Assessing thermoelectric membrane distillation performance: An experimental design approach.

Thermoelectric membrane distillation has shown promise as a new membrane distillation technique capable of improving energy consumption metrics. This study features an experimental design approach to investigating the performance of a thermoelectric membrane distillation system. Screening and full factorial designs were implemented in Minitab 16 to determine the optimal process conditions for minimizing the specific energy consumption of the system. The process parameter with the most significant impact on the specific energy consumption of thermoelectric membrane distillation systems was determined and a mathematical model for predicting the specific energy consumption was derived. The study showed that adjusting the feed flowrate, the most influential continuous parameter, from a sub-optimal level to an optimal level, while keeping other process variables at their optimal levels, could lead to a 34% reduction in the system's specific energy consumption. At the optimized process parameters of the thermoelectric membrane distillation system, the minimized specific energy consumption fell about 35% below the threshold value of 1,000 kWh/m3 found among the efficient membrane distillation systems in the literature.•Thermoelectric heat exchanger provides the driving force for the membrane distillation process•Seven process variables are assumed to influence the energy consumption of the distillation process•The variables are screened before being analyzed in a full factorial experimental design.

Valorization of Seawater Reverse Osmosis Brine by Monovalent Ion-Selective Membranes through Electrodialysis.

This paper proposes the use of monovalent selective electrodialysis technology to concentrate the valuable sodium chloride (NaCl) component present in seawater reverse osmosis (SWRO) brine for direct utilization in the chlor-alkali industry. To enhance monovalent selectivity, a polyamide selective layer was fabricated on commercial ion exchange membranes (IEMs) through interfacial polymerization (IP) of piperazine (PIP) and 1,3,5-Benzenetricarbonyl chloride (TMC). The IP-modified IEMs were characterized using various techniques to investigate changes in chemical structure, morphology, and surface charge. Ion chromatography (IC) analysis showed that the divalent rejection rate was more than 90% for IP-modified IEMs, compared to less than 65% for commercial IEMs. Electrodialysis results demonstrated that the SWRO brine was successfully concentrated to 14.9 g/L NaCl at a power consumption rate of 3.041 kWh/kg, indicating the advantageous performance of the IP-modified IEMs. Overall, the proposed monovalent selective electrodialysis technology using IP-modified IEMs has the potential to provide a sustainable solution for the direct utilization of NaCl in the chlor-alkali industry.

Fine-tuning of carbon nanostructures/alginate nanofiltration performance: Towards electrically-conductive and self-cleaning properties.

Electrically-conductive membranes became the center of attention owing to their enhanced ion selectivity and self-cleaning properties. Carbon nanostructures (CNS) attain high electrical conductivity, and fast water transport. Herein, we adopt a water-based, simple method to entrap CNS within Alginate network to fabricate self-cleaning nanofiltration membranes. CNS are embedded into membranes to improve the swelling/shrinkage resistivity, and to achieve electrical-conductivity. The CaAlg PEG-formed pores are tuned by organic-inorganic network via silane crosslinking. Flux/rejection profiles of Na2SO4 are studied/optimized in reference to fabrication parameters. 90% Na2SO4 rejection (7 LMH) is achieved for silane-CaAlg200-10% CNS membranes. Membranes exhibit outstanding electrical conductivity (∼2858 S m-1), which is attractive for fouling control. CaAlg/CNS membranes are tested to treat dye/saline water via two-stage filtration, namely, dye/salt separation and desalination. A successful dye/salt separation is achieved at the first stage with a rejection of 100%-RB and only 3.1% Na2SO4, and 54% Na2SO4 rejection in the second stage.

Fabrication of Thin Film Composite Membranes on Nanozeolite Modified Support Layer for Tailored Nanofiltration Performance.

Thin-film composite (TFC) structure has been widely employed in polymeric membrane fabrication to achieve superior performance for desalination and water treatment. In particular, TFC membranes with a thin active polyamide (PA) selective layer are proven to offer improved permeability without compromising salt rejection. Several modifications to TFCs have been proposed over the years to enhance their performance by altering the selective, intermediate, or support layer. This study proposes the modification of the membrane support using nanozeolites prepared by a unique ball milling technique for tailoring the nanofiltration performance. TFC membranes were fabricated by the interfacial polymerization of Piperazine (PIP) and 1,3,5-Benzenetricarbonyl trichloride (TMC) on Polysulfone (PSf) supports modified with nanozeolites. The nanozeolite concentration in the casting solution varied from 0 to 0.2%. Supports prepared with different nanozeolite concentrations resulted in varied hydrophilicity, porosity, and permeability. Results showed that optimum membrane performance was obtained for supports modified with 0.1% nanozeolites where pure water permeance of 17.1 ± 2.1 Lm-2 h-1 bar-1 was observed with a salt rejection of 11.47%, 33.84%, 94%, and 95.1% for NaCl, MgCl2, MgSO4, and Na2SO4 respectively.

Breaking and Connecting: Highly Hazy and Transparent Regenerated Networked-Nanofibrous Cellulose Films via Combination of Hydrolysis and Crosslinking.

High optical transparency combined with high optical haze are essential requirements for optoelectronic substrates. Light scattering caused by haze is responsible for increasing light harvesting in photon-absorbing active materials, hence increasing efficiencies. A trade-off between transparency and haze is common in solar substrates with high transparency (~90%) and low optical haze (~20%), or vice versa. In this study, we report a novel, highly transparent film fabricated from regenerated cellulose after controlled acid-hydrolysis of microcrystalline cellulose (MCC). The developed networked-nanofibrous cellulose was chemically crosslinked with glutaraldehyde (GA) and vacuum-cured to facilitate the fabrication of mechanically stable films. The effects of crosslinker concentration, crosslinking time, and curing temperature were investigated. Optimum conditions for fabrication unveils high optical transparency (~94%) and high haze (~60%), using 25% GA for 24 hr with a curing temperature of 25 °C; therefore, conveying an optimal substrate for optoelectronics applications. The high haze arises primarily from the crystalline, networked crystals of cellulose II structure formed within the regenerated cellulose upon hydrolysis. Moreover, the developed crosslinked film presents high thermal stability, water resistance, and good mechanical resilience. This high-performance crosslinked cellulose film can be considered a potential material for new environmentally-friendly optical substrates.

Shifting to Transparent/Hazy Properties: The Case of Alginate/Network Cellulose All-Polysaccharide Composite Films.

Light-management films made entirely from natural polymers with tunable haze properties are developed via a facile approach. A novel green method based simply on the blending of network cellulose (NC)/water suspension with alginate (CaAlg) aqueous solution is proposed. The unique NC suspension created by a controlled hydrolysis of microcrystalline cellulose acts as the scatterer media while alginate serves as the transparent host matrix. NC features isotropic intertwined network of nanofibers that contributes to light scattering and produces optical haze. The opaque but hazy NC is dispersed purposefully in the alginate film, where its original properties are preserved owing to its poor solubility in water. Additionally, the dispersion notably increases the roughness of the composite film surface and acts as a light scatterer. Eventually, composite CaAlg/NC film with high transparency (>94%) and customized haze (15-73%) at 550 cm-1 wavelength is fabricated. Herein, the transparent alginate is successfully combined with the hazy cellulose of uniformly distributed nanofibers by blending to fabricate transparent/hazy all-natural films. The fabricated films exhibit high transparency with tailored transmission haze. The film is highly fitting for large-scale production and adequate to meet different haze requirements to accommodate different applications such as privacy protection films and antiglare/antireflection coatings.

Cellulose Nanofibrils as a Damping Material for the Production of Highly Crystalline Nanosized Zeolite Y via Ball Milling.

Nanosized zeolite Y is used in various applications from catalysis in petroleum refining to nanofillers in water treatment membranes. Ball milling is a potential and fast technique to decrease the particle size of zeolite Y to the nano range. However, this technique is associated with a significant loss of crystallinity. Therefore, in this study, we investigate the effect of adding biodegradable and recyclable cellulose nanofibrils (CNFs) to zeolite Y in a wet ball milling approach. CNFs are added to shield the zeolite Y particles from harsh milling conditions due to their high surface area, mechanical strength, and water gel-like format. Different zeolite Y to CNFs ratios were studied and compared to optimize the ball milling process. The results showed that the optimal zeolite Y to CNFs ratio is 1:1 to produce a median particle size diameter of 100 nm and crystallinity index of 32%. The size reduction process provided accessibility to the zeolite pores and as a result increased their adsorption capacity. The adsorption capacity of ball-milled particles for methylene blue increased to 29.26 mg/g compared to 10.66 mg/g of the pristine Zeolite. These results demonstrate the potential of using CNF in protecting zeolite Y particles and possibly other micro particles during ball milling.

Simultaneous Enzymatic Cellulose Hydrolysis and Product Separation in a Radial-Flow Membrane Bioreactor.

Hydrolysis is the heart of the lignocellulose-to-bioethanol conversion process. Using enzymes to catalyze the hydrolysis represents a more environmentally friendly pathway compared to other techniques. However, for the process to be economically feasible, solving the product inhibition problem and enhancing enzyme reusability are essential. Prior research demonstrated that a flat-sheet membrane bioreactor (MBR), using an inverted dead-end filtration system, could achieve 86.7% glucose yield from purified cellulose in 6 h. In this study, the effectiveness of flat-sheet versus radial-flow MBR designs was assessed using real, complex lignocellulose biomass, namely date seeds (DSs). The tubular radial-flow MBR used here had more than a 10-fold higher membrane surface area than the flat-sheet MBR design. With simultaneous product separation using the flat-sheet inverted dead-end filtration MBR, a glucose yield of 10.8% from pretreated DSs was achieved within 8 h of reaction, which was three times higher than the yield without product separation, which was only 3.5% within the same time and under the same conditions. The superiority of the tubular radial-flow MBR to hydrolyze pretreated DSs was confirmed with a glucose yield of 60% within 8 h. The promising results obtained by the novel tubular MBR could pave the way for an economic lignocellulose-to-bioethanol process.

Proton Conductive, Low Methanol Crossover Cellulose-Based Membranes.

This work describes the development of sulfated cellulose (SC) polymer and explores its potential as an electrolyte-membrane for direct methanol fuel cells (DMFC). The fabrication of our membranes was initiated by the preparation of the novel sulfated cellulose solution via controlled acid hydrolysis of microcrystalline cellulose (MCC). Ion-conductive crosslinked SC membranes were prepared following a chemical crosslinking reaction. SC solution was chemically crosslinked with glutaraldehyde (GA) and cured at 30 °C to produce the aforementioned membranes. Effects of GA concentration on methanol permeability, proton conductivity, water uptake and thermal stabilities were investigated. The crosslinking reaction is confirmed by FTIR technique where a bond between the primary OH groups of cellulose and the GA aldehyde groups was achieved, leading to the increased hydrophobic backbone domains in the membrane. The results show that the time of crosslinking reaction highly affects the proton conduction and methanol permeability. The proton conductivity and methanol crossover (3M) of our GA crosslinked SC membranes are 3.7 × 10-2 mS cm-1 and 8.2 × 10-9 cm2 s-1, respectively. Crosslinked sulfated cellulose films have lower ion conductivity than the state-of-the-art Nafion (10.2 mS cm-1); however, the methanol crossover is three orders of magnitude lower than Nafion membranes (1.0 × 10-5 cm2 s-1 at 1 M). Such biofilms with high methanol resistivity address the major hurdle that prevents the widespread applications of direct alcohol fuel cells.

Nanoscopic and Macro-Porous Carbon Nano-foam Electrodes with Improved Mass Transport for Vanadium Redox Flow Batteries.

Although free-standing sheets of multiwalled carbon nanotubes (MWCNT) can provide interesting electrochemical and physical properties as electrodes for redox flow batteries, the full potential of this class of materials has not been accessible as of yet. The conventional fabrication methods produce sheets with micro-porous and meso-porous structures, which significantly resist mass transport of the electrolyte during high-current flow-cell operation. Herein, we developed a method to fabricate high performance macro-porous carbon nano-foam free standing sheets (Puffy Fibers, PF), by implementing a freeze-drying step into our low cost and scalable surface-engineered tape-casting (SETC) fabrication method, and we show the improvement in the performance attained as compared with a MWCNT sheet lacking any macro pores (Tape-cast, TC). We attribute the higher performance attained by our in-lab fabricated PF papers to the presence of macro pores which provided channels that acted as pathways for electrolytic transport within the bulk of the electrode. Moreover, we propose an electrolytic transport mechanism to relate ion diffusivity to different pore sizes to explain the different modes of charge transfer in the negative and the positive electrolytes. Overall, the PF papers had a high wettability, high porosity, and a large surface area, resulting in improved electrochemical and flow-cell performances.

Hierarchical nano zeolite-Y hydrocracking composite fibers with highly efficient hydrocracking capability.

In this work, a hydrocracking catalyst, nano zeolite Y-NiO-WO3 is reshaped into nanofibrous form. This novel composite fiber show good mechanical strength together with a uniform elemental distribution for both the acidic and hydrogenation components as confirmed through scanning transmission electron microscopy. The catalyst is tested for n-heptane hydrocracking in a continuous flow fixed-bed reactor at reaction temperatures of 350 °C and 400 °C with a time on stream of 180 minutes. The fibers produced from nano zeolite-Y show superior performance with a total conversion of 98.81 wt% and 96.8 wt% at 350 °C and 400 °C respectively. In addition, a low amount of coke (0.40 wt% and 1.05 wt% at 350 °C and 400 °C respectively) was formed with the nano zeolite Y fibers. This superior performance is related to the enhanced accessibility due to the nanofiber shape where the non-woven mesh/network of catalytic fibers prevents the agglomeration of the nanoparticles. Agglomeration is a major cause of hindered accessibility of the reactants to the catalyst active sites. The zeolite particle size, and the shape of the fibrous catalyst, together with its mesoporous character (as confirmed through BET analysis) enhances diffusion and improves accessibility for the reactants to react on the catalytic active sites as proven by the high total n-heptane conversions and high hexane and iso hexane selectivity for n-heptane hydrocracking.

Fog-harvesting potential of lubricant-impregnated electrospun nanomats.

Hydrophobic PVDF-HFP nanowebs were fabricated by a facile electrospinning method and proposed for harvesting fog from the atmosphere. A strong adhesive force between the surface and a water droplet has been observed, which resists the water being shed from the surface. The water droplets on the inhomogeneous nanomats showed high contact angle hysteresis. The impregnation of nanomats with lubricants (total quartz oil and Krytox 1506) decreased the contact angle hysteresis and hence improved the roll off of water droplets on the nanomat surface. It was found that water droplets of 5 µL size (diameter = 2.1 mm) and larger roll down on an oil-impregnated surface, held vertically, compared to 38 µL (diameter = 4.2 mm) on a plain nanoweb. The contact angle hysteresis decreased from ~95 to ~23° with the Krytox 1506 impregnation.

Nanocrystalline cellulose extraction process and utilization of the byproduct for biofuels production.

Cellulose consists of amorphous and crystalline regions. It is the crystalline regions which may be exploited to produce nanocrystalline cellulose (NCC). In order to extract nanocrystalline cellulose from native cellulose, sulfuric acid hydrolysis is typically used. The amorphous regions of cellulose are hydrolyzed and degraded into soluble products while the crystalline regions remain intact. In an effort to make the NCC extraction process more feasible, a new process was developed to recover and utilize the hydrolyzed regions of cellulose as a byproduct. The acid hydrolyzed amorphous regions were separated and then recovered (regenerated) into solid particles. XRD data revealed that the recovered material is characteristic of cellulose II. Hydrolysis conditions were optimized to maximize the yield of the recovered material and at the same time produce NCC material. Preliminary experiments showed yield values of approximately 61% for the cellulose I crystalline portions and values of about 21.7% for the recovered material (cellulose II). Enzymatic hydrolysis experiments of the recovered material revealed high susceptibility to enzymatic hydrolysis which makes it a promising source for biofuels production.

Modified cellulose morphologies and its composites; SEM and TEM analysis.

The complex, multi-level super molecular architecture of cellulose has been the subject of interest for several decades. The mechanical, physical, and environmental properties of cellulose depend on the molecular, supramolecular and morphological structure of the cellulose. This paper gives a brief overview to micro structural analysis of cellulose, as studied using transmission electron microscopy and scanning electron microscopy. The application of these techniques to study the diverse morphology of cellulose and its composites is illustrated using several examples.