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•Carbon molecular sieve membranes were developed for ethanol dehydration.•alumina supports result in 48% thicker membranes than zirconia supports.•Higher performance compared with ...other membranes are reported.•Membranes are stable over a long period of time in permeation mode.
Tubular supported carbon molecular sieve membranes (CMSMs) with high hydrophilicity and perm-selectivities for water suitable for ethanol dehydration were developed from a Novolac oligomer phenolic resin as precursor. Alpha alumina supported CMSMs resulted in 1.69 times higher surface roughness than zirconia supports. The higher surface roughness resulted in 48% higher selective layer thickness. According to pervaporation results, water permeance decreased by the increase in selective layer thickness and mole based selectivity of water- ethanol was enhanced. The oligomer with 3982 g/mol molecular weight enabled membrane to reach high selectivity with one-layer coating. Performance of the membranes are compared with literature data in terms of mole-based selectivity vs. water permeance. CMSMs could be a potential substitution for traditional ethanol dehydration methods with offering higher performance and as a result reducing the final price of bioethanol to be used as a sustainable energy source.
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.
•Scale-up of thin Pd-based membrane manufacturing.•Long-term stability of thin Pd-based supported membranes.•Performance of fluidized bed membrane reactors including thin Pd-based supported membranes.
Textile wastewater is widely produced and its discharge without treatment contributes to environmental pollution. The adsorption process is a suitable and eco-friendly process due to its low initial ...cost, no formation of degradation products, operation simplicity, insensitivity to toxic compounds, and the possibility of removal from greatly diluted solutions. Orange seed (OS) powder, from which lipids were removed by hexane extraction, was evaluated as a bio-adsorbent to remove dyes from real textile wastewater. In the screening step, pH was a more significant variable (p-value < 0.05) than bio-adsorbent dosage, temperature, stirring speed, and process time. Moreover, under optimized conditions (pH = 2.6, 0.58 g/L from OS powder and 26 °C), more than 95% of the dye was removed from real textile wastewater. Additionally, the dye removal percentage was reduced by only 4% when the volume of textile wastewater was increased from 0.05 L to 10 L. Then, 96% turbidity was removed using a 3 µm tubular ceramic membrane at a pH of 11. Furthermore, the permeate flux through the membrane was kept constant for longer than was observed at low pH (<11). Therefore, the proposed process is an interesting option, due to the fact that orange seeds are currently not valorized and, combined with the membrane process, this could prove a suitable option for the treatment of real textile wastewater.
In hydrogen production, the syngas streams produced by reformers and/or coal gasification plants contain a large amount of H2 and CO in need of upgrading. To this purpose, reactors using Pd-based ...membranes have been widely studied as they allow separation and recovery of a pure hydrogen stream. However, the high cost of Pd-membranes is one of the main limitations for scaling up technology. Therefore, many researchers are now pursuing the possibility of using supported membranes with as thin as possible Pd-alloy layers.
In this work, the upgrading of a syngas stream is experimentally investigated in a water gas shift membrane reactor operated in a high temperature range with an ultra-thin supported membrane (3.6 micron-thick). The membrane permeance was measured before and after catalyst packing and also after reaction for 2100 h of operation in total.
Membrane reactor performance was evaluated as a function of operating conditions such as temperature, pressure, gas hourly space velocity, feed molar ratio, and sweep gas. A CO conversion significantly higher than the thermodynamics upper limit of a traditional reactor was achieved, even at high gas hourly space velocities and a 25% less reaction volume than that of a traditional reactor was enough to achieve a 90% equilibrium conversion.
•Upgrading of a syngas stream in a membrane reactor with thin Pd–Ag membrane (3.6 micron).•Analysis of membrane permeance after reaction (in a total 2100 h of operation).•CO conversion significantly higher than traditional reactor equilibrium conversion.•Significant reduction of the MR reaction volume with respect to traditional reactor.
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Red-G dye is one of the main dyes used in the textile industry to dye alpaca wool. Therefore, considering the large volume of processed wool in Perú, the development of efficient ...technologies for its removal is a present scientific issue. In this study, an integrated system based on hydrodynamic cavitation (HC) and photo-Fenton process was evaluated to remove the Red-G dye. Using a hybrid cavitation device (venturi + orifice plate), the effect of pH was evaluated, achieving 21 % of removal at pH 2 which was more than 80 % higher compared to pH 4 and 6. The effect of temperature was also evaluated in HC-system at pH 2, where percentage of dye degradation increased at lower temperatures (around 20 °C). Then, 50.7 % of dye was removed under optimized condition of HC-assisted Fenton process (FeSO4:H2O2 of 1:30), that value was improved strongly by UV-light incorporation in the HC-system, increasing to 99 % removal efficiency with respect to HC-assisted Fenton process and reducing the time to 15 min. Finally, the developed cavitation device in combination with photo-Fenton process removed efficiently the dye and thus could be considered an interesting option for application to real wastewater.
•Metallic supported Pd–Ag membranes (5μm thick) with ceramic barrier layer.•2 deposition techniques for ceramic layers: APS and powder suspension deposition.•Optimized membranes showed very high ...H2/N2 ideal selectivity (>200,000).
This paper reports the preparation and characterization of thin-film (4–5μm thick) Pd–Ag metallic supported membranes for high temperature applications. Various thin film membranes have been prepared by depositing a ceramic interdiffusion barrier layer prior to the simultaneous Pd–Ag electroless plating deposition. Two deposition techniques for ceramic layers (made of zirconia and alumina) have been evaluated: Atmospheric Plasma Spraying and dip coating of a powder suspension. Initially, the prepared ceramic layers have been characterized for nitrogen permeation at room temperature and surface roughness for the selection of the appropriate type of ceramic layer. The most promising membranes have been tested at 400–600°C for single gas permeation (H2 and N2), and have shown extremely high H2/N2 permselectivities (>200,000).
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•A new reactor concept has been experimentally demonstrated at lab-scale.•A phenomenological model has been developed and validated with experimental data.•Methane conversions above ...90% at intermediate temperatures.•Hydrogen recoveries above 30% at low pressure operation.
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.
This work reports the integration of thin (∼3–4 μm thick) Pd-based membranes for H2 separation in a fluidized bed catalytic reactor for ethanol auto-thermal reforming. The performance of a fluidized ...bed membrane reactor has been investigated from an experimental and numerical point of view. The demonstration of the technology has been carried out over 50 h under reactive conditions using 5 thin Pd-based alumina-supported membranes and a 3 wt%Pt-10 wt%Ni catalyst deposited on a mixed CeO2/SiO2 support. The results have confirmed the feasibility of the concept, in particular the capacity to reach a hydrogen recovery factor up to 70%, while the operation at different fluidization regimes, oxygen-to-ethanol and steam-to-ethanol ratios, feed pressures and reactor temperatures have been studied. The most critical part of the system is the sealing of the membranes, where most of the gas leakage was detected. A fluidized bed membrane reactor model for ethanol reforming has been developed and validated with the obtained experimental results. The model has been subsequently used to design a small reactor unit for domestic use, showing that 0.45 m2 membrane area is needed to produce the amount of H2 required for a 5 kWe PEM fuel-cell based micro-CHP system.
•Ethanol membrane reactor demonstrated for more than 50 h operation.•100% ethanol conversion achieved using Pt/Ni-based catalyst.•Overall HRF of 67% achieved in auto-thermal operation.•Validation of a membrane fluidized bed reactor model successfully achieved.
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•Carbon membranes have been investigated experimentally for biogas upgrading.•The performance of carbon membranes exceeds the Robeson limit of polymeric membranes.•The economics of ...biogas upgrading with carbon membranes have been evaluated.•Carbon membranes can be installed in existing reforming plants for H2 production.•95% of carbon emissions can be avoided by using biogas for H2 production.
The 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.
This paper reports the preparation, characterization and stability tests of thin-film Pd–Ag supported membranes for high-temperature fluidized bed membrane reactor applications. Various thin-film ...supported membranes have been prepared by simultaneous Pd–Ag electroless plating and have been initially sealed with a sealing procedure previously validated for Water gas shift (WGS) application (400 °C). The membranes have been characterized for single gas and mixed gas permeation, and for methane steam and autothermal reforming in a fluidized bed membrane reactor at 550–600 °C using a Ru-based catalyst. In addition, the performance of these membranes was compared to commercial membranes from REB Research & Consulting under the same reaction conditions. The applied sealing showed nitrogen leaks at 600 °C and different sealing approaches were tested solving this problem. Finally, also the long-term stability of the thin-film Pd–Ag supported membrane at 600 °C has been investigated.
•Thin Pd-based membranes for high temperature applications are prepared and tested.•The membranes are stable in fluidized bed reactor for SMR and ATR.•The membrane flux is higher than literature membranes for the same temperatures.•Hydrogen recovery of 30% is achieved with high purity.
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