Studies on the development of improved reverse osmosis membranes from cellulose acetate–acetone–formamide casting solutions

Improved membranes from cellulose acetate–acetone–formamide casting solutions have been prepared for low-pressure reverse osmosis applications. The film-casting details for one such type of membranes (Batch 400) are as follows. Casting solution composition: cellulose acetate (E-398-3), 17 wt-%, acetone, 56 wt-%, formamide, 27 wt-%; temperature of casting solution, 24°C; temperature of casting atmosphere, 24°C; casting atmosphere, ambient air in contact with 30 wt-% acetone in aqueous solution; solvent evaporation period, 30 sec; gelation medium, ice-cold water. Using aqueous feed solutions containing 3500 ppm of NaCl, the product rates obtained with the above membranes at 95, 90, and 60% levels of solute separation were 15.9, 22.1, and 58.7 gallons/(day ft²), respectively, at 250 psig under feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec on the high-pressure side of the membrane. The effects of casting solution composition, presence of acetone in the casting atmosphere, evaporation period, evaporation rate constant, and the remoteness of casting solution composition from the corresponding phase boundary composition on membrane performance and shrinkage temperature profile were found to be similar to those reported earlier for membranes obtained from cellulose acetate–acetone–aqueous magnesium perchlorate casting solutions. The results illustrate the practical utility of the approach based on the solution structure–evaporation rate concept for creating more productive reverse osmosis membranes.     

Preparation and performance of sulfonated polysulfone flat ultrafiltration membranes

Sulfonated polysulfone (SPSF) flat ultrafiltration membranes were successfully prepared by immersion precipitation phase inversion method. N‐Methyl pyrrolidone was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a polymeric additive in the casting solution. The effects of casting solution formulation and preparation conditions on membrane structure and properties were investigated in present study, and the morphology of the membranes was analyzed by scanning electron microscopy. The results indicated that the performances of SPSF membranes made by chemical modification were better than polysulfone membrane. The SPSF concentration played a vital role in restricting the pure water flux (PWF), promoting the rejection coefficient, and improving the hydrophilicity. A maximum PWF and minimum egg albumin rejection coefficient were obtained when the PVP content was 10%. When the coagulation bath temperature was set to 25°C, the PWF reached 480 L·m^?2·h^?1 and the ovalbumin rejection coefficient reached 92%. Longer evaporation times improved the PWF. Specifically, when the evaporation time was 70 s, the comprehensive performance was good. POLYM. ENG. SCI., 55:1003–1011, 2015. © 2014 Society of Plastics Engineers     

Poly(ether sulfone) supported hybrid poly(vinyl alcohol)–maleic acid–silicone dioxide membranes for the pervaporation separation of ethanol–water mixtures

Microporous poly(ether sulfone) (PES) supported hybrid polymer–inorganic membranes were prepared by the crosslinking of poly(vinyl alcohol) (PVA), maleic acid (MA), and SiO₂ via an aqueous sol–gel route and a solution‐casting method. The membrane performance was tested for the pervaporation separation of ethanol–water mixtures from 20 to 60 °C with a feed ethanol concentration of 96 wt %. The membrane characterization results reveal that different SiO₂ loadings affected the crystallinity and roughness of the membranes. The PVA–MA–SiO₂ membrane containing 10 wt % SiO₂ showed that SiO₂ nanoparticles were well dispersed within the polymer matrix; this resulted in significant enhancements in both the flux and selectivity. The membrane achieved a high water permeability of 1202 g·μm·m^?2 h^?1 kPa^?1 and a selectivity of 1027 for the separation of a 96 wt % ethanol‐containing aqueous solution. This enhanced membrane performance might have been due to the dense crosslinking membrane network, increased free volume, and uniform distribution of SiO₂ nanoparticles. Both the water and ethanol fluxes increased with the feed water concentration and temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44839.     

Physicochemical processes occurring during the formation of cellulose diacetate membranes. Research of criteria for optimizing membrane performance. V. Cellulose diacetate–acetone–water–inorganic salt casting solutions

Consideration was given to the effects of casting conditions upon the performance and structure of membranes prepared from CA–acetone–water–inorganic salt solutions. Treating casting solutions as polymer–solvent–nonsolvent ternary systems, the data on equilibrium phase separation conditions were plotted in a triangular diagram for solutions containing Al(NO₃)₃, KSCN, Mg(ClO₄)₂ or no additive. Measurements of casting solution viscosity, membrane thickness, freezing and nonfreezing water contents were used to supplement flux and retention data of membranes made by varying the inorganic salt and holding time in a systematic way. With the aid of scanning and transmission electron microscopy, it was concluded that membranes may consist of one, two, three, or four layers. The data and correlations obtained allow us to propose a mechanism of formation for each of these layers.     

Potential of DMSO as greener solvent for PES ultra‐ and nanofiltration membrane preparation

In this article, the performance of polyethersulfone (PES) ultra‐ and nanofiltration membranes, prepared with the non‐toxic solvent dimethyl sulfoxide (DMSO), was investigated. The membranes were prepared by immersion precipitation via phase inversion. Experimental results proved that DMSO is a better alternative to N‐methyl‐2‐pyrrolidone (NMP) as solvent for PES ultrafiltration membranes as the membranes had a higher permeability and rejection of bovine serum albumin (BSA). An explanation was found based on experimental cloud point data and scanning electron microscopy images showing the morphology. The rejection of BSA and rose Bengal (RB) was proportional to the polymer concentration. On the contrary, the permeability decreased with increasing polymer concentration. For a casting thickness of 250 µm, an optimal balance between permeability and rejection of macromolecules for ultrafiltration was found at 24 wt % PES. The permeability was inversely proportional to the casting thickness, but a small decrease in rejection was observed when lowering the thickness. A good balance between permeability and rejection of RB was found, using a reference nanofiltration membrane of 28.5 wt % PES with 150 µm casting thickness. This membrane achieved a RB rejection of 95.3% and a pure water flux of 2.03 L m^?2 h^?1 bar^?1. The membrane thickness and polymer concentration did not have a clear influence on the hydrophilicity of the membranes. It can be concluded that DMSO is a benign alternative as compared to traditional solvents such as NMP and also results in better PES membrane performances. DMSO is a perfectly suitable solvent for ultrafiltration applications and has potential to be used for nanofiltration applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46494.     

Conducting blends of poly(o‐toluidine) and ethylene–propylene–diene terpolymer

Poly(o‐toluidine) (POT) is an electroactive polymer with poor mechanical and thermal characteristics. We examined the scope for improving such properties by making blends of POT with ethylene–propylene–diene rubber (EPDM). We prepared POT–EPDM blends containing different weight fractions of POT by intimately mixing known volumes of separate solutions of the two polymers (POT in THF and EPDM in toluene). Films of EPDM and POT–EPDM blends in solution were obtained by spreading, solvent evaporation, and film casting techniques. POT, EPDM, and their blends were characterized in solution by ultraviolet‐visible spectroscopy, and the respective dried samples were analyzed by Fourier transform infrared spectroscopy and thermogravimetry. The polymer samples were further analyzed morphologically by scanning electron microscopy, and their tensile strengths were also evaluated. Spectroscopic and thermal studies of the blends indicated some sort of interaction between the two constituent polymers. The direct current electrical conductivity of the blends in increasing order of POT loading (12.5–100%) was in the range 9.9 × 10^?5 to 11.6 × 10^?2 S cm^?1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2550–2555, 2003     

The effect of short air exposure periods on the performance of cellulose acetate membranes from casting solutions with high cellulose acetate content

Highly productive cellulose acetate membranes were cast under conditions of very short air exposure periods from cellulose acetate–acetone–formamide casting solutions having a high cellulose acetate (CA) content and lying close to the phase boundary. Air exposure periods as short as 0.05 sec were used with CA content up to 32 wt-%. Membranes from a casting solution containing 30 wt-% cellulose acetate (E-398-3), 45 wt-% acetone, and 25 wt-% formamide perform as well as membranes from other compositions at all salt rejection levels for a 0.5 wt-% NaCl feed at 600 psig. Partial replacement of acetone by dioxane in the casting solution substantially increases the water flux from membranes cast with short air exposure periods at any given salt rejection level below 96% salt rejection. Addition of small amounts of ZnCl₂ to nondioxane casting solutions with 32 wt-% CA improves membrane performances remarkably for lower salt rejection levels, while the improvement in performance of membranes from 30 wt-% CA casting solutions with dioxane due to ZnCl₂ addition is marginal. Variation in air exposure from 0.05 to 2 sec results in minor performance variations in the membranes having any of these compositions. With air exposure periods beyond 2–3 sec, membrane fluxes drop drastically. The concept of a thinner skin satisfactorily explains the improvement in mixed solvent systems, whereas ZnCl₂ acts as a swelling salt. A Kimura-Sourirajan-type membrane performance plot indicates that for a 0.5 wt-% NaCl feed at 600 psig, membranes of the present work perform as well as the best performing membranes reported in the literature for conversion of brackish water.     

Taurine as an additive for improving the fouling resistance of nanofiltration composite membranes

A hydrophilic compound, taurine, was investigated as an additive in the interfacial polymerization between piperazine (PIP) and trimesoyl chloride (TMC) to prepare thin‐film composite (TFC) membranes. The resulting membranes were characterized by X‐ray photoelectron spectroscopy and attenuated total reflectance–Fourier transform infrared spectroscopy. The morphology and hydrophilicity of the membranes were investigated through scanning electronic microscopy and water contact angle measurements. The separation performance of the TFC membranes was investigated through water flux and salt rejection tests. The protein‐fouling resistance of the films was evaluated by water recovery rate measurements after the treatment of bovine serum albumin. The membrane containing 0.2 wt % taurine showed the best performance of 92% MgSO₄ rejection at a flux of 31 L m^?2 h^?1 and better antifouling properties than the PIP–TMC membranes. An appropriately low concentration of taurine showed the same MgSO₄ rejection as the PIP–TMC membranes but a better fouling resistance performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41620.     

Preparation and properties of poly(acrylic acid) composite membranes

A new type of membrane has been prepared for hyperfiltration (reverse osmosis) desalination that is essentially a very thin polyelectrolyte membrane. It is prepared by casting an aqueous solution of a polyelectrolyte, specifically poly(acrylic acid) (PAA), directly on one surface of a finely porous support membrane. In hyperfiltration tests, these composite membranes exhibit desalination performance comparable in dilute solutions to that observed with cellulose acetate membranes of the Loeb-Sourirajan type. The water flux through these membranes is linear in the pressure up to 100 atm. Salt rejection is a function of pressure; it is also a function of the concentration of the feed solution and the charge of the counterion, in qualitative agreement with the Donnan ion-exclusion mechanism. Typical long-term results range from water fluxes of 2 × 10^?3 g/cm²-sec (50 gal/ft²-day) and 80% salt rejection to 0.2 × 10^?3 g/cm²-sec (5 gal/ft²-day) and >99.5% salt rejection at 1500 psi with 0.3 wt-% NaCl. These membranes appear to be useful for brackish water desalination.     

Ionically crosslinked poly(acrylic acid) membranes. III. Reverse osmosis results for dry cast membranes

The reverse osmosis properties of ionically crosslinked polyacrylic acid membranes were investigated in terms of the salt separation of a 0.1% NaCl solution and water flux. The membranes were synthesized and crosslinked with the metal ion Al³⁺ via the dry casting technique described in a previous paper. The effect of such variables as the polymer concentration in the casting solution, the ratios of solvents used (DMF/H₂O), the ratio of monomer to the crosslinking agent (AA/Al), the evaporation time and temperature, and the nonsolvent nature and treatment times were studied in some detail. The most important variable was found to be the length and nature of the treatment in the nonsolvents acetone and methanol. In the best series of the membranes that were synthesized, fluxes of more than 3.0 gfd, with salt separations at the 80%–85% level, were obtained.     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Codeposition of catechol–polyethyleneimine followed by interfacial polymerization for nanofiltration membranes with enhanced stability

Thin‐film composite (TFC) nanofiltration (NF) membranes were fabricated via the codeposition of catechol (CCh) and polyethyleneimine (PEI) followed by subsequent interfacial polymerization with trimesoyl chloride (TMC) on the surface of polysulfone ultrafiltration substrates. The detailed structures and surface properties were characterized by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, ζ potential analysis, and water contact angle measurement. The surface properties, including the roughness, hydrophilicity, surface potential, and NF performances, were facilely tuned through variation of the codeposition time of CCh–PEI for the prepared TFC membranes. The optimized membrane achieved a high rejection (ca. 93%) of MgCl₂ with a flux of around 31 L m^?2 h^?1 under 0.7 MPa. The results also reveal that the codeposition process endowed the final membranes with much better structural stability in alcohol and improved chlorine resistance compared to commonly interfacial polymerized ones with PEI and TMC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45422.     

Correlation of the polymer hydrophilicity and membrane fabrication process on the properties of asymmetric membranes in a vapor‐induced phase‐inversion process

In this study, we sought a better understanding of how the hydrophilicity of a polymer affects the morphology and performance of membranes. Three types of polymer with different hydrophilicity solution systems were considered: poly(aryl ether ketone) bearing a hydroxyl group (PEK–OH‐100) with N,N ‐dimethylformamide (DMF); poly(aryl ether ketone) bearing a 50% fraction hydroxyl group with DMF, and cardo poly(aryl ether ketone) with DMF. These systems were used to investigate the evolution of the morphology and variation in performance versus a change in the hydrophilicity of the polymer. In addition, the fundamental thermodynamic influence of the solution systems on the phase‐inversion process was investigated by cloud‐point measurement and Hansen solubility parameter theory to determine the role of polymer hydrophilicity on the stability of the polymer solution in humid surroundings. The performance of the membranes was tested via testing of the pure water flux, porosity, and rejection of bovine serum albumin (BSA) with respect to variations in the polymer hydrophilicity, evaporation time, relative humidity, and molecular weight of the polymer. The resulting optimal membrane exhibited a flux of 329.3 L m^?2 h^?1 and a 99.3% rejection of BSA at a relative humidity of 90% and an evaporation time of 3 s. The hydrophilic PEK–OH‐100 membranes have promising applications in protein separation and the porous support of reverse‐osmosis membranes and so on. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44701.     

High‐performance composite nanofiltration membranes fabricated via ternary mixture: Complementary preponderance of the fluorine‐containing monomer 2,2′‐bis(1‐hydroxyl‐1‐trifluoromethyl‐2,2,2‐triflutoethyl)‐4,4′‐methylene dianiline and the rigid monomer bisphenol F

In a previous study, we proved that tailoring the polyamide backbone stiffness is an effective way to fabricate high‐performance polyamide nanofiltration (NF) membranes. However, in the previous study, we mainly focused on the flat membrane and did not consider its chlorine tolerance. In this study, by regulating the aqueous‐phase compositions in the interfacial polymerization process, chlorine tolerance on NF hollow‐fiber membranes was endowed while the membrane performance stayed high. The experimental results show that when the ratio of Piperazine (PIP)–bisphenol F (BPF)/2,2′‐bis(1‐hydroxyl‐1‐trifluoromethyl‐2,2,2‐triflutoethyl)‐4,4′‐methylene dianiline (BHTTM) was 5:1:4, the NF membrane possessed a permeate flux of 21.0 L m^?2 h^?1 bar^?1 and an Na₂SO₄ rejection up to 90.0%. X‐ray photoelectron spectroscopy analysis also confirmed that the polymerization degree of the PIP–BPF–BHTTM NF membrane was the highest. Moreover, the NF membrane could tolerate active chlorine to over 10,000 ppm h Cl. After the active chlorine treatment, the permeate flux increased over 30.0 L m^?2 h^?1 bar^?1, and the Na₂SO₄ rejection was about 90.0%. Although the PIP–BHTTM NF membrane also possessed good chlorine tolerance, its permeate flux (after active chlorine treatment) was only 60% of that of the PIP–BPF–BHTTM NF membrane. Therefore, the PIP–BPF–BHTTM NF membrane possessed a combination of high flux and high chlorine tolerance and showed good potential in water treatment in rigorous environments. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46482.     

Physicochemical processes occurring during the formation of cellulose diacetate membranes. Research of criteria for optimizing membrane performance. IV. Cellulose diacetate-acetone-organic additive casting solutions

Asymmetric membranes were prepared from cellulose diacetate using a mixture of acetone and formamide, DMF, DMSO, NMP, dioxane or acetic acid as a basic solvent and water as the precipitation agent. The membrane water flux and salt rejection were determined by reverse osmosis tests. The change in mobility of the polymer chains during the evaporation and coagulation phases was studied by fluorescence depolarization. The main parameters such as casting solution composition, evaporation time, water concentration required for polymer precipitation, speed of coagulation and their effect on membrane structure and performance are discussed.     

Concentration of gelatin solution with polyethersulfone ultrafiltration membranes

In this work, polyethersulfone (PES) flat sheet ultrafiltration (UF) membranes were prepared by immersion precipitation phase inversion process with polyvinylpyrrolidone (PVP 30K) and acetone as additives. The best preparation condition for PES membranes with high water flux and rejection (to BSA) was decided. It was found that the optimal composition of the polymer casting solution was: 16 wt% (PES), 2 wt% (PVP 30K), and 1 wt% (acetone). Pure water flux of the membrane prepared at this condition reached to 373 L/m² h at 0.1 MPa, and the rejection to BSA was 91%. Compared with other reports, the rejection was slightly low but the flux of the PES membrane was high. When the membrane was used to concentrate gelatin solutions, the rejection value was over 75%. It was found that increasing the feed temperature and transmembrane pressure enhanced the permeation flux, but the rejection decreased slightly. However, increasing the cross-flow velocity of the feed solution simultaneously increased both the permeation flux and the rejection.     

Effects of mixed solvents and PVDF types on performances of PVDF microporous membranes

Polyvinylidene fluoride (PVDF) microporous flat membranes were cast with different kinds of PVDFs and four mixed solvents [trimethyl phosphate (TMP)–N,N‐dimethylacetamide (DMAc), triethyl phosphate (TEP)–DMAc, tricresyl phosphate (TCP)–DMAc, and tri‐n‐butyl phosphate (TBP)–DMAc]. The effects of different commercial PVDFs (Solef® 1015, FR 904, Kynar 761, Kynar 741, Kynar 2801) on membrane morphologies and membrane performances of PVDF/TEP–DMAc/PEG200 system were investigated. The membrane morphologies were examined by scanning electron microscopy (SEM). The membrane performances in terms of pure water flux, rejection, porosity, and mean pore radius were measured. The membrane had the high flux of 143.0 ± 0.9 L m^?2 h^?1 when the content of TMP in the TMP–DMAc mixed solvent reached 60 wt %, which was 2.89 times that of the membrane cast with DMAc as single solvent and was 3.36 times that of the membrane cast with TMP as single solvent. Using mixed solvent with different solvent solubility parameters, different morphologies of PVDF microporous membranes were obtained. TMP–DMAc mixed solvent and TEP–DMAc mixed solvent indicated the stronger solvent power to PVDF due to the lower solubility parameter difference of 1.45 MPa^1/2 and the prepared membranes showed the faster precipitation rate and the higher flux. The less macrovoids of the membrane prepared with TEP (60 wt %)–DMAc (40 wt %) as mixed solvent contributed to the higher elongation ratio of 96.61% ± 0.41%. Therefore, using TEP(60 wt %)–DMAc (40 wt %) as mixed solvent, the casting solution had the better solvent power to PVDF, and the membrane possessed the excellent mechanical property. The microporous membranes prepared from casting solutions with different commercial PVDFs exhibited similar morphology, but the water flux increased with the increment of polymer solution viscosity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Sulfonated poly(ether ether ketone)‐induced porous poly(ether sulfone) blend membranes for the separation of proteins and metal ions

Asymmetric ultrafiltration (UF) membranes were prepared by the blending of poly(ether sulfone) (PES) and sulfonated poly(ether ether ketone) (SPEEK) polymers with N,N′‐dimethylformamide solvent by the phase‐inversion method. SPEEK was selected as the hydrophilic polymer in a blend with different composition of PES and SPEEK. The solution‐cast PES/SPEEK blend membranes were homogeneous for all of the studied compositions from 100/0 to 60/40 wt % in a total of 17.5 wt % polymer and 82.5 wt % solvent. The presence of SPEEK beyond 40 wt % in the casting solution did not form membranes. The prepared membranes were characterized for their UF performances, such as pure water flux, water content, porosity, and membrane hydraulic resistance, and morphology and melting temperature. We estimated that the pure water flux of the PES/SPEEK blend membranes increased from 17.3 to 85.6 L m^?2 h^?1 when the concentration of SPEEK increased from 0 to 40 wt % in the casting solution. The membranes were also characterized their separation performance with proteins and metal‐ion solutions. The results indicate significant improvement in the performance characteristics of the blend membranes with the addition of SPEEK. In particular, the rejection of proteins and metal ions was marginally decreased, whereas the permeate flux was radically improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of THF as cosolvent in the preparation of polydimethylsiloxane/polyethersulfone membrane for gas separation

Polydimethylsiloxane/polyethersulfone (PDMS/PES) asymmetric membranes are widely applied in gas separation. However, the effects of common cosolvent on these membranes remain unknown. In order to study the changes in membrane morphology and gas separation properties, asymmetric PDMS/PES membranes were prepared. The studied parameters were types of cosolvents, tetrahydrofuran (THF) concentration, evaporation time, and PDMS concentration. Membrane morphology was examined using scanning electron microscopy and gas separation was conducted using pure CO₂, N₂, CH₄, and Hat 25°C. The addition of cosolvent into the polymer solution decreased the dope viscosity and delayed liquid–liquid demixing during phase inversion. Macrovoids formation was observed in substructure layer after adding THF and these macrovoids elongated with the reduction in THF content. There were microvoids formed on top of macrovoids and microvoids layer became thicker due to the increasing evaporation time of solvents before coagulation in nonsolvent. The PDMS coating on the PES membrane formed a dense skin layer and exhibited higher selectivity compared to the uncoated membrane. Membrane contained THF cosolvent with 60 s evaporation time and 3 wt% coated PDMS is the optimum membrane among other membranes in this work. The CO₂/N₂ selectivity was enhanced by 73.3% with CO₂ permeance of 44.86 GPU. POLYM. ENG. SCI., 54:2177–2186, 2014. © 2013 Society of Plastics Engineers     

Hydrophilic modification of a poly(ether sulfone) flat‐sheet ultrafiltration membrane applied to coking sewage

In this article, a new modified poly(ether sulfone) flat‐sheet ultrafiltration membrane, which is expected to effectively handle coking sewage, was prepared by an immersion precipitation phase‐inversion technique to settle the wastewater treatment problem in coking plants. Nanometer TiO₂ particle–poly(ethylene glycol) (PEG) blends were used as additives to modify the membranes by a blending method. The effects of different PEG mass concentrations on the membrane structure and properties were studied. The pure water flux and chemical oxygen demand (COD) rejection rate were analyzed as aggregative indicators by the comprehensive evaluation method, and then, the optimal PEG mass concentration was determined. The results show that the best modified effect was obtained at a PEG mass concentration of 0.25%. When coking sewage in a secondary settling tank was filtered with such membranes, the COD rejection rate reached 90.68%, and the water flux was 127.21 L m^?2 h^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45149.