Bingjun Pan

Development of polymer-based nanosized hydrated ferric oxides (HFOs) for enhanced phosphate removal from waste effluents

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 ArsenX(np), 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 0.01 mg/L, with the treatment capacity of approximately 700 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.

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.

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.

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.

Equilibrium and heat of adsorption of diethyl phthalate on heterogeneous adsorbents

Removal of phthalate esters from water has been of considerable concern recently. In the present study, the adsorptive removal performance of diethyl phthalate (DEP) from water was investigated with the aminated polystyrene resin (NDA-101) and oxidized polystyrene resin (NDA-702). In addition, the commercial homogeneous polystyrene resin (XAD-4) and acrylic ester resin (Amberlite XAD-7) as well as coal-based granular activated carbon (AC-750) were chosen for comparison. The corresponding equilibrium isotherms are well described by the Freundlich equation and the adsorption capacities for DEP followed the order NDA-702 > NDA-101 > AC-750 > XAD-4 > XAD-7. Analysis of adsorption mechanisms suggested that these adsorbents spontaneously adsorb DEP molecules driven mainly by enthalpy change, and the adsorption process was derived by multiple adsorbent-adsorbate interactions such as hydrogen bonding, pi-pi stacking, and micropore filling. The information related to the adsorbent surface heterogeneity and the adsorbate-adsorbate interaction was obtained by Dos model. All the results indicate that heterogeneous resins NDA-702 and NDA-101 have excellent potential as an adsorption material for the removal of DEP from the contaminated water.

Impregnating titanium phosphate nanoparticles onto a porous cation exchanger for enhanced lead removal from waters

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 characterized 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 0.010 mg/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.

Selective removal of Pb(II), Cd(II), and Zn(II) ions from waters by an inorganic exchanger Zr(HPO3S)2.

The present study reported synthesis of a new inorganic exchanger, i.e., zirconium hydrogen monothiophosphate [Zr(HPO3S)2, denoted ZrPS] and its selective sorption toward Pb(II), Cd(II) and Zn(II) ions. ZrPS sorption toward all the three metals is dependent upon solution pH due to the ion-exchange nature. As compared to another inorganic exchanger zirconium phosphate [Zr(HPO4)2, denoted ZrP], ZrPS exhibits highly selective sorption toward these toxic metals from the background of calcium ions at great levels. Such sorption preference is mainly attributed to the presence of -SH group in ZrPS, as further demonstrated by FT-IR analysis and XPS study. Moreover, ZrPS particles preloaded with heavy metals could be efficiently regenerated with 6M HCl for multiple use without any noticeable capacity loss. All the experimental results indicated that ZrPS is a promising sorbent for enhanced heavy metals removal from contaminated water.