Preparation of core–shell glass bead/polysulfone microspheres with two‐step sol–gel process

Core–shell microspheres made from glass beads as the core phase and polysulfone (PSf) as the shell phase can act as an absorbent in the separation process or a supporter for chemical reactions. Based on phase‐inversion principles, a two‐step sol–gel method was developed in this work in which ether was added first and H₂O was added second to a PSf‐containing dimethyformamide (DMF) solution to help PSf solidify on the surface of glass beads. The results from scanning electron microscopy, Fourier transform IR, and X‐ray photoelectron spectroscopy showed that a dense layer of PSf (thin to several microns) was coated on the glass beads and the core–shell microspheres were almost monodispersed. The utilization percentages of the glass beads and PSf were high as 100 and 80%, respectively. The thickness of the PSf membrane was calculated to be about 4.3 μm. To obtain well‐monodispersed microspheres, the practical volume ratio of ether to DMF was recommended to be larger than 4.5. The results suggested that the two‐step sol–gel method is a highly efficient process for preparation of glass bead/PSf core–shell microspheres. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3365–3369, 2006     

DNA‐loaded porous polyethersulfone particles for environmental applications II. Utilization

DNA‐loaded porous polyethersulfone (PES) particles are fabricated using a liquid–liquid phase separation technique. The particles are then used for environmental applications. Both the DNA‐loaded porous PES particles and the DNA‐loaded PES porous particle column could accumulate and remove DNA intercalating pollutants, such as ethidium bromide, acridine orange, endocrine disruptors, and heavy metal ions. The microsphere column shows more high removal efficiency. These results proved that the DNA‐loaded porous particles have the potential to serve as absorbents for environmental applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1674–1678, 2005     

Use of chitosan for removal of bisphenol a from aqueous solutions through quinone oxidation by polyphenol oxidase

In this study, a combined use of biopolymer chitosan and oxidoreductase polyphenol oxidase (PPO) was applied to the removal of bisphenol A (BPA) as an endocrine disrupting chemical from aqueous solutions. The optimum conditions for the enzymatic quinone oxidation of BPA were determined to be pH 7.0 and 40°C. Quinone derivatives generated were chemisorbed on chitosan beads, and BPA was completely removed at 4–7 h. The removal time was shortened with an increase in the amount of dispersed chitosan beads or the PPO concentration. In addition, the initial velocity of quinone oxidation increased with an increase in the amount of chitosan beads. The use of chitosan in the form of porous beads was more effective than the use of chitosan in the form of solutions or powder. It was found that an important factor for this procedure was a high‐specific surface area of chitosan beads and heterogeneous reaction of quinone derivatives enzymatically generated with chitosan. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polysulfone‐Activated Carbon Hybrid Particles for the Removal of BPA

Abstract

Polysulfone‐activated carbon (PSF‐AC) hybrid particles are prepared using a liquid–liquid phase separation technique. The PSF‐AC hybrid particles are then used for the removal of bisphenol A (BPA) from its aqueous solutions. The PSF‐AC hybrid particles have similar structure as the polysulfone beads; both of them have a skin layer outside and a porous structure inside. The adsorption ability increased significantly when activated carbons were embedded into the particles, and the hybrid particles showed relatively more adsorption ability when the activated carbon content was 50%. The adsorbed BPA to the hybrid particles could be effectively removed by ethanol, which indicates that the hybrid particles can be reused. It is easy to prepare the particle column using these kinds of hybrid particles and the hybrid particle column could more effectively remove BPA. The results suggested that the PSF‐AC hybrid particles have a potential to be used for the removal of BPA in environmental application.     

常规水处理工艺对内分泌干扰物的去除

介绍了上海杨树浦水厂、宁波水系、天津水司常规水处理工艺净化去除内分泌干扰物及降低内分泌干扰活性的生产规模的测定情况。常规水处理工艺对13种中的11种内分泌干扰物有一定的去除效果，对内分泌干扰活性为阳性的水能转变为阴性，但也有小部分情况出厂水的干扰物浓度高于水源水，水源水内分泌干扰活性为阴性，而出厂水反而为阳性的情况，作者对这一情况进行了分析和探讨。     

Preparation of spherical polymer beads of maleic anhydride–styrene–divinylbenzene and metal sorption of its derivatives

Compounds having acid anhydride moiety have been used for starting materials for many useful derivatives. Spherical crosslinked polymer beads of porous maleic anhydride–styrene–divinylbenzene copolymer are obtained by suspension polymerization. Glycerol is found to be a preferable dispersant to make spherical beads. The beads contained 93% of the anhydride and 7% of the free carboxyls. As one of applications, the beads were hydrolyzed or reacted with anhydrous hydrazine, and the metal sorption behavior of them was examined. The hydrolyzed beads show a similar sorption manner as a conventional cation exchange resin having carboxylic acid groups, but the hydrazide beads sorbed mercury (II) selectively over a wide pH range. This investigation suggests a simple preparative method for the insoluble spherical porous beads of the maleic anhydride copolymer.     

Removal efficiencies of endocrine disrupting chemicals by coagulation/flocculation, ozonation, powdered/granular activated carbon adsorption, and chlorination

Removal efficiencies of endocrine disrupting chemicals (EDCs), bisphenol A and nonylphenol, during various types of water treatment processes were evaluated extensively using laboratory- and pilot-scale experiments. The specific processes of interest were coagulation/flocculation sedimentation/filtration (conventional water treatment process), powdered activated carbon (PAC), granular activated carbon (GAC), ozonation and chlorination. Batch sorption tests, coagulation tests, and ozone oxidation tests were also performed at higher concentrations with 14 EDCs including bisphenol A. The conventional water treatment process had very low removal efficiencies (0 to 7%) for all the EDCs except DEHP, DBP and DEP that were removed by 53%, 49%, and 46%, respectively. Ozonation at 1 mgO₃/ L removed 60% of bisphenol A and 89% of nonylphenol, while chlorination at 1 mg/L removed 58% and 5%, respectively. When ozone and chlorine doses were 4 and 5 mg/L, respectively, both EDCs were not detected. PAC removal efficiencies ranged from 15% to 40% at 3 to 10 mg/L of PAC with a contact time of 15 minutes. In the high concentration batch sorption tests, EDC removal efficiencies by PAC were closely related to octanol-water partition coefficient (K_ow). GAC adsorption was very effective water treatment process. The type and service time of GAC did not affect EDC removal efficiencies. The combination of ozonation and GAC in series appears to remove EDCs effectively to safe levels while conventional water treatment could not.     

Removal of endocrine disruptors in milk by circulation through polydimethylsiloxane tubing

A simple circulating system was developed, in which an aqueous solution, cow milk, or human milk was circulated through hydrophobic polymeric tubing to remove the endocrine disruptors from the solution by sorption into the tubing. The effect of circulating parameters, such as tube length, circulating time, and flow rate, against the removal ratio (R) of endocrine disruptors was investigated. R of 1,2,3,4,5,6‐hexachlorocyclohexane (γ‐HCH, lindane) increased with the length of the hydrophobic polymeric tubing, circulating time, and flow rate when cow milk containing 1 ppm γ‐HCH was circulated through polydimethylsiloxane tubing. The R values of several endocrine disruptors with different octanol–water distribution coefficients (log P_ow) was investigated for γ‐HCH and dichlorodiphenyltrichloroethane in an aqueous solution, cow milk, and human milk. A similar trend for R versus log P_ow of the human milk to that of the aqueous solution and cow milk was observed. The R values of the endocrine disruptors decreased in the following order: Aqueous solution > Human milk > Cow milk. Stable micelles in cow milk disturbed the shift of the endocrine disruptors from the milk micelles into the hydrophobic tubing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3634–3640, 2006     

Cyclodextrin‐dendrimer functionalized polysulfone membrane for the removal of humic acid in water

Commercial polysulfone (PSf) membranes were crosslinked with a β‐cyclodextrin‐poly (propyleneimine) (β‐CD‐PPI) conjugate which had β‐CD pendant arms using trimesoyl chloride (TMC) by interfacial polymerization. The morphology and physicochemical properties of the nanofiltration membranes were characterized using Fourier transform infrared/attenuated total reflectance (FT‐IR/ATR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cross‐flow filtration system. Water‐contact angle, water‐intake capacity, and rejection capacities of the membranes were evaluated. The β‐CD‐G4 (generation 4)‐PPI‐PSf and β‐CD‐G3 (generation 3)‐PPI‐PSf membranes both exhibited high humic acid rejection of 72% as compared to the commercial PSf which exhibited 57%. The modified membranes were also more hydrophilic (36° to 41°) than PSf (76°). These results suggest that β‐CD‐PPI nanostructures are promising materials for the synthesis of membranes for the removal of humic acid from water. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4428–4439, 2013     

Enhanced water flux through ultrafiltration polysulfone membrane via addition‐removal of silica nano‐particles: Synthesis and characterization

In the present paper, hierarchically structured ultrafiltration polysulfone (PSf) membrane was prepared to explore the effect of addition and subsequent removal of SiO₂ nano‐particles on the membrane morphology, hydrophilicity, and separation properties. The PSf based membranes namely PSf, PSf/SiO₂ and PSf/WSiO₂ (i.e. SiO₂ nano‐particles was acid‐washed and removed from PSf/SiO₂), were synthesized and characterized by different characterization methods. Pure water flux through the membranes was determined using a filtration unit operating at a continuous dead‐end flow mode. The modification enhanced the morphology, hydrophobicity, porosity and transport properties of the modified membranes, although the molecular weight cut‐off (MWCO) of the membranes was not changed considerably. In comparison, PSf/WSiO₂ membrane exhibited excellent pure water flux (about 4.5 times the flux of PSf, and 17 times the flux of PSf/SiO₂), although antifouling property of PSf/SiO₂ in separation of bovine serum albumin (BSA) was better than that of PSf and PSf/WSiO₂ membranes. The results suggested that the addition/removal of sacrificial solid fillers within/from a membrane matrix may provide a promising strategy to enhance PSf membrane transport property. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43556.     

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

Porous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of crosslinked β‐cyclodextrin polymer beads and their application as a sorbent for removal of phenol from wastewater

BACKGROUND: Phenols are commonly encountered in aqueous effluents from various manufacturing processes such as oil refineries, coke plants, and phenolic resin plants, and are toxic substances that should be removed from the aquatic environment. This paper reports on the preparation of beaded crosslinked β‐CyD polymers, and the removal of phenol by the β‐CyD adsorbent from raw industrial wastewater discarded from phenolic resin processing. RESULTS: Crosslinked β‐CyD prepolymer was synthesized by treatment of β‐CyD with hexamethylene diisocyanate (HDI) at a molar ratio of 1:8. The suspension of the resulting powdery prepolymer in aqueous sodium alginate was added dropwise into an aqueous calcium chloride solution to precipitate the spherical β‐CyD prepolymer gels. The spherical prepolymer gel was lyophilized and re‐crosslinked with HDI to provide the β‐CyD polymer beads. The physical properties of the beads were as follows: average diameter: 3.4 mm; average compressive strength: 2.17 MPa; porosity: 47.0%; specific surface area: 3.48 m² g^?1. The removal of phenol from raw industrial phenolic wastewater with the β‐CyD polymer beads was carried out in either a shaker or an upflow column at 25 °C. After seven episodes of accumulated adsorption, the initial phenol concentration of 89000 ppm decreased to as low as 350 ppm in the shaker and 490 ppm in the upflow column. CONCLUSION: Adsorbent [β‐CyD/HDI(1/8)]/HDI polymer beads having a good regular shape and high mechanical stability were newly prepared by a stepwise crosslinking method. The results of sorption experiments show that the beads exhibit high sorption capacities for phenolics in raw industrial wastewater. Copyright © 2008 Society of Chemical Industry     

Potential of carbon nanomaterials for removal of heavy metals from water

Heavy metals, such as, cadmium, lead, nickel and zinc can be removed from water using sorbents. The rate and extent of removal may be enhanced by choice of appropriate sorbents. In this study heavy metal sorption was studied on indigenously synthesized carbon nanomaterials (CNMs). Two CNMs differing in surface morphology were synthesized using turpentine oil in a chemical vapour deposition (CVD) setup by varying the process parameters. Activation and catalyst removal were achieved by post-treatment with HNO₃ and KOH. Characterization of the CNMs produced revealed that both comprised of graphitic amorphous carbon, however, while the nanocarbon (NC) produced using cobalt catalyst in N₂ atmosphere comprised of varying grain sizes indicative of soot, the nanoporous carbon (NPC) produced using silica catalyst in H₂ atmosphere had a distinctive uniformly porous surface morphology. Comparative sorption studies with cadmium, lead, nickel and zinc also revealed greater sorption on NPC compared to NC. Batch isotherms for the various heavy metals using NPC and a commercial activated carbon (AC) widely used for metal sorption revealed that NPC is characterized by significantly higher metal sorption capacity and more favourable sorption energetics. The superior performance of NPC as a sorbent may be due to its unique nanoporous structure.     

Removal of alkylphenols by the combined use of tyrosinase immobilized on ion‐exchange resins and chitosan beads

Mushroom tyrosinase was covalently immobilized on a poly(acrylic acid)‐type, weakly acidic cation‐exchange resin (Daiaion WK10, Mitsubishi Chemical Corp., Tokyo, Japan) with 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide hydrochloride salt as a water‐soluble carbodiimide. Ion‐exchange resins immobilized with tyrosinase were packed in one column, and crosslinked chitosan beads prepared with epichlorohydrin were packed in another column. The enzymatic activity was modified by covalent immobilization, and the immobilized tyrosinase had a high activity in the temperature range of 30–45°C and in the pH range of 7–10. When solutions of various alkylphenols were circulated through the two columns packed with tyrosinase‐immobilized ion‐exchange resins and crosslinked chitosan beads at 45°C and pH 7 (the optimum conditions determined for p‐cresol), alkylphenols were effectively removed through quinone oxidation with immobilized tyrosinase and subsequent quinone adsorption on chitosan beads. The use of chemically crosslinked chitosan beads in place of commercially available chitosan beads was effective in removing alkylphenols from aqueous solutions in shorter treatment times. The removal efficiency increased with an increase in the amount of crosslinked chitosan beads packed in the column because the rate of quinone adsorption became higher than the rate of enzymatic quinone generation. The activity of tyrosinase was iteratively used by covalent immobilization on ion‐exchange resins. One of the most important findings obtained in this study is the fact that linear and branched alkylphenols suspected of weak endocrine‐disrupting effects were effectively removed from aqueous solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Removal of As(V) species from extremely contaminated mining water

The effective removal of arsenic compounds from strongly contaminated mining water with a high content of As (about 50 mg/l) and other metals, especially iron (about 5000 mg/l) has been studied. The process ran in two steps. At first, the raw acid mining water containing predominantly Fe²⁺ ions was partially precipitated with a small amount of an alkaline agent. On a small portion of the precipitated iron (about 30–40%), more then 90% of the arsenic was adsorbed forming a toxic precipitate, which was then stirred under an inert agent (Ar) and further in air for 1 h. Secondly, the precipitation of the first step liquid residue (using the same or a different alkaline agent) enabled the final treatment of the mining water at pH 8.5. While arsenic was substantially removed by the first precipitation, the other components including residual iron, manganese, zinc and sulfates were precipitated quantitatively during the second step. The mass of the second precipitate depended strongly on the alkaline agent used in the second step.The mechanism and kinetics of arsenic sorption onto iron species, and phase changes of the sorbent during the sorption process were investigated. The composition of the precipitates was verified by XRD and XRF analyses, as well as by infrared and Raman spectroscopy. The precipitation of a raw mining water resulted in formation of a complex inorganic system where amorphous phases dominated. Various crystalline phases, predominantly concerning Fe(II)–Fe(III), As, Zn and sulfates also appeared, depending on the actual oxidizing state of the whole system and on redistribution of its components.The two-step precipitation of arsenic contaminated mining water results in a significant ecological and economical improvement due to the decrease in the amount of waste toxic mass.     

Hollow carbon beads fabricated by phase inversion method for efficient oil sorption

Hollow carbon beads of around 3.0 mm in diameter were prepared by a simple phase inversion method and subsequent carbonisation. Due to the low density and hydrophobic property, the hollow carbon beads were floatable on water. Different organic solvents and oils were used to study the oil sorption properties of the carbon beads. Their toluene sorption capacity was as high as 55% of their own volume. For long-chain oil like motor oil, the hollow carbon beads still adsorbed 40% of their volume. In addition, the hollow carbon beads could be refreshed by heat treatment, and the oil sorption capacity remained the same after being recycled five times. This work provides a facile and low-cost method for preparing highly efficient carbon-based sorbents for oil spill clean-up.     

The Removal of Atrazine from Water using Specific Polymeric Adsorbent

In order to obtain a specific polymer adsorbent for atrazine removal, the poly(divinylbenzene) beads were synthesized in radical polymerization using suspension polymerization, and modified with maleic anhydride in Diels-Alder reaction with subsequent base hydrolysis. The porous structure of the adsorbent was obtained by using various mixtures of solvents during the polymerization step; both porous and gel materials were prepared. The objective of the study was to investigate the sorption of atrazine by polymeric adsorbent and thereby evaluate the possibility of the pesticide residues’ removal from the aqueous solution. Implementation of carboxylic groups into the polymer structure resulted in obtaining specific interactions between modified poly(divinylbenzene) and atrazine, and therefore, intensification of adsorption was observed. To characterize the hydrogen bond between the herbicide and the adsorbent, quantum mechanics calculations were performed.     

Sorption capacity of a new generation granular activated carbon—Bio‐Sep® bead—and its use in a suspended growth bioreactor

BACKGROUND: A new generation granular activated carbon—Bio‐Sep® beads—consist of 25% polymer (Nomex) and 75% powdered activated carbon. The porous structure and high surface area of these beads make them suitable for sorbent in adsorption columns, and for immobilization media in bioreactors. The aim of this study was to study the sorption characteristics of Bio‐Sep® beads for methyl t‐butyl ether (MTBE) and t‐butyl alcohol (TBA), and to demonstrate the advantage of their usage in a suspended growth bioreactor. RESULTS: The maximum uptake capacity of Bio‐Sep® beads for MTBE and TBA, in the studied concentration range (10–100 mg L^?1), was observed to be 9.73 and 6.23 mg g^?1, respectively. A 52 h desorption experiment resulted in 13.6–42.2% MTBE and 33–53% TBA desorption corresponding to the initial solid phase concentrations of 1.68–9.73 mg g^?1 and 1.41–6.23 mg g^?1, respectively. The sorption of TBA on the Bio‐Sep® beads was significantly hindered by the presence of MTBE. The addition of 10 g Bio‐Sep® beads (dry weight) in a suspended growth bioreactor was able to eliminate the inhibitory effect of 150 mg L^?1 MTBE. CONCLUSIONS: At an equilibrium aqueous phase concentration (C_e) of 1 mg L^?1, the solid phase concentration (q_e) on Bio‐Sep® beads were observed as 1.44 and 0.47 mg g^?1 for MTBE and TBA, respectively. The results obtained in this study indicate that Bio‐Sep® beads have reasonable sorption and desorption characteristics, which can be successfully exploited for the removal/degradation of toxic organic pollutants in high rate bioreactors. Copyright © 2007 Society of Chemical Industry     

Film formation and crack development in plasma polymerized hexamethyldisiloxane

Plasma polymer thin coatings can be used in a variety of applications that require thin ultrasmooth, defect-free homogeneous films. In this study both film formation and crack development are described and related to the structure of the plasma polymer. The growth of a plasma polymer film reproduces the topography of the porous (polysulfone) PSf support and the time needed for complete coverage depends on the rate of deposition which is a function of the plasma power and monomer flow rate. The plasma polymerized hexamethyldisiloxane, PPHMDSO, film on a PSf porous support is under compressive internal stress causing the membrane to bend convexly with respect to the film. Despite these stresses, the composite membrane (film/support) did not crack when freely immersed in water and alcohols. Cracks developed in the mechanically constrained PPHMDSO composite membrane on exposure to alcohols. Films with more organic character showed high adhesion among the plasma polymer nodules and between the plasma polymer and the PSf substrate, resulting in substrate tearing and cracking straight through the plasma polymer layer.