Membranes, Volume 9, Issue 9 (September 2019) – 18 articles

In this study, a series of novel modified graphene oxide (MGO)/polyacrylonitrile (PAN) hybrid nanofiber membranes were fabricated by electrospinning a PAN solution containing up to 1.0 wt.% MGO. The GO was initially prepared by a time-saving improved Hummer’s method. Subsequently, the formation of GO was confirmed by scanning electron microscopy (SEM), AFM, Fourier-transform infrared spectroscopy (FT–IR), and Raman spectroscopy. This study also prepared the modified GO with polydiallyldimethylammonium chloride (GP) by using a simple surface post-treatment method to improve its dispersion. Varying amounts of GP were incorporated into PAN nanofibers for the better properties of GP/PAN nanofibers, such as hydrophilicity, mechanical properties, and so on. The resulting GP/PAN hybrid nanofiber membranes were characterized by SEM, FTIR, contact angle, and thermal and mechanical properties. These results showed that the hydrophilic and mechanical properties of GP/PAN hybrid nanofiber membranes were dramatically improved, i.e., 50% improvement for hydrophilicity and 3–4 times higher strength for mechanical property, which indicated the possibility for water treatment application. In addition, the notably improved thermal stability results showed that the hybrid nanofiber membranes could also be a potential candidate for the secondary battery separator. Full article

In this study, the properties of the initial fouling layer on the membrane surface of a bioreactor were investigated under different operating modes (with or without permeate flux) to improve the understanding of the effect of permeation drag on the formation of the initial fouling layer. It was found that protein was the major component in the two types of initial fouling layers, and that the permeation drag enhanced the tryptophan protein-like substances. The attraction of the initial foulants to the polyvinylidene fluoride (PVDF) membrane was ascribed to the high zeta potential and electron donor component (γ−) of the membrane. Thermodynamic analyses showed that the permeation drag-induced fouling layer possessed high hydrophobicity and low γ−. Due to permeation drag, a portion of the foulants overcame an energy barrier before they contacted the membrane surface, which itself possessed a higher fouling propensity. A declining trend of the cohesive strength among the foulants was found with the increasing development of both fouling layers. Full article

BaZr_0.9Y_0.1O_3-δ (BZY10), a promising proton conducting material, exhibits p-type conduction under oxidative conditions. Holes in BZY10 are of the small polaron type. However, there is no clear understanding at which places in the lattice they are localized. The main objectives of this work were, therefore, to discuss the nature of electronic defects in BZY10 on the basis of the combined measurements of the thermo-EMF and conductivity. Total electrical conductivity and Seebeck coefficient of BZY10 were simultaneously studied depending on partial pressures of oxygen (pO₂), water (pH₂O) and temperature (T). The model equation for total conductivity and Seebeck coefficient derived on the basis of the proposed defect chemical approach was successfully fitted to the experimental data. Transference numbers of all the charge carriers in BZY10 were calculated. The heat of transport of oxide ions was found to be about one half the activation energy of their mobility, while that of protons was almost equal to the activation energy of their mobility. The results of the Seebeck coefficient modeling indicate that cation impurities, rather than oxygen sites, should be considered as a place of hole localization. Full article

In the present study, the separation performance of new self-standing polyvinylamine (PVAm) membranes loaded with few-layer graphene (G) and graphene oxide (GO) was evaluated, in view of their use in carbon capture applications. PVAm, provided by BASF as commercial product named Lupamin^TM, was purified obtaining PVAm films with two degrees of purification: Low Grade (PVAm-LG) and High Grade (PVAm-HG). These two-grade purified PVAm were loaded with 3 wt% of graphene and graphene oxide to improve mechanical stability: indeed, pristine tested materials proved to be brittle when dry, while highly susceptible to swelling in humid conditions. Purification performances were assessed through FTIR-ATR spectroscopy, DSC and TGA analysis, which were carried out to characterize the pristine polymer and its nanocomposites. In addition, the membranes′ fracture surfaces were observed through SEM analysis to evaluate the degree of dispersion. Water sorption and gas permeation tests were performed at 35 °C at different relative humidity (RH), ranging from 50% to 95%. Overall, composite membranes showed improved mechanical stability at high humidity, and higher glass transition temperature (T_g) with respect to neat PVAm. Ideal CO₂/N₂ selectivity up to 80 was measured, paired with a CO₂ permeability of 70 Barrer. The membranes’ increased mechanical stability against swelling, even at high RH, without the need of any crosslinking, represents an interesting result in view of possible further development of new types of facilitated transport composite membranes. Full article

Membrane distillation (MD) is an up and coming technology for concentration and separation on the verge of reaching commercialization. One of the remaining boundaries is the lack of available full-scale MD modules and systems suitable to meet the requirements of potential industrial applications. In this work a new type of feed gap air gap MD (FGAGMD) plate and frame module is introduced, designed and characterized with tap water and NaCl–H₂O solution. The main feature of the new channel configuration is the separation of the heating and cooling channel from the feed channel, enabling a very high recovery ratio in a single pass. Key performance indicators (KPIs) such as flux, gained output ratio (GOR), recovery ratio and thermal efficiency are used to analyze the performance of the novel module concept within this work. A recovery rate of 93% was reached with tap water and between 32–53% with salt solutions ranging between 117 and 214 g NaCl/kg solution with this particular prototype module. Other than recovery ratio, the KPIs of the FGAGMD are similar to those of an air gap membrane distillation (AGMD) channel configuration. From the experimental results, furthermore, a new MD KPI was defined as the ratio of heating and cooling flow to feed flow. This R_F ratio can be used for optimization of the module design and efficiency. Full article

Routine chemical cleaning with the combined use of sodium hydroxide (NaOH) and hydrochloric acid (HCl) is carried out as a means of biofouling control in reverse osmosis (RO) membranes. The novelty of the research presented herein is in the application of urea, instead of NaOH, as a chemical cleaning agent to full-scale spiral-wound RO membrane elements. A comparative study was carried out at a pilot-scale facility at the Evides Industriewater DECO water treatment plant in the Netherlands. Three fouled 8-inch diameter membrane modules were harvested from the lead position of one of the full-scale RO units treating membrane bioreactor (MBR) permeate. One membrane module was not cleaned and was assessed as the control. The second membrane module was cleaned by the standard alkali/acid cleaning protocol. The third membrane module was cleaned with concentrated urea solution followed by acid rinse. The results showed that urea cleaning is as effective as the conventional chemical cleaning with regards to restoring the normalized feed channel pressure drop, and more effective in terms of (i) improving membrane permeability, and (ii) solubilizing organic foulants and the subsequent removal of the surface fouling layer. Higher biomass removal by urea cleaning was also indicated by the fact that the total organic carbon (TOC) content in the HCl rinse solution post-urea-cleaning was an order of magnitude greater than in the HCl rinse after standard cleaning. Further optimization of urea-based membrane cleaning protocols and urea recovery and/or waste treatment methods is proposed for full-scale applications. Full article

This paper investigates the influence of the support material and its thickness on the hydrogen flux in Palladium membranes in the presence of sweep gas in fluidized bed membrane reactors. The analysis is performed considering both ceramic and metallic supports with different properties. In general, ceramic supports are cheaper but suffer sealing problems, while metallic ones are more expensive but with much less sealing problems. Firstly, a preliminary analysis is performed to assess the impact of the support in the permeation flux, which shows that the membrane permeance can be halved when the H₂ diffusion through the support is considered. The most relevant parameter which affects the permeation is the porosity over tortuosity ratio of the porous support. Afterward, the different supports are compared from an economic point of view when applied to a membrane reactor designed for 100 kg/day of hydrogen, using biogas as feedstock. The stainless steel supports have lower impact on the hydrogen permeation so the required membrane surface area is 2.6 m² compared to 3.6 m² of the best ceramic support. This ends up as 5.6 €/kg H_2@20bar and 6.6 €/kg H_2@700bar for the best stainless steel support, which is 3% lower than the price calculated for the best ceramic support. Full article

Air separation is very important from the viewpoint of the economic and environmental advantages. In this work, defect-free facilitated transport membranes based on poly(amide-12-b-ethylene oxide) (Pebax-2533) and tetra(p-methoxylphenyl)porphyrin cobalt chloride (T(p-OCH₃)PPCoCl) were fabricated in systematically varied compositions for O₂/N₂ separation. T(p-OCH₃)PPCoCl was introduced as carriers that selectively and reversibly interacted with O₂ and facilitated O₂ transport in the membrane. The T(p-OCH₃)PPCoCl had good compatibility with the Pebax-2533 via the hydrogen bond interaction and formed a uniform and thin selective layer on the substrate. The O₂ separation performance of the thin film composite (TFC) membranes was improved by adding a small amount of the T(p-OCH₃)PPCoCl and decreasing the feed pressure. At the pressure of 0.035 MPa, the O₂ permeability and O₂/N₂ selectivity of the 0.6 wt % T(p-OCH₃)PPCoCl/Pebax-2533 was more than 3.5 times that of the Pebax-2533 TFC membrane, which reached the 2008 Robeson upper bound. It provides a candidate membrane material for O₂/N₂ efficient separation in moderate conditions. Full article

The use of enzymatic agents as biological solutions for cleaning ion-exchange membranes fouled by organic compounds during electrodialysis (ED) treatments in the food industry could be an interesting alternative to chemical cleanings implemented at an industrial scale. This paper is focused on testing the cleaning efficiency of three enzyme classes (β-glucanase, protease, and polyphenol oxidase) chosen for their specific actions on polysaccharides, proteins, and phenolic compounds, respectively, fouled on a homogeneous cation-exchange membrane (referred CMX-Sb) used for tartaric stabilization of red wine by ED in industry. First, enzymatic cleaning tests were performed using each enzyme solution separately with two different concentrations (0.1 and 1.0 g/L) at different incubation temperatures (30, 35, 40, 45, and 50 °C). The evolution of membrane parameters (electrical conductivity, ion-exchange capacity, and contact angle) was determined to estimate the efficiency of the membrane′s principal action as well as its side activities. Based on these tests, we determined the optimal operating conditions for optimal recovery of the studied characteristics. Then, cleaning with three successive enzyme solutions or the use of two enzymes simultaneously in an enzyme mixture were tested taking into account the optimal conditions of their enzymatic activity (concentration, temperatures, and pH). This study led to significant results, indicating effective external and internal cleaning by the studied enzymes (a recovery of at least 25% of the electrical conductivity, 14% of the ion-exchange capacity, and 12% of the contact angle), and demonstrated the presence of possible enzyme combinations for the enhancement of the global cleaning efficiency or reducing cleaning durations. These results prove, for the first time, the applicability of enzymatic cleanings to membranes, the inertia of their action towards polymer matrix to the extent that the choice of enzymes is specific to the fouling substrates. Full article

Random copolymers made of both (PIM-polyimide) and (6FDA-durene-PI) were prepared for the first time by a facile one-step polycondensation reaction. By combining the highly porous and contorted structure of PIM (polymers with intrinsic microporosity) and high thermomechanical properties of PI (polyimide), the membranes obtained from these random copolymers [(PIM-PI)-(6FDA-durene-PI)] showed high CO₂ permeability (>1047 Barrer) with moderate CO₂/N₂ (> 16.5) and CO₂/CH₄ (> 18) selectivity, together with excellent thermal and mechanical properties. The membranes prepared from three different compositions of two comonomers (1:4, 1:6 and 1:10 of x:y), all showed similar morphological and physical properties, and gas separating performance, indicating ease of synthesis and practicability for production in large scale. The gas separation performance of these membranes at various pressure ranges (100–1500 torr) was also investigated. Full article

Ammonia is a key chemical produced in huge quantities worldwide. Its primary industrial production is via the Haber-Bosch method; a process requiring high temperatures and pressures, and consuming large amounts of energy. In the past two decades, several alternatives to the existing process have been proposed, including the electrochemical synthesis. The present paper reviews literature concerning this approach and the experimental research carried out in aqueous, molten salt, or solid electrolyte cells, over the past three years. The electrochemical systems are grouped, described, and discussed according to the operating temperature, which is determined by the electrolyte used, and their performance is valuated. The problems which need to be addressed further in order to scale-up the electrochemical synthesis of ammonia to the industrial level are examined. Full article

Reverse osmosis and nanofiltration systems are continuously challenged with biofouling of polyamide membranes that are used almost exclusively for these desalination techniques. Traditionally, pretreatment and reactive membrane cleanings are employed as biofouling control methods. This in-depth review paper discusses the mechanisms of membrane biofouling and effects on performance. Current industrial disinfection techniques are reviewed, including chlorine and other chemical and non-chemical alternatives to chlorine. Operational techniques such as reactive membrane cleaning are also covered. Based on this review, there are three suggested areas of additional research offering promising, polyamide membrane-targeted biofouling minimization that are discussed. One area is membrane modification. Modification using surface coatings with inclusion of various nanoparticles, and graphene oxide within the polymer or membrane matrix, are covered. This work is in the infancy stage and shows promise for minimizing the contributions of current membranes themselves in promoting biofouling, as well as creating oxidant-resistant membranes. Another area of suggested research is chemical disinfectants for possible application directly on the membrane. Likely disinfectants discussed herein include nitric oxide donor compounds, dichloroisocyanurate, and chlorine dioxide. Finally, proactive cleaning, which aims to control the extent of biofouling by cleaning before it negatively affects membrane performance, shows potential for low- to middle-risk systems. Full article

The main purposes of this study are to evaluate the performance of graphene membranes in the separation/purification of hydrogen from nitrogen from a theoretical point of view using the molecular dynamic (MD) simulation method, and to present details about molecular mechanisms of selective gas diffusion through nanoscale pores of graphene membranes at the simulated set conditions. On the other hand, permeance and perm-selectivity are two significant parameters of such a membrane that can be controlled by several variables such as pressure gradient, pore density, pore layer angles etc. Hence, in this work, the hydrogen and nitrogen permeating fluxes as well as the H₂/N₂ ideal perm-selectivity are investigated from a theoretical point of view in a two-layer nanoporous graphene (NPG) membrane through classical MD simulations, wherein the effects of pressure gradient, pore density, and pore angle on the NPG membrane performance are evaluated and discussed. Simulation outcomes suggest that hydrogen and nitrogen permeating fluxes increase as a consequence of an increment of pressure gradient across the membrane and pore density. Full article

Organic/inorganic hybrid membranes that are based on GTT (GPTMS-TMES-TPTE) system while using 3-Glycidoxypropyl-trimethoxysilane (GPTMS), Trimethyletoxisilane (TMES), and Trimethylolpropane triglycidyl ether (TPTE) as precursors have been obtained while using a combination of organic polymerization and sol-gel synthesis to be used as electrolytes in Li-ion batteries. Self-supported materials and thin-films solid hybrid electrolytes that were doped with Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared. The hybrid network is based on highly cross-linked structures with high ionic conductivity. The dependency of the crosslinked hybrid structure and polymerization grade on ionic conductivity is studied. Ionic conductivity depends on triepoxy precursor (TPTE) and the accessibility of Li ions in the organic network, reaching a maximum ionic conductivity of 1.3 × 10⁻⁴ and 1.4 × 10⁻³ S cm⁻¹ at room temperature and 60 °C, respectively. A wide electrochemical stability window in the range of 1.5–5 V facilitates its use as solid electrolytes in next-generation of Li-ion batteries. Full article

Dual-phase membranes for high-temperature carbon dioxide separation have emerged as promising technology to mitigate anthropogenic greenhouse gases emissions, especially as a pre- and post-combustion separation technique in coal burning power plants. To implement these membranes industrially, the carbon dioxide permeability must be improved. In this study, Ce_0.8Sm_0.2O_2−δ (SDC) and Ce_0.8Sm_0.19Fe_0.01O_2−δ (FSDC) ceramic powders were used to form the skeleton in dual-phase membranes. The use of MgO as an environmentally friendly pore generator allows control over the membrane porosity and microstructure in order to compare the effect of the membrane’s ceramic phase. The ceramic powders and the resulting membranes were characterized using ICP-OES, HSM, gravimetric analysis, SEM/EDX, and XRD, and the carbon dioxide flux density was quantified using a high-temperature membrane permeation setup. The carbon dioxide permeability slightly increases with the addition of iron in the FSDC membranes compared to the SDC membranes mainly due to the reported scavenging effect of iron with the siliceous impurities, with an additional potential contribution of an increased crystallite size due to viscous flow sintering. The increased permeability of the FSDC system and the proper microstructure control by MgO can be further extended to optimize carbon dioxide permeability in this membrane system. Full article

Organosilica membranes are a type of novel materials derived from organoalkoxysilane precursors. These membranes have tunable networks, functional properties and excellent hydrothermal stability that allow them to maintain high levels of separation performance for extend periods of time in either a gas-phase with steam or a liquid-phase under high temperature. These attributes make them outperform pure silica membranes. In this review, types of precursors, preparation method, and synthesis factors for the construction of organosilica membranes are covered. The effects that these factors exert on characteristics and performance of these membranes are also discussed. The incorporation of metals, alkoxysilanes, or other functional materials into organosilica membranes is an effective and simple way to improve their hydrothermal stability and achieve preferable chemical properties. These hybrid organosilica membranes have demonstrated effective performance in gas and liquid-phase separation. Full article

Forward osmosis (FO) has rarely been investigated as a treatment technology for industrial wastewaters. Within this study, common FO model equations were applied to simulate forward osmosis treatment of industrial wastewaters from the automobile industry. Three different models from literature were used and compared. Permeate and reverse solute flux modelling was implemented using MS Excel with a Generalized Reduced Gradient (GRG) Nonlinear Solver. For the industrial effluents, the unknown diffusion coefficients were calibrated and the influences of the membrane parameters were investigated. Experimental data was used to evaluate the models. It could be proven that common model equations can describe FO treatment of industrial effluents from the automobile industry. Even with few known solution properties, it was possible to determine permeate fluxes and draw conclusions about mass transport. However, the membrane parameters, which are apparently not solution independent and seem to differ for each industrial effluent, are critical values. Fouling was not included in the model equations although it is a crucial point in FO treatment of industrial wastewaters. But precisely for this reason, modelling is a good complement to laboratory experiments since the difference between the results allows conclusions to be drawn about fouling. Full article

In water treatment applications, the use of ceramic membranes is associated with numerous advantages relative to polymer-based filtration systems. High-temperature stability, fouling resistance, and low maintenance requirements contribute to lower lifecycle costs in such systems. However, the high production costs of most commercially available ceramic membranes, stemming from raw materials and processing, are uneconomical for such systems in most water treatment applications. For this reason, there is a growing demand for new ceramic membranes based on low-cost raw materials and processes. The use of unrefined mineral feedstocks, clays, cement, sands, and ash as the basis for the fabrication of ceramic membranes offers a promising pathway towards the obtainment of effective filtration systems that can be economically implemented in large volumes. The design of effective ceramic filtration membranes based on low-cost raw materials and energy-efficient processes requires a balance of pore structure, mass flow, and robustness, all of which are highly dependent on the composition of materials used, the inclusion of various pore-forming and binding additives, and the thermal treatments to which membranes are subjected. In this review, we present recent developments in materials and processes for the fabrication of low-cost membranes from unrefined raw materials, including clays, zeolites, apatite, waste products, including fly ash and rice husk ash, and cement. We examine multiple aspects of materials design and address the challenges relating to their further development. Full article