a Pd–Ag membrane (3 μm-thick ca.) and two Pd–Ru (1.8 μm-thick ca.). The former is set as a benchmark for comparison. The membranes were characterised using different methodologies: permeation tests, thermal treatment and SEM analysis. Preliminary leakage tests performed with nitrogen has revealed that the two Pd–Ru membranes, namely PdRu#1 and PdRu#2, show a non-ideal (non-infinite) selectivity, which is relatively low for the former (around 830 at 400 °C) and sufficiently high for the latter (2645 at 400 °C). This indicates a relevant presence of defects in the PdRu#2 membrane, differently from what observed for the Pd–Ag and PdRu#1 ones. The permeation tests show that the hydrogen permeating flux is stable up to around 550 °C, with an apparently unusual behaviour at higher temperatures (600 °C), where we observe a slightly decrease of hydrogen flux with an increase of the nitrogen one. Moreover, a peculiar bubble-shaped structure is observed in the metal layer of all membranes after usage by means of SEM image analysis. This is explained by considering the effect of the Pd-alloy grain surface energy, which tends to minimise the exposed surface area of the grain interface by creating sphere-like bubble in the lattice, similar to what occurs for soap bubbles in water. The above-mentioned decrease in hydrogen flux at 600 °C is explained to be caused by the bubble formation, which pushes the alloy deeper in the support pores.

In this paper, the main achievements of several European research projects on Pd based membranes and Pd membrane reactors for hydrogen production are reported. Pd-based membranes have received an increasing interest for separation and purification of hydrogen. In addition, the integration of such membranes in membrane reactors has been widely studied for enhancing the efficiency of several dehydrogenation reactions. The integration of reaction and separation in one multifunctional reactor allows obtaining higher conversion degrees, smaller reactor volumes and higher efficiencies compared with conventional systems. In the last decade, much thinner dense Pd-based membranes have been produced that can be used in membrane reactors. However, the thinner the membranes the higher the flux and the higher the effect of concentration polarization in packed bed membrane reactors. A reactor concept that can circumvent (or at least strongly reduce) concentration polarization is the fluidized bed membrane reactor configuration, which improves the heat transfer as well. Tecnalia and TU/e are involved in several European projects that are related to development of fluidized bed membrane reactors for hydrogen production using thin Pd-based (<5 μm) supported membranes for different application: In DEMCAMER project a water gas shift (WGS) membrane reactor was developed for high purity hydrogen production. ReforCELL aims at developing a high efficient heat and power micro-cogeneration system (m-CHP) using a methane reforming fluidized membrane reactor. The main objective of FERRET is the development of a flexible natural gas membrane reformer directly linked to the fuel processor of the micro-CHP system. FluidCELL aims the Proof-of-Concept of a m-CHP system for decentralized off-grid using a bioethanol reforming membrane reactor. BIONICO aims at applying membrane reactors for biogas conversion to hydrogen. The fluidized bed system allows operating at a virtually uniform temperature which is beneficial in terms of both membrane stability and durability and for the reaction selectivity and yield.

In 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.

Abstract Stand-alone graphene-based films were prepared from graphene oxide (GO) nanoplatelets and their use as counter-electrodes (CEs) in dye-sensitized solar cells (DSCs) was investigated. The graphene-based CEs were produced by spray deposition of GO and chemically reduced GO, followed by thermal annealing under an inert atmosphere. These GO-based CEs were shown to have similar transparency as a reference CE made of Pt. Consistent with impedance data from symmetrical half-cells, DSCs assembled with such GO-based CEs exhibited relative efficiencies of ca. 75% comparatively to the reference Pt CE. The possibility of obtaining transparent (transmittance higher than 80%) and reasonable catalytic films for DSCs (energy conversion efficiency of 2.64%) from GO nanoplatelets was demonstrated. The need for reduction of the graphene oxide nanoplatelets prior to deposition was not observed, allowing for a simplified CE manufacturing process. However, further work is still needed to equal or surpass the performance of Pt CEs.

Distributed power generation via Micro Combined Heat and Power (m-CHP) systems, has been proven to over-come disadvantages of centralized generation since it can give savings in terms of Primary Energy consumption and energy costs. The FluidCELL FCH JU/FP7 project aims at providing the Proof of Concept of an advanced high performance, cost effective bio-ethanol m-CHP cogeneration Fuel Cell system for decentralized off-grid applications by end of 2017. The main idea of FluidCELL is to develop a new bio-ethanol membrane reformer for pure hydrogen production (3.2 Nm3/h) based on Membrane Reactors in order to intensify the process of hydrogen production through the integration of reforming and purification in one single unit. The novel reactor could be more efficient than the state-of-the-art technology due to an optimal design aimed at circumventing mass and heat transfer resistances. Moreover, the design and optimization of the subcomponents for the BoP could also be improved. Particular attention has to be devoted to the optimized thermal integration that can improve the overall efficiency of the system at >90% and reducing the cost due to low temperature reforming. The main results obtained until now in terms of performance of the catalysts, membranes and the membrane reactors will be presented in this work.