High temperature H2/CO2 separation using cobalt oxide silica membranes

In this work high quality cobalt oxide silica membranes were synthesized on alumina supports using a sol–gel, dip coating method. The membranes were subsequently connected into a steel module using a graphite based proprietary sealing method. The sealed membranes were tested for single gas permeance of He, H₂, N₂ and CO₂ at temperatures up to 600 °C and feed pressures up to 600 kPa. Pressure tests confirmed that the sealing system was effective as no gas leaks were observed during testing. A H₂ permeance of 1.9 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ was measured in conjunction with a H₂/CO₂ permselectivity of more than 1500, suggesting that the membranes had a very narrow pore size distribution and an average pore diameter of approximately 3 Å. The high temperature testing demonstrated that the incorporation of cobalt oxide into the silica matrix produced a structure with a higher thermal stability, able to resist thermally induced densification up to at least 600 °C. Furthermore, the membranes were tested for H₂/CO₂ binary feed mixtures between 400 and 600 °C. At these conditions, the reverse of the water gas shift reaction occurred, inadvertently generating CO and water which increased as a function of CO₂ feed concentration. The purity of H₂ in the permeate stream significantly decreased for CO₂ feed concentrations in excess of 50 vol%. However, the gas mixtures (H₂, CO₂, CO and water) had a more profound effect on the H₂ permeate flow rates which significantly decreased, almost exponentially as the CO₂ feed concentration increased.     

Gas sorption in H2-selective mixed matrix membranes: Experimental and neural network modeling

Robust artificial neural network (ANN) was developed to forecast sorption of gases in membranes comprised of porous nanoparticles dispersed homogenously within polymer matrix. The main purpose of this study was to predict sorption of light gases (H₂, CH₄, CO₂) within mixed matrix membranes (MMMs) as function of critical temperature, nanoparticles loading and upstream pressure. Collected data were distributed into three portions of training (70%), validation (19%), and testing (11%). The optimum network structure was determined by trial-error method (4:6:2:1) and was applied for modeling the gas sorption. The prediction results were remarkably agreed with the experimental data with MSE of 0.00005 and correlation coefficient of 0.9994.     

CO2-selective membranes for hydrogen purification and the effect of carbon monoxide (CO) on its gas separation performance

Industrial hydrogen production may prefer CO₂-selective membranes because high-pressure H₂ can therefore be produced without additional recompression. In this study, high performance CO₂-selective membranes are fabricated by modifying a polymer–silica hybrid matrix (PSHM) with a low molecular weight poly(ethylene glycol) dimethyl ether (PEGDME). The liquid state of PEGDME and its unique end groups eliminate the crystallization tendency of poly(ethylene glycol) (PEG). The methyl end groups in PEGDME hinder hydrogen bonding between the polymer chains and significantly enhance the gas diffusivity. In pure gas tests, the membrane containing 50 wt% additive shows CO₂ gas permeability and CO₂/H₂ selectivity of 1637 Barrers and 13 at 35 °C, respectively. In order to explore the effect of real industrial conditions, the gas separation performance of the newly developed membranes has been studied extensively using binary (CO₂/H₂) and ternary gas mixtures (CO₂/H₂/carbon monoxide (CO)). Compared to pure gas performance, the second component (H₂) in the binary mixed gas test reduces the CO₂ permeability. The presence of CO in the feed gas stream decreases both CO₂ and H₂ permeability as well as CO₂/H₂ selectivity as it reduces the concentration of CO₂ molecules in the polymer matrix. The mixed gas results affirm the promising applications of the newly developed membranes for H₂ purification.     

CNT/PDMS composite membranes for H2 and CH4 gas separation

Polydimethylsiloxane (PDMS) composites with different weight amounts of multi-walled carbon nanotubes (MWCNT) were synthesised as membranes to evaluate their gas separation properties. The selectivity of the membranes was investigated for the separation of H₂ from CH₄ gas species. Membranes with MWCNT concentrations of 1% increased the selectivity to H₂ gas by 94.8%. Furthermore, CH₄ permeation was almost totally blocked through membranes with MWCNT concentrations greater than 5%. Vibrational spectroscopy and X-ray photoelectron spectroscopy techniques revealed that upon the incorporation of MWCNT a decrease in the number of available Si–CH₃ and Si–O bonds as well as an increase in the formation of Si–C bonds occurred that initiated the reduction in CH₄ permeation. As a result, the developed membranes can be an efficient and low cost solution for separating H₂ from larger gas molecules such as CH₄.     

Hydrogen permeation through a Pd-based membrane and RWGS conversion in H2/CO2, H2/N2/CO2 and H2/H2O/CO2 mixtures

This study investigated the effect of gases such as CO₂, N₂, H₂O on hydrogen permeation through a Pd-based membrane −0.012 m² – in a bench-scale reactor. Different mixtures were chosen of H₂/CO₂, H₂/N₂/CO₂ and H₂/H₂O/CO₂ at temperatures of 593–723 K and a hydrogen partial pressure of 150 kPa. Operating conditions were determined to minimize H₂ loss due to the reverse water gas shift (RWGS) reaction. It was found that the feed flow rate had an important effect on hydrogen recovery (HR). Furthermore, an identification of the inhibition factors to permeability was determined. Additionally, under the selected conditions, the maximum hydrogen permeation was determined in pure H₂ and the H₂/CO₂ mixtures. The best operating conditions to separate hydrogen from the mixtures were identified.     

Macrovoid-free high performance polybenzimidazole hollow fiber membranes for elevated temperature H2/CO2 separations

Thermally robust membranes are required for H₂ production and carbon capture from hydrocarbon fuel derived synthesis (syn) gas. Polybenzimidaole (PBI) materials have exceptional thermal, chemical and mechanical characteristics and high H₂ perm-selectivity for efficient syngas separations at process relevant conditions. The large gas volumes processed mandate the use of a high-throughput, small footprint hollow fiber membrane (HFM) platform. In this work, an industrially attractive spinning protocol is developed to fabricate PBI HFMs with unprecedented H₂/CO₂ separation performance. A unique dope composition incorporating an acetonitrile diluent is discovered enabling asymmetric macro-void free PBI HFM fabrication using a water coagulant. The influences of dope viscosity, coagulant chemistry, and air gap on HFM morphology are evaluated. Elevated temperature (up to 350 °C) H₂ permeances of 400 GPU with H₂/CO₂ selectivities > 20 are achieved. This unprecedented separation performance is a ground breaking achievement at temperatures traditionally considered out-of-reach for polymeric membranes.     

Effect of UV irradiation on PC membrane and use of Pd nanoparticles with/without PVP for H2 selectivity enhancement over CO2 and N2 gases

The hydrogen-based economy is one of the possible approaches toward to eliminate the problem of global warming, which are increases because of the gathering of greenhouse gases. Palladium (Pd) is well-known material having a strong affinity to the hydrogen absorbing property and thus appropriate material to embed in the membrane for the improvement of selective permeation of hydrogen gas. In present work, we have functionalized polycarbonate (PC) membranes with the help of UV irradiation to embed the Pd nanoparticles in pores as well as on the surface of the PC membrane. Use of Pd Nanoparticles is helpful to enhance the H₂ selectivity over other gases (CO₂, N_2, etc.). Also, the UV based modification of membrane increases the attachment of Pd Nanoparticles. Further to enhance the Pd nanoparticles attachment, we used PVP binder with Pd nanoparticles solution. Gas permeability measurements of functionalized PC membranes have been carried out, and better selectivity of hydrogen has been found in the functionalized and Pd nanoparticle binded membrane. PC membrane with 48 h UV irradiated and Pd NPs with PVP have been found to have maximum selectivity and permeability for H₂ gas. All the samples being characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy and UV–Vis spectroscopy for their morphological and structural investigation.     

Development of CMS/Al2O3-supported PPO composite membrane for hydrogen separation

A novel composite membrane consisting of a poly(phenylene oxide) (PPO) selective layer and a CMS/Al₂O₃ substrate was fabricated by a spin-coating method. This new class of PPO/CMS/Al₂O₃ multilayer composite membranes showed an H₂ permeability of 134 Barrer, two times greater than that for the corresponding self-supported PPO polymeric membrane. High selectivities for H₂/CH₄ and H₂/N₂ of 31.8 and 37.1, respectively, were also obtained with this composite membrane. According to field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) observations, using the CMS/Al₂O₃ material as the substrate provided a smooth surface for the support of the PPO selective layer and increased the roughness from the top to bottom surfaces. The effects of the substrate materials on the permselectivity of the resulting membrane were also investigated.     

Characterizations of polybenzimidazole based electrochemical hydrogen pumps with various Pt loadings for H2/CO2 gas separation

Carbon capture and storage (CCS) technologies have been intensively researched and developed to cope with climate change, by reducing atmospheric CO₂ concentration. The electrochemical hydrogen pumps with phosphoric acid doped polybenzimidazole (PBI) membrane are evaluated as a process to concentrate CO₂ and produce pure H₂ from anode outlet gases (H₂/CO₂ mixture) of molten carbonate fuel cells (MCFC). The PBI-based hydrogen pump without humidification (160 °C) can provide higher hydrogen separation performances than the cells with perfluorosulfonic-acid membranes at a relative humidity of 43% (80 °C), suggesting that the pre-treatment steps can be decreased for PBI-based systems. With the H₂/CO₂ mixture feed, the current efficiency for the hydrogen separation is very high, but the cell voltage increase, compared to the pure hydrogen operation, mainly due to the larger polarization resistance at electrodes, as confirmed by electrochemical impedance spectroscopy (EIS). The performance evaluation with various Pt loadings indicates that the hydrogen oxidation reaction at anodes is rate determining, and therefore the Pt loading at cathodes can be decreased from 1.1 mg/cm² to 0.2 mg/cm² without significant performance decay. The EIS analysis also confirms that the polarization resistances are largely dependent on the Pt loading in anodes.     

Polyurethane-based membranes for CO2 separation: A comprehensive review

The membrane process has been considered a promising technology for effective CO₂ capture due to its outstanding features, including a small environmental footprint, reduced energy consumption, simplicity of operation, compact design, ease of scalability and maintenance, and low capital cost. Among the developed polymeric materials for membrane fabrication, polyurethane (PU) and poly(urethane-urea) (PUU) as multi-block copolymers have exhibited great potential for CO₂ capture because of their excellent mechanical properties, high thermal stability, good film formation ability, favorable permeation properties, and a large diversity of monomers (i.e., polyol, diisocyanate, and chain extender) for the synthesis of desired polymers with prescribed properties. However, PU- and PUU-based membranes' gas selectivity is relatively low and thus not attractive for practical gas separation (GS) applications. Therefore, the present review scrutinizes the main influential factors on the gas transport properties and GS performance of these membranes. In this regard, we summarize the recent progress in the PU-based membranes in view of (I) design and synthesis of new PUs, (II) blending with other polymeric matrices, (III) cross-linking PU membranes, and (IV) fabricating PU-based mixed-matrix membranes (MMMs) with deep insight into an increase in CO₂ permeability, as well as CO₂/other gases selectivity. Finally, the challenges and future direction of PU-based membranes will be presented.     

Influence of coating conditions on the H2 separation performance from H2/CH4 gas mixtures by the PDMS/PEI composite membrane

In the present study, the composite polyetherimide (PEI) membrane coated with poly dimethyl siloxane (PDMS) was synthesized and optimum conditions of coating were obtained for separation of hydrogen from methane. Three coating techniques “pouring solution inclined by 45°”, “film casting” and “dip-coating” were used. The effect of sequential coating for different methods on permselectivity of the membranes was investigated. In addition, the influences of coating conditions including coating solution concentration, coating and curing temperatures were examined. The results showed that when the concentration of PDMS coating solution was increased; the permeance of H₂ was initially declined rapidly and was then gradually leveled off. The optimum concentration of coating solution was 15 wt.%. The examination of the curing and coating temperatures showed no significant effect on H₂ permeance and selectivity. In the “dip coating” method, two times coating showed superior permeance and selectivity and in “film casting”, the performance of triple coating was promising. Higher selectivities for the composite membrane prepared by “dip-coating” introduced this method as the best method. The sequential dip-coating with different PDMS concentrations was applied and the selectivity was enhanced significantly from 26 to 96 for pure gases and from 22 to 70 for the binary gas mixture. Finally, the influence of pressure on the separation performance of the fabricated membrane was investigated.     

Aluminizing and oxidation treatments on the porous stainless steel substrate for preparation of H2-permeable composite palladium membranes

Composite palladium membranes based on porous stainless steel (PSS) substrate are idea hydrogen separators and purifiers for hydrogen energy systems, and the surface modification of the PSS is of key importance. In this work, the macroporous PSS tubes were aluminized through pack cementation at 850 °C in argon, followed by an oxidation with air at 600 °C. Palladium membranes were prepared by electroless plating. Their permeation performances were tested, and the hydrogen permeation kinetics was discussed. The substrate materials and the palladium membranes were characterized by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD). An Al₂O₃-enriched surface layer with small pore size was created through aluminizing and oxidation treatments, which greatly improves the membrane integrity. The intermetallic diffusion between the palladium membranes and the PSS substrate material was not observed after a heat-treatment at 500 °C under hydrogen for 200 h. However, the aluminizing and oxidation treatments still need to be further optimized in order to improve the membrane permeability and selectivity, and particularly, the high diffusion resistance of the substrate materials greatly limited the hydrogen flux.     

PVDF/ionic liquid polymer blends with superior separation performance for removing CO2 from hydrogen and flue gas

We have demonstrated, for the first time, a polymer blend comprising poly(vinylidene fluoride) (PVDF) and a room-temperature ionic liquid (RTIL) that shows a high CO₂ permeability of 1778 Barrer with CO₂/H₂ and CO₂/N₂ selectivity of 12.9 and 41.1, respectively. The low viscosity RTIL, 1-ethyl-3-methylimidazolium tetracyanoborate ([emim][B(CN)₄]) possesses a high CO₂ solubility, and plays a significant role in CO₂ separation, whereas PVDF provides the mechanical strength to the blend membranes. A series of PVDF/[emim][B(CN)₄] polymer blends with different compositions were tested for their gas separation performance involving H₂, N₂ and CO₂ in both pure gas and mixed gas conditions. Both optical observation and Maxwell predictions confirm the heterogeneous nature of the PVDF/[emim][B(CN)₄] system. However, compared to miscible ionic liquid based blends, where molecular level interactions may restrain chain flexibility and reduce gas permeability, heterogeneous PVDF/RTIL blend systems show far superior gas transport properties. Most of these blend membranes outperform most reported materials and their gas transport and separation capabilities fall within the attractive region bound by the “2008 Robeson Upper Limit” for CO₂/H₂ and CO₂/N₂ gas pairs, and are also very stable at trans-membrane pressure up to 5 atm. Therefore, they are potential materials for H₂ purification and CO₂ capture from hydrogen production and flue gas.     

Preparation and characterization of multi-walled carbon nanotube/PBNPI nanocomposite membrane for H2/CH4 separation

By combining organic polymers normally used to make membrane filters with inorganic substances, multi-walled carbon nanotube (MWCNTs), an extraordinary ability to separate H₂ from CH₄ was developed in this study. A series of MWCNTs/PBNPI nanocomposite membrane with a nominal MWCNTs content between 1 and 15 wt% were prepared by solution casting method, in which the very fine MWCNTs were embedded into glassy polymer membrane. Detailed characterizations, such as morphology, thermal stability and crystalline structure have been conducted to understand the structures, composition and properties of nanocomposite membranes. The results found that this new class of membrane had increased permeability and enhanced selectivity, and a useful ability to filter gases and organic vapours at the molecular level.     

Novel La0.7Sr0.3FeO3 − δ/(La0.5Sr0.5)2CoO4 + δ composite hollow fiber membrane for O2 separation with high CO2 resistance

Recently, the reported Perovskite/Ruddlesden‐Popper composite with significant improvement of oxygen surface kinetics has been adopted into gas separation process. Here, we report a novel La_0.7Sr_0.3FeO_{3 ? δ}/(La_0.5Sr_0.5)₂CoO_{4 + δ} (LSF‐LSC) composite hollow fiber membrane (HFM), which was characterized by X‐ray diffraction (XRD), scanning electron microscope (SEM), and thermal expansion test, etc. The O₂ permeation test results indicated that, under sweeping gas of pure He (100 mL min^?1), the composite HFM exhibited the superior O₂ permeability (0.72 mL min^?1 cm^?2) at the temperature of 950^°C with respect to the single La_0.7Sr_0.3FeO_{3 ? δ} (LSF) membrane, acid‐etched membrane, and (La_0.5Sr_0.5)₂CoO_{4 + δ} (LSC)‐coated membrane. Moreover, the composite membrane exhibited high CO₂ tolerance as well as phase stability. The generation of hetero‐interface between Ruddlesden‐Popper phase and perovskite phase could be responsible for the improvement of the oxygen transportation over the fabricated composite membrane.     

Dye-sensitized solar cells based on anatase TiO2 hollow spheres/carbon nanotube composite films

Dye-sensitized solar cells (DSSCs) based on anatase TiO₂ hollow spheres (TiO2HS)/multi-walled carbon nanotubes (CNT) nanocomposite films are prepared by a directly mechanical mixing and doctor blade method. The prepared samples are characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy and N₂ adsorption-desorption isotherms. The photoelectric conversion performances of the DSSCs based on TiO2HS/CNT composite film electrodes are also compared with commercial-grade Degussa P25 TiO₂ nanoparticles (P25)/CNT composite solar cells at the same film thickness. The results indicate that the photoelectric conversion efficiencies (η) of the TiO2HS/CNT composite DSSCs are dependent on CNT loading in the electrodes. A small amount of CNT clearly enhances DSSC efficiency, while excessive CNT loading significantly lowers their performance. The former is because CNT enhance the transport of electrons from the films to FTO substrates. The latter is due to high CNT loading shielding the visible light from being adsorbed by dyes.     

Explosion behavior of CH4/O2/N2/CO2 and H2/O2/N2/CO2 mixtures

In this work, the explosion behavior of stoichiometric CH₄/O₂/N₂/CO₂ and H₂/O₂/N₂/CO₂ mixtures has been studied both experimentally and theoretically at different CO₂ contents and oxygen air enrichment factors. Peak pressure, maximum rate of pressure rise and laminar burning velocity were measured from pressure time records of explosions occurring in a closed cylindrical vessel. The laminar burning velocity was also computed through CHEMKIN–PREMIX simulations.     

微孔型膜接触器分离模拟烟气中二氧化碳的研究

本文通过聚丙烯中空纤维微孔膜接触器分离模拟烟气中二氧化碳的实验研究，考察了膜组件的联接方式、气体流量：气相中二氧化碳浓度、吸收液种类、浓度及流速等因素对二氧化碳脱除率的影响，结果表明，膜组件串联方式、提高吸收液的浓度和流速均可提高二氧化碳的脱除率；同时发现氨基酸盐溶液是一种较好的吸收剂。     

Effect of dry/wet-phase inversion method on fabricating polyetherimide-derived CMS membrane for H2/N2 separation

The research investigated carbon molecular sieve (CMS) membranes through the dry/wet-phase inversion method from the casting polyetherimide (PEI) on alumina support for hydrogen separation. Different coating techniques such as dry method (slide casting followed by drying under vacuum; and spin coating followed by drying under vacuum); and wet method (spin coating and then later kept in an isopropyl alcohol (IPA)/water coagulating bath) at different pyrolysis temperatures of 550, 600, 650 °C min⁻¹ were also investigated.     

Toward low-cost Pd/ceramic composite membranes for hydrogen separation: A case study on reuse of the recycled porous Al2O3 substrates in membrane fabrication

The development of hydrogen energy systems has placed a high demand on hydrogen-permeable membranes as compact hydrogen separators and purifiers. Although Pd/Ceramic composite membranes are particularly effective in this role, the high cost of these membranes has greatly limited their applications; this high cost stems largely from the use of expensive substrate material. This problem may be solved by substrate recycling and the use of lower cost substrates. As a case study, we employed expensive asymmetric microporous Al₂O₃ and low-cost macroporous symmetric Al₂O₃ as membrane substrates (average pore sizes are 0.2 and 3.3 μm, respectively). The palladium membranes were fabricated by electroless plating, and substrate recycling was carried out by palladium dissolution with a hot HNO₃ solution. The functional surface layer of the microporous Al₂O₃ was damaged during substrate recycling, and the reuse of the substrate led to poor membrane selectivity. With the assistance of pencil coating as a facile and environmentally benign surface treatment, the macroporous Al₂O₃ can be successfully utilized. Furthermore, the macroporous Al₂O₃ can be also recycled and reused as membrane substrate, yielding highly permeable, selective and stable palladium membranes. Consequently, the substrate cost can be further decreased, and the applications of this kind of membranes would expand.