Novel mixed matrix dense and supported membranes based on biopolymer sodium alginate (SA) modified by fullerenol were developed. Two kinds of SA–fullerenol membranes were investigated: untreated and cross-linked by immersing the dry membranes in 1.25 wt % calcium chloride (CaCl2) in water for 10 min. The structural and physicochemical characteristics features of the SA–fullerenol composite were investigated by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopic methods, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), and swelling experiments. Transport properties were evaluated in pervaporation dehydration of isopropanol in a wide concentration range. It was found that the developed supported cross-linked SA-5/PANCaCl2 membrane (modified by 5 wt % fullerenol) possessed the best transport properties (the highest permeation fluxes 0.64–2.9 kg/(m2 h) and separation factors 26–73,326) for the pervaporation separation of the water–isopropanol mixture in the wide concentration range (12–90 wt % water) at 22 °C and is suitable for the promising application in industry.
Membrane methods, especially pervaporation, are quickly growing up. In line with that, effective membrane materials based on biopolymers are required for the industrially significant mixtures separation. To essentially improve membrane transport characteristics, the application of the surface or/and bulk modifications can be carried out. In the present study, novel dense and supported membranes based on hydroxyethyl cellulose (HEC)/sodium alginate (SA) were developed for pervaporation dehydration of isopropanol using several approaches: (1) the selection of the optimal ratio of polymers, (2) the introduction of fullerenol in blend polymer matrix, (3) the selection of the optimal cross-linking agent for the membranes, (4) the application of layer-by-layer deposition of polyelectrolytes on supported membrane surface (poly(sodium 4-styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) and PSS/SA). Structural and physicochemical characteristics of the membranes were analyzed by different methods. A cross-linked supported membrane based on HEC/SA/fullerenol (5%) composite possessed the following transport characteristics in pervaporation dehydration of isopropanol (12–50 wt.% water): 0.42–1.72 kg/(m2h) permeation flux, and 77.8–99.99 wt.% water content in the permeate. The surface modification of this membrane with 5 bilayers of PSS/PAH and PSS/SA resulted in the increase of permeation flux up to 0.47–3.0 and 0.46–1.9 kg/(m2h), respectively, with lower selectivity.
Ethylene glycol (EG) is widely used in various economic and industrial fields. The demand for its efficient separation and recovery from water is constantly growing. To improve the pervaporation characteristics of a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membrane in dehydration of ethylene glycol, the modification with graphene oxide (GO) nanoparticles was used. The effects of the introduction of various GO quantities into the PPO matrix on the structure and physicochemical properties were studied by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), swelling experiments, and contact angle measurements. Two types of membranes based on PPO and PPO/GO composite were developed: dense membranes and supported membranes on a fluoroplast substrate (MFFC). Transport properties of the developed membranes were evaluated in the pervaporation dehydration of EG in a wide concentration range (10–90 wt.% and 10–30 wt.% water for the dense and supported membranes, respectively). The supported PPO/GO(0.7%)/MFFC membrane demonstrated the best transport properties in pervaporation dehydration of EG (10–30 wt.% water) at 22 °C: permeation flux ca. 15 times higher compared to dense PPO membrane—180–230 g/(m2·h)), 99.8–99.6 wt.% water in the permeate. The membrane is suitable for the promising industrial application.
Transport characteristics of sodium alginate (SA) membranes cross-linked with CaCl2 and modified with fullerenol and fullerene derivative with L-arginine for pervaporation dehydration were improved applying various approaches, including the selection of a porous substrate for the creation of a thin selective SA-based layer, and the deposition of nano-sized polyelectrolyte (PEL) layers through the use of a layer-by-layer (Lbl) method. The impacts of commercial porous substrates made of polyacrylonitrile (PAN), regenerated cellulose, and aromatic polysulfone amide were investigated by scanning electron microscopy (SEM), atomic force microscopy (AFM), standard porosimetry method, and water filtration. The effects of PEL combinations (such as poly(sodium 4-styrene sulfonate) (PSS)/SA, PSS/chitosan, PSS/polyacrylic acid, PSS/poly(allylamine hydrochloride)) and the number of PEL bilayers deposited with the Lbl technique on the properties of the SA and SA/fullerene derivative membranes were studied by SEM, AFM, and contact angle measurements. The best characteristics were exhibited by a cross-linked PAN-supported SA/fullerenol (5%) membrane with five PSS/SA bilayers: permeation flux of 0.68–1.38 kg/(m2h), 0.18–1.55 kg/(m2h), and 0.50–1.15 kg/(m2h), and over 99.7, 99.0, and 89.0 wt.% water in the permeate for the pervaporation dehydration of isopropanol (12–70 wt.% water), ethanol (4–70 wt.% water), and tetrahydrofuran (5.7–70 wt.% water), respectively. It was demonstrated that the mutual application of bulk and surface modifications essentially improved the membrane’s characteristics in pervaporation dehydration.
Wide application of ultrafiltration in different industrial fields requires the development of new membranes with tailored properties and good antifouling stability. This study is devoted to the improvement of ultrafiltration properties of poly(m-phenylene isophtalamide) (PA) membranes by modification with titanium oxide (TiO2) particles. The introduction of TiO2 particles improved membrane separation performance and increased antifouling stability and cleaning ability under UV irradiation. The developed membranes were characterized by scanning electron and atomic force microscopy methods, the measurements of water contact angle, and total porosimetry. The transport properties of the PA and PA/TiO2 membranes were tested in ultrafiltration of industrially important feeds: coolant lubricant (cutting fluid) emulsion (5 wt.% in water) and bovine serum albumin (BSA) solution (0.5 wt.%). The PA/TiO2 (0.3 wt.%) membrane was found to possess optimal transport characteristics in ultrafiltration of coolant lubricant emulsion due to the highest pure water and coolant lubricant fluxes (1146 and 32 L/(m2 h), respectively), rejection coefficient (100%), and flux recovery ratio (84%). Furthermore, this membrane featured improved ability of surface contamination degradation after UV irradiation in prolonged ultrafiltration of BSA, demonstrating a high flux recovery ratio (89–94%).
The aim of the study is to improve the performance of thin-film composite (TFC) membranes with a thin selective layer based on chitosan (CS) via different approaches by: (1) varying the concentration of the CS solution; (2) changing the porosity of substrates from polyacrylonitrile (PAN); (3) deposition of the additional ultrathin layers on the surface of the selective CS layer using interfacial polymerization and layer-by-layer assembly. The developed membranes were characterized by different methods of analyses (SEM and AFM, IR spectroscopy, measuring of water contact angles and porosity). The transport characteristics of the developed TFC membranes were studied in pervaporation separation of isopropanol/water mixtures. It was found that the application of the most porous PAN-4 substrate with combination of formation of an additional polyamide selective layer by interfacial polymerization on the surface of a dense selective CS layer with the subsequent layer-by-layer deposition of five bilayers of poly (sodium 4-styrenesulfonate)/CS polyelectrolyte pair led to the significant improvement of permeance and high selectivity for the entire concentration feed range. Thus, for TFC membrane on the PAN-4 substrate the optimal transport characteristics in pervaporation dehydration of isopropanol (12–90 wt.% water) were achieved: 0.22–1.30 kg/(m2h), 99.9 wt.% water in the permeate.