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-SO3Na), 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～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.

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, whichwould 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 395mg/g. As compared to D-001,HMO-001 exhibited highly selective lead retention fromwaters in the presence of competing Ca2+,Mg2+, andNa+atmuch 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.

Phosphate originated from industrial effluents is one of the key factors responsible for eutrophication of the receiving waterways especially in the developing countries such as China. In the current study we proposed a novel process to immobilize nanoparticulate hydrated ferric oxide (HFO) within a macroporous anion exchange resin D-201, and obtained a hybrid adsorbent (HFO-201) for enhanced phosphate removal from aqueous system. The resulting HFO-201 possesses two types of adsorption sites for phosphate removal, the ammonium groups bound to the D-201 matrix and the loaded HFO nanoparticles. The coexisting sulfate anion strongly competes for ammonium groups, which bind phosphate through electrostatic interaction. However, it does not pose any noticeable effect on phosphate adsorption by the loaded HFO nanoparticles, which is driven by the formation of the inner-sphere complexes. Batch adsorption experiments also indicated that HFO-201 exhibits a little higher capacity for phosphate than the commercially available phosphate-specific adsorbent ArsenXnp, which possesses similar structure of HFO-201 and is produced by another patented technique. Fixed-bed column tests indicate that phosphate retention by HFO-201 from the synthetic waters results in the significant decrease of P from 2mg/L to less than 0.01mg/L, with the treatment capacity of w700 bed volume (BV) per run, while that for D-201 was less than 200 BV under otherwise identical conditions. Such satisfactory performance of the hybrid adsorbent is mainly attributed to the specific affinity of HFO toward phosphate as well as the Donnan membrane effect exerted by the anion exchanger support D-201. Moreover, the exhausted HFO-201 was amenable to efficient in situ regeneration with a binary NaOH-NaCl solution for repeated use without any significant capacity loss. Similar satisfactory results were also observed by using a phosphate-containing industrial effluent as the feeding solution.

Titanium phosphate (TiP) exhibits preferable sorption toward lead ion in the presence of competing calcium ions at high levels, however, it is present as fine or ultrafine particles and cannot be directly employed in fixed-bed or any flow-through systems due to the excessive pressure drop and poor mechanical strength. In the present study a new hybrid sorbent TiP-001 was fabricated by impregnating titanium phosphate (TiP) nanoparticles onto a strongly acidic cation exchanger D-001 for enhanced lead removal from waters. D-001 was selected as a host material mainly because of the Donnan membrane effect resulting from the immobilized sulfonic acid groups bound on the exchanger matrix, which would enhance permeation of the target metal cation prior to effective sequestration. TiP-001 was charac-terized by transmission electron micrograph (TEM), X-ray diffraction (XRD), and pH-titration. Batch and column sorption onto TiP-001 was assayed to evaluate its performance as compared to the host exchanger D-001. Lead sorption onto TiP-001 is a pH-dependent process due to the ion-exchange nature, and its sorption kinetics follows the pseudo-second-order model well. Compared to D-001, TiP-001 displays highly selective lead sorption in the presence of competing calcium cations at concentration of several orders higher than the target metal. Fixed-bed sorption of a synthetic feeding solution indicates that lead retention by TiP-001 results in a conspicuous decrease of this toxic metal from 0.50 to below 0.010mg/L (drinking water standard recommended by WHO). Moreover, its feasible regeneration by dilute HCl solution also favors TiP-001 to be a feasible sorbent for enhanced lead removal from water.

The adsorption equilibria of dimethyl phthalate (DMP) and diethyl phthalate (DEP) on two hyper-cross-linked polymer resins (NDA-99 and NDA-150) in aqueous solution were investigated at 298 K. And a coal-based granular activated carbon (AC-750) was chosen for comparison. All the adsorption equilibrium data of DMP were well fitted by the Polanyi-based isotherm modeling (Polanyi-Manes (PM) equation), and the characteristic curves of the three adsorbents were obtained. It is noteworthy that a reasonably good agreement was obtained between the combined micropore and mesopore volume of adsorbents and the corresponding adsorption volume capacity for phthalates. Compared to the granular activated carbon (AC-750), the greater adsorption performances of the two resins (NDA-99 and NDA-150) were assumed to result from their more abundant micro- and mesopore structure, where phthalates can be intensively adsorbed by pore-filling mechanism. According to the exponent b value of the PM equation, NDA-99 and NDA-150 show the more micro-and mesopore heterogeneity than AC-750. On the other hand, the functional groups on the adsorbent surfaces did not take a notable effect on the adsorption equilibria of phthalates. The theory equilibrium adsorption amounts of DEP, predicted by the specific characteristic curve of each adsorbent, agree well with the experimental ones, respectively. The characteristic curve of hyper-cross-linked polymer resins and its prediction of phthalates adsorption calculated by Polanyi-based isotherm modeling have a potential applicability for field applications.

The subject study revealed several unique properties of polymer-based zirconium phosphate (ZrP) for lead removal from waters. ZrP particles were impregnated within two porous polymers, namely, a chloromethylated polystyrene (CP) and a polystyrene cation exchange resin (D-001). Both as-prepared hybrid sorbents (designated ZrP-CP and ZrP-001, respectively) were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and a N2 adsorption-desorption test at 77K. As compared to the fresh particles, ZrP impregnated onto CP exhibits a slight increase in sorption capacity, which may result from their nanosized particles after impregnation. More attractively, ZrP-001 displays much higher sorption preference toward lead ions over calcium ions than ZrP, D-001, and ZrP-CP. Such significant phenomena is mainly attributed to the Donnan membrane effect exerted by the immobilized sulfonate groups on D-001 and further validates its potential application for enhanced removal of the toxic metal from contaminated waters.

The current study reports a potential process to selectively separate and preconcentrate tartaric acid from its simulated industrial effluent. It was achieved by sorption onto a tailored polymeric ligand exchanger. The polymeric ligand exchanger is essentially a copper(II)-bound specialty chelating polymer (denoted D-Cu). Effect of solution pH and competing sulfate on tartaric acid sorption onto D-Cu was also included in the study. Compared to a weakly basic anion exchanger D-301, D-Cu exhibits more favorable sorption of tartaric acid from aqueous media coexisting with Na2SO4 at a high level. The exhausted D-Cu was amenable to an entire regeneration by the diluted NaCl solution. Results of column sorption tests further demonstrated the feasibility of D-Cu for selective separation and preconcentration of tartaric acid from the simulated wastewater for its further recovery.

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 (△H), entropy (△S) and free energy (△G) 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.

Removal and recovery of aromatic pollutants from water by solid adsorbents have been of considerable concern recently. Relatively limited information is available on desorption kinetics and isotherms aspects. In the present study, batch desorption experiments of loaded 4-nitrophenol on a hyper-cross-linked polymer resin NDA-701, a polymeric adsorbent Amberlite XAD-4 and a granular activated carbon GAC-1 were carried out to study the effects of reaction temperature and pore-size distribution of adsorbents. 4-Nitrophenol desorbed rapidly in the early stages, followed by a much slower release, whichwas described well by a first-order two-component four-parameter model. The adsorption and desorption equilibrium isotherms were well described by Freundlich equation and the apparent adsorption-desorption hysteresis (hysteresis index) for 4-nitrophenol followed an order as: NDA-701≈XAD-4 GAC-1. Analysis of adsorption-desorption process suggested that higher reaction temperature and larger proportion of macropore of adsorbents favoured desorption kinetic and reduced adsorption-desorption hysteresis. All the results indicated that NDA-701, with a specific bimodal property in macro-and micropore region, had excellent potential as an adsorption material for achieving high removal and recovery of 4-nitrophenol from the contaminated water. These results will also advance the understanding of the adsorption and desorption behavior of hyper-cross-linked polymer resin in the wastewater treatment systems.