Covalently intercalated graphene oxide for oil–water separation

We report the transformation of hydrophilic graphene oxide (GO) sheets into superhydrophobic nanomaterial by direct esterification with epoxy-functionalized polyhedral oligomeric silsesquioxane (ePOSS). The covalently functionalized GO–ePOSS composite shows superhydrophobicity with a water/air contact angle of ∼145°. The highest dispersion limits for GO in selected organic solvents are obtained in the literature. The dispersion of GO–ePOSS can be extended to solvents with Hansen solubility parameters as low as 3.4. Efficient oil–water separation is also demonstrated by using a GO–ePOSS membrane.     

Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation

Blend PES/CA hydrophilic membranes were prepared via a phase-inversion process for oil–water separation. PEG-400 was introduced into the polymer solution in order to enhance phase-inversion and produce high permeability membranes. A gas permeation test was conducted to estimate mean pore size and surface porosity of the membranes. The membranes were characterized in terms of morphology, overall porosity, water contact angle, water flux and hydraulic resistance. A cross-flow separation system was used to evaluate oil–water separation performance of the membranes. From FESEM examination, the prepared PES/CA membrane presented thinner outer skin layer, higher surface porosity with larger pore sizes. The outer surface water contact angle of the prepared membrane significantly decreased when CA was added into the polymer solution. The higher water flux of the PES/CA membrane was related to the higher hydrophilicity and larger pore sizes of the membrane. From oil–water separation test, the PES/CA membrane showed stable oil rejection of 88 % and water flux of 27 l/m² s after 150 min of the operation. In conclusion, by controlling fabrication parameters a developed membrane structure with high hydrophilicity, high surface porosity and low resistance can be achieved to improve oil rejection and water productivity.     

Simultaneously spray-assisted assembling reversible superwetting coatings for oil–water separation

Here, superhydrophobic cuprous oxide(Cu_2O) with hierarchical micro/nanosized structures was synthesized via spray-assisted layer by layer assembling. The as-prepared superhydrophobic meshes with high contact angle(159.6°) and low sliding angle(1°) are covered with Cu_2O ‘‘coral reef"-like micro/nanosized structures. Interestingly, the superhydrophobic mesh surfaces became superhydrophilic again due to the oxidization of Cu_2O to CuO by annealing at a higher temperature(300 ℃). And the superhydrophobic properties would be recovered by heating at 120 ℃. Furthermore, the superwetting meshes were applied to design a miniature device to separate light or heavy oil from the water–oil mixtures with excellent separation efficiency. These superwetting surfaces by simultaneously spray-assisted layer by layer assembling technique show the potential application in universal oil–water separation.     

Superhydrophobic silk fibroin-silica melamine sponge for efficient oil–water separation

Journal of Porous Materials - This study developed a facile and environmentally-friendly method to prepare SiO2/silk fibroin (SF) composite melamine sponges modified using SF and hydrophobic SiO2...     

Recyclable porous polyurethane sponge for highly efficient oil–water separation

Oil spills and chemical leakages have caused severe environmental problems. Physical absorption of the spilled oils and chemical reagents by absorbing materials is an efficient and economical approach to solve these problems. Herein, we have prepared a porous thermoplastic polyurethane (TPU) sponge by combining the thermally induced phase separation method with the selective dissolution of water-soluble PEG components. The selective removal of PEG components from the walls of TPU sponges could increase the intensities of free volume holes and surface areas of TPU sponges. The content of free volume holes and surface areas of TPU sponge reached its maximum with the TPU/PEG ratio of 1:1. The increased roughness could improve the absorption capacities of TPU sponges for various oils/organic solvents. Moreover, due to its excellent compressibility, this TPU sponge could be reused 20 times with little loss of saturated absorption capacity. In addition, this TPU sponge exhibited excellent separation ability for the toluene from the toluene/water mixture and emulsion. In all, we have developed a facile method to prepare TPU sponge absorbent with excellent absorption performance, which holds great potential in the application of large-scale oil/water separation.     

Superhydrophobic–superoleophilic electrospun nanofibrous membrane modified by the chemical vapor deposition of dimethyl dichlorosilane for efficient oil–water separation

Superhydrophobic and superoleophilic functionalized electrospun poly(vinylidene fluoride) (PVDF) membranes with water repellence, breathability, and oil-sorption and oil–water separation properties were achieved with a combination of an electrospinning technique and the chemical vapor deposition of dichlorodimethyl silane. The samples were laterally characterized by scanning electron microscopy, atomic force microscopy, water contact angle measurement, and Fourier transform infrared spectroscopy. The maximum water contact angle value was 152.0 ± 2.5° for the PVDF nanofibrous membranes with 500 μL of deposited silane (PMS2) obtained under certain conditions. The PMS2 membranes showed 100.0, 93.7, 23.3, 35.0, and 100.0% separation efficiencies for n-hexane, kerosene, crude oil, frying oil, and toluene, respectively. The understudy membrane exhibited reasonable waterproofness and remarkable breathability (water vapor transition rate = 215.21 g/m².h). Moreover, the superhydrophobic and superoleophilic nanofibrous membranes also showed good reusability, stability, moderate water-repellent properties, breathability, antifouling properties, and oil–water separation ability after several cycles. These properties confirmed potential in feasible applications, including protective cloths and in the purification of oil-polluted water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47621.     

Electrospinning superhydrophobic–superoleophilic PVDF-SiO2 nanofibers membrane for oil–water separation

Oil–water separation has attracted research interest due to the damages of oily wastewater caused to the environment and human beings. Electrospun fiber membrane has high oil–water separation performance. A nanofibers membrane with multi-stage roughness was prepared by electrospinning using poly(vinylidene fluoride)(PVDF)-silica blend solution as raw material. The result shows that the water contact angle (WCA) of the nanofibers membrane was promoted from 138.5 ± 1° to 150.0 ± 1.5° when the SiO₂ content was increased from 0 to 3 wt%. The nanofibers membranes exhibited excellent separation efficiency (99 ± 0.1%) under gravity drive, with high separation flux of 1857 ± 101 L·m⁻²·h⁻¹. More importantly, the obtained PVDF-SiO₂ nanofibers membranes showed excellent multi-cycle performance and stable chemical resistance, which would make them great advantages for the practical application of oil–water separation.     

Hierarchical amphiphilic high-efficiency oil–water separation membranes from fermentation derived cellulose and recycled polystyrene

A high-efficiency separation of oil and water can be achieved by using specially designed amphiphilic porous membrane. However, the preparation of such membranes often involves complex multistep chemical processes. Herein, we report an amphiphilic composite membrane (polystyrene [PS]/bacterial cellulose [BC] membrane) consisting of hydrophobic recycled PS and hydrophilic BC, fabricated by a facile in situ fermentation process. Not only these membranes exhibit a combination of contrasting wettability but also comprise of a hierarchical network of microfibers and nanofibers, which makes them ideal for oil–water separation. The structural and morphological properties of as-produced BC, recycled PS membrane, and PS/BC composite membrane were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The ability of the membranes to separate oil and water was tested by using an emulsion of hexane-in-water as the feed and the collected filtrates were characterized by optical microscopy and UV–Vis spectroscopy. PS membranes were unable to separate oil and water, while the PS/BC membrane efficiently separated water from the emulsion. PS/BC composite membranes showed a high water recovery of more than 90%, against only 57% recovery shown by BC. Mechanisms of oil–water separation for each membrane are discussed. The reusability of the PS/BC composite membrane was also demonstrated.     

Experimental study of a vane-type pipe separator for oil–water separation

An experimental study of a new vane-type pipe separator (VTPS) was conducted for the possible application in the well-bore for oil–water separation and reinjection. Results by using particle image velocimetry (PIV) reveal a better flow field distribution for oil–water separation, which is formed in VTPS than that in hydrocyclone. The effects of split ratio, the oil content, guide vanes’ installation and number of guide vanes on oil–water separation performance have been investigated experimentally. Compared to a traditional single hydrocyclone, VTPS shows a good separation performance as the water content at the inlet of VTPS reaches 79.9%, the oil content at the water-rich outlet is about 400 ppm while the split is near 0.70. These results are helpful to provide a possibly new design for downhole oil–water separation.     

Using a simple method to prepare UiO-66-NH2/chitosan composite membranes for oil–water separation

Chitosan (CS) was used as a cross-linking agent to modify UiO-66-NH₂, and the modified UiO-66-NH₂ was fixed on the mixed cellulose membrane (MCE) through vacuum filtration technology to prepare a new type of membrane. The membrane exhibited excellent hydrophilicity in the air and excellent super-oleophobic performance underwater, and effectively separated various oil–water emulsions. When separating petroleum ether-water emulsion, the filtration flux of the modified membrane was 2000 L m⁻² h⁻¹ higher than that of MCE, and the separation efficiency can reach more than 95%. After 10 cycles, the flux of the modified membrane was about four times of that MCE, which was 500 L m⁻² h⁻¹. Most importantly, the membrane still maintained underwater superoleophobicity in the environment of strong acid, strong base, and salt solution.     

Modification of poly(vinylidene fluoride) membranes with aluminum oxide nanowires and graphene oxide nanosheets for oil–water separation

To improve the hydrophilic and oleophobic properties of membrane, we adopted aluminum oxide (Al₂O₃) nanowires and graphene oxide (GO) nanosheets to modify poly(vinylidene fluoride) (PVDF) membranes. The experimental results show that the intercalation of Al₂O₃ nanowires between GO nanosheets effectively improved the roughness of the GO–Al₂O₃–PVDF membrane, and the permeability of the membrane with an optimal mass ratio of Al₂O₃ to GO of 7.5 was 31 times that of the GO–PVDF membrane. Furthermore, the addition of Al₂O₃ nanowires significantly enhanced both the hydrophilic and oleophobic properties of the GO–Al₂O₃–PVDF membrane. On the basis of the extended Derjaguin–Landau–Verwey–Overbeek theory, the energy barriers between the oil droplets and GO–PVDF and GO–Al₂O₃–PVDF membranes were 0.63 and 0.9 KT, respectively; this indicated improvements in the anti-oil-fouling ability of the GO–Al₂O₃–PVDF membranes. We also found that both the GO–PVDF and GO–Al₂O₃–PVDF membranes had great oil–water separation rates (97.9 and 99.4%, respectively) with an initial oil concentration of 200 mg/L. The findings of this study show that the GO–Al₂O₃–PVDF membrane is a promising oil–water separation membrane, and further investigation of the cleaning procedure is needed to promote its practical application in oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47493.     

Enhancing oil–solid and oil–water separation in heavy oil recovery by CO2-responsive surfactants

Interfacial properties are of critical importance to various separation applications. In heavy oil recovery, for example, a low oil–water interfacial tension (IFT) benefits the separation of heavy oil from their host rocks, which becomes problematic in the later stage of oil–water separation. CO₂-responsive surfactants were investigated to enhance the overall heavy oil recovery by switching their interfacial activity to the desired state in each stage. The surfactants at interfacially active state greatly enhanced the separation of heavy oil from hosting solids, as demonstrated by measuring contact angle and oil liberation using a custom-designed on-line visualization system. Meanwhile, the resulting heavy oil-in-water emulsions could also be easily demulsified by the bubbling of CO₂ gas, which switched off the interfacial activity of the surfactants. Furthermore, CO₂-responsive surfactants could be partially recycled in process water to improve sustainability, making CO₂-responsive surfactants to be promising chemical aids in heavy oil production and many other vital industries.     

Mechanical milling of thermoresponsive poly(N-isopropylacrylamide) hydrogel for particle-oriented oil–water separation

The separation of oil and water is widely studied because of the promise of cleaning up oil spills. One pathway is with thermosensitive polymer-based hydrogels. As hydrogels are raised to the lower critical solution temperature (LCST), they undergo a change of state, from hydrophilic to hydrophobic. Oil–water separation using hydrogels in particle form that are responsive to external stimuli (e.g., magnetic field and temperature) are of great interest. This work uses a novel approach of ball milling dry hydrogel into different sizes and testing oil–water separation efficacy. This study investigated the potential for ball milling P(NIPAAm) bulk hydrogel into small particles size ranges (0–45, 45–90, 90–106, 106–150, and 150+ μm) and the resulting impact on oil–water separation. It was observed that the LCST for the p(NIPAAm) in gel form was 32 °C while increasing to ~40 °C for the powdered form. It was found that the hydrogel particles of different size ranges managed to capture 196, 207, 208, 162, and 124% of its weight in oil, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48771.     

Mathematical modelling of a hydrocyclone for the down-hole oil–water separation (DOWS)

In this study, a mathematical model is developed to predict the efficiency of a down-hole oil–water separation hydrocyclone. In the proposed model, the separation efficiency is determined based on droplet trajectory of a single oil droplet through the continuous-phase. The droplet trajectory model is developed using a Lagrangian approach in which single droplets are traced in the continuous-phase. The droplet trajectory model uses the swirling flow of the continuous-phase to trace the oil droplets. By applying the droplet trajectory, a trial and error approach is used to determine the size of the oil droplet that reaches the reverse flow region, where they can be separated. The required input for the proposed model is hydrocyclone geometry, fluid properties, inlet droplet size distribution and operational conditions at the down hole. The model is capable of predicting the hydrocyclone hydrodynamic flow field, namely, the axial, tangential and radial velocity distributions of the continuous-phase. The model was then applied for some case studies from the field tested DOWS systems which exist in the literature. The results show that the proposed model can predict well the split ratio and separation efficiency of the hydrocyclone. Moreover, the results of the proposed model can be used as a preliminary evaluation for installing a down-hole oil–water separation hydrocyclone system in a producing well.     

An oil-contamination-resistant PVP/PAN electrospinning membrane for high-efficient oil–water mixture and emulsion separation

Oil–water separation is an urgent issue due to the frequently occurred oil leakages and increasing discharge of oily wastewater. The pollutional and wastewater can not only damage the environment, but endanger human health. Owing to the small particle size of the oil contamination, it is still a challenge for the separation of oil–water emulsion. In this study, we developed a facile strategy to prepare a hydrophilic polyvinylpyrrolidone/polyacrylonitrile (PVP/PAN) nanofibrous membrane for oil–water mixture and emulsion separation. The lowest water contact angle on the membrane surface can achieve 16.7°, thus the membranes can effectively resist the oil contamination on them. Moreover, the membrane can efficiently separate oil–water mixtures and emulsion by gravity. In addition, it can separate oil–water mixtures in harsh conditions (pH = 1 and 14). Membranes prepared in this work would hold a great potential in the practical use of water treatment and environmental industry.     

Fabrication of superhydrophobic electrospun polyimide nanofibers modified with polydopamine and polytetrafluoroethylene nanoparticles for oil–water separation

The oil–water separation technologies of removing oil pollutants from water in an efficient and economical way is a challenge. The current methods used for oil–water separation suffer many shortcomings, including a low separation efficiency, complex separation equipment, high operation costs, and secondary pollution. In this study, we fabricated a highly flexible, high-intensity, quite stable superhydrophobic and superoleophilic polyimide (PI) nanofibrous membranes, which are much more efficient and cost efficient for oil–water separation by modifying the membranes with a polydopamine (PDA) solution and polytetrafluoroethylene (PTFE) dispersion. The fabricated membrane (PDA–PTFE–PI) possesses both the high tensile stress of PI and the superhydrophobic and superlipophilic properties of the PDA–PTFE coating. The modified membrane could separate various oil–water mixtures efficiently at a high flux (6000 L·m⁻²·h⁻¹) and an extremely high efficiency (>99%). Furthermore, even when the membrane was under an extremely hostile environment (with an ultrahigh temperature, strong acidity, or strong basicity), it still remained quickly stable with a good separation efficiency and recyclability after 10 cycles. We anticipate that our study will provide a new technology for the highly efficient mass production of oil–water mixture management. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47638.     

A facile method to functionalize engineering solid membrane supports for rapid and efficient oil–water separation

A facile and low-cost method is developed to functionalize engineering metal membrane supports, such as stainless steel (SS), with epoxy-containing polymer poly(glycidyl methacrylate) (PGMA) to produce a versatile and universal platform for subsequent surface modification. With a PGMA anchoring layer, we have demonstrated that hydrogel particles, such as polyacrylamide-co-poly(acrylic acid) (PAM-co-PAA), can be subsequently grafted to form functional polymer membranes for rapid and efficient oil–water separation. By contact angle and AFM measurement, we have confirmed that PAM-co-PAA hydrogel particle layer grafted on a PGMA-modified SS surface exhibits excellent selectivity as required for liquid–liquid separation, showing high affinity to water but not to oils as an ideal membrane for oil–water separation. To evaluate the separation efficiency, a simple flow-through device is employed to separate free-floating oil from water in the mixture of varied initial oil volume fraction and oil composition. Under substantially high pump flow rate up to 1.3 L/min, PAM-co-PAA hydrogel treated SS mesh can achieve excellent separation efficiency with less than 5% oil or water in the respective filtrate at the flux of as high as 540 m³/(m²·h) and retentate at the flux of 1.95 m³/(m²·h). This separation efficiency is better than, or comparable to, the maximal performance achieved using conventional gravity methods at much lower flow rate. Similar approach could be also adapted to graft superhydrophobic and superoleophilic polymer membranes with PGMA-treated engineering support to separate water from oil.     

Hydrophobic and fire-resistant carbon monolith from melamine sponge: A recyclable sorbent for oil–water separation

Here we report a new strategy for fabrication of macro/mesoporous carbon monolith from commercially available and low-cost melamine sponge. This synthesis route involves the cooperative self-assembly and coating of block copolymer mixed with resol on the melamine sponge, followed by pyrolysis at different temperatures. The as-fabricated carbon monolith exhibits high porosity and excellent hydrophobicity, thus can be used as a potential sorbent for the removal of oil from water. The intrinsic fire-resistant property of obtained carbon monolith makes it a recyclable sorbent for oil–water separation. More importantly, benefiting from the low-cost, available raw material and simple synthesis route, the production of the carbon monolith can be easily scaled up. This work offers a simple pathway to prepare carbon monolith, which is a promising candidate in the field of oil spill cleanup.     

Development of novel grafted hybrid PVA membranes using glycidyltrimethylammonium chloride for pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate incorporated hybrid poly(vinyl alcohol) membranes were grafted with glycidyltrimethylammonium chloride (GTMAC) in different mass%. The resulting membranes were subjected to physico-chemical investigations using Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and scanning electron microscopy (SEM). The effects of grafting and feed composition on pervaporation performance of the membranes were systematically investigated. The membrane containing 30 mass% of GTMAC exhibited the highest separation selectivity of 1570 with a flux of 1.92 × 10^?2 kg/m² h at 30 °C for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that these membranes could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are two to three times lower than those of isopropanol permeation (E_pIPA), suggesting that the developed membranes have higher separation ability for water–isopropanol system. The E_p and E_D values ranged between 63.73 and 33.07, and 62.78 and 32.75 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Henry's mode of sorption is predominant in the process.