Quanxing Zhang

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent.

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.

Adsorption of phenolic compounds on Amberlite XAD-4 and its acetylated derivative MX-4

Amberlite XAD-4 polymeric resin was chemically modified with an acetyl group, which enables the resin to be used directly without a wetting process. The modified resin was comparatively evaluated using four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol. The capacities of equilibrium adsorption for all four phenolic compounds from their aqueous solutions increased around 20% on the acetylated resins within temperature range of 283–323 K. Freundlich isotherm equations, as well as the relative adsorptive capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate a physical and multiple-layer adsorption process on the Amberlite XAD-4 resins either with or without the chemical modification. Mini-column adsorption studies showed that the breakthrough adsorption capacity and the total adsorption capacity at designated conditions for all four phenolic compounds also increased over 20% after chemical modification.

Highly efficient removal of heavy metals by polymer-supported nanosized hydrated Fe(III) oxides: Behavior and XPS study

The present study developed a polymer-based hybrid sorbent (HFO-001) for highly efficient removal of heavy metals [e.g., Pb(II), Cd(II), and Cu(II)] by irreversibly impregnating hydrated Fe(III) oxide (HFO) nanoparticles within a cation-exchange resin D-001 (R-SO(3)Na), and revealed the underlying mechanism based on X-ray photoelectron spectroscopy (XPS) study. HFO-001 combines the excellent handling, flow characteristics, and attrition resistance of conventional cation-exchange resins with the specific affinity of HFOs toward heavy metal cations. As compared to D-001, sorption selectivity of HFO-001 toward Pb(II), Cu(II), and Cd(II) was greatly improved from the Ca(II) competition at greater concentration. Column sorption results indicated that the working capacity of HFO-001 was about 4-6 times more than D-001 with respect to removal of three heavy metals from simulated electroplating water (pH approximately 4.0). Also, HFO-001 is particularly effective in removing trace Pb(II) and Cd(II) from simulated natural waters to meet the drinking water standard, with treatment volume orders of magnitude higher than D-001. The superior performance of HFO-001 was attributed to the Donnan membrane effect exerted by the host D-001 as well as to the impregnated HFO nanoparticles of specific interaction toward heavy metal cations, as further confirmed by XPS study on lead sorption. More attractively, the exhausted HFO-001 beads can be effectively regenerated by HCl-NaCl solution (pH 3) for repeated use without any significant capacity loss.

Nitrate reduction using nanosized zero-valent iron supported by polystyrene resins: role of surface functional groups.

To probe the role of host chemistry in formation and properties of the inside nano-zero valent iron (nZVI), we encapsulated nZVI within porous polystyrene resins functionalized with -CH(2)Cl and -CH(2)N(+)(CH(3))(3) respectively and obtained two hybrid nZVIs denoted Cl-S-ZVI and N-S-ZVI. 14.5% (in Fe mass) of nZVI particles were distributed in N-S within a ring-like region (about 0.10 mm in thickness) of size around ∼ 5 nm, whereas only 4.0% of nZVI particles were entrapped near the outer surface of Cl-S of size > 20 nm. -CH(2)N(+)(CH(3))(3) is more favorable than -CH(2)Cl to inhibit nZVI dissolution into Fe(2+) ions under acidic pH (3.0-5.5). 97.2% of nitrate was converted into ammonium when introducing 0.12 g N-S-ZVI into 50 mL 50 mg N/L nitrate solution, while that for Cl-S-ZVI was 79.8% under identical Fe/N molar ratio. Under pH = 2 of the effectiveness of nZVI was 88.8% for nitrate reduction, whereas that for Cl-S-ZVI was only 14.6% under similar conditions. Nitrate reduction by N-S-ZVI exhibits relatively slower kinetics than Cl-S-ZVI, which may be related to different nZVI distribution of both composites. The coexisting chloride and sulfate co-ions are favorable for the reactivity enhancement of N-S-ZVI whereas slightly unfavorable for Cl-S-ZVI. The results demonstrated that support chemistry plays a significant role in formation and reactivity of the encapsulated nZVI, and may shed new light on design and fabrication of hybrid nZVIs for environmental remediation.

Facile Fabrication of Magnetic Chitosan Beads of Fast Kinetics and High Capacity for Copper Removal

In this study, magnetic chitosan (CS) beads of ∼200 nm in diameter were successfully prepared by a facile one-step method. The resultant composite Fe3O4-CS was characterized using transmission electron microscopy (TEM), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). Its adsorption toward Cu(II) ions was investigated as a function of solution pH, CS dosage, Cu(II) concentration, and contact time. The maximum capacity of Fe3O4-CS was 129.6 mg of Cu(II)/g of beads (617.1 mg/g of CS). More attractively, the adsorption equilibrium could be achieved within 10 min, which showed superior properties among the available CS-based adsorbents. Continuous adsorption-desorption cyclic results demonstrated that Cu(II)-loaded Fe3O4-CS can be effectively regenerated by ethylenediaminetetraacetic acid (EDTA) solution, and the regenerated composite beads could be employed for repeated use without significant capacity loss. Additionally, Fe3O4-CS beads can be readily separated from water within 30 s under a low magnetic field (<0.035 T).

Fabrication of polymer-supported nanosized hydrous manganese dioxide (HMO) for enhanced lead removal from waters

In the current study, a new hybrid adsorbent HMO-001 was fabricated by impregnating nanosized hydrous manganese dioxide (HMO) onto a porous polystyrene cation exchanger resin (D-001) for enhanced lead removal from aqueous media. D-001 was selected as a support material mainly because of the potential Donnan membrane effect exerted by the immobilized negatively charged sulfonic acid groups bound to the polymeric matrix, which would result in preconcentration and permeation enhancement of lead ions prior to their effective sequestration by the impregnated HMO. HMO-001 was characterized by scanning electron micrograph (SEM), transmission electron micrograph (TEM), and X-ray diffraction (XRD). Lead adsorption onto HMO-001 was dependent upon solution pH due to the ion-exchange nature, and it can be represented by the Freundlich isotherm model and pseudo-first order kinetic model well. The maximum capacity of HMO-001 toward lead ion was about 395 mg/g. As compared to D-001, HMO-001 exhibited highly selective lead retention from waters in the presence of competing Ca(2+), Mg(2+), and Na(+) at much greater levels than the target toxic metal. Fixed-bed column adsorption of a simulated water indicated that lead retention on HMO-001 resulted in a conspicuous decrease of this toxic metal from 1 mg/L to below 0.01 mg/L (the drinking water standard recommended by WHO). The exhausted adsorbent particles are amenable to efficient regeneration by the binary NaAc-HAc solution for repeated use without any significant capacity loss. All the results validated the feasibility of HMO-001 for highly effective removal of lead from contaminated waters.

Adsorption of naphthalene derivatives on hypercrosslinked polymeric adsorbents

Abstract Two hypercrosslinked resins CHA-101 and CHA-111 were used as polymeric adsorbents and the behaviours against the adsorption of four naphthalene derivatives-- l-naphthol, 2-naphthol, 1-naphthylamil and 2-naphthylamine were studied. Equilibrium adsorption data were obtained and fitted to the Freundlit isotherms. Results indicated that the CHA series resins were far more superior to macroporous Amberli XAD-4 in adsorbing naphthalene derivatives, and the CHA-101 resin demonstrated the highest adsorptic capacity. The difference in the adsorption property between the hypercrosslinked resins and tl conventional macroporous resin was attributed to the large specific surface area, uniform pore structul appropriate pore size and partial polarity of the network of the hypercrosslinked resins.

Adsorptive removal of phenol from aqueous phase by using a porous acrylic ester polymer.

The removal of phenol from aqueous solution was examined by using a porous acrylic ester polymer (Amberlite XAD-7) as an adsorbent. Favorable phenol adsorption was observed at acidic solution pH and further increase of solution pH results in a marked decrease of adsorption capacity, and the coexisting inorganic salt NaCl exerts positive effect on the adsorption process. Adsorption isotherms of phenol were linearly correlated and found to be well represented by either the Langmuir or Freundlich isotherm model. Thermodynamic parameters such as changes in the enthalpy (DeltaH), entropy (DeltaS) and free energy (DeltaG) indicate that phenol adsorption onto XAD-7 is an exothermic and spontaneous process in nature, and lower ambient temperature results in more favorable adsorption. Kinetic experiments at different initial solute concentrations were investigated and the pseudo-second-order kinetic model was successfully represented the kinetic data. Additionally, the column adsorption result showed that a complete removal of phenol from aqueous phase can be achieved by XAD-7 beads and the exhausted adsorbent was amenable to an entire regeneration by using ethanol as the regenerant. More interestingly, relatively more volume of hot water in place of ethanol can also achieve a similar result for repeated use of the adsorbent.

Bifunctional resin-ZVI composites for effective removal of arsenite through simultaneous adsorption and oxidation

Bifunctional resin-supported nanosized zero-valent iron (N-S-ZVI) composite was developed by combining the oxidation properties of nZVI/O2 with adsorption features of iron oxides and anion-exchange resin N-S. In batch culture experiments, N-S and the N-S-ZVI composite were examined for As(III) and As(V). The results reveal that ZVI in the composite played a key role in enhancing As(III) removal. The N-S-ZVI composites could oxidize more toxic As(III) to less toxic As(V) with high efficiency under ambient conditions without the need of noble metals. At the same time, the oxidized As(V) could be effectively removed by adsorption onto the surface of composites. The mechanisms for the oxidation of As(III) to As(V) and the simultaneous removal of As(V) are proposed. In order to investigate the potential performance of N-S-ZVI in practical use, the effects of solution pH and coexisting anions on arsenite removal and on fixed-bed column treatment of simulated waters were studied. All the results indicated that the bifunctional composites have a great potential for As(III) removal from contaminated waters.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin.

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henrys constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.