Novel metal-complexing membrane containing poly(4-vinylpyridine) for removal of Hg(II) from aqueous solution.

A novel poly(vinyl alcohol)/poly(4-vinylpyridine) (PVA/P(4)VP) complexing membrane for removal of Hg(II) ions from aqueous solutions represents a significant improvement over a previously reported PVA/poly(ethylenimine) (PEI) membrane. This membrane was prepared by the semi-interpenetrating polymer network technique, and its cross-linking by three different agents was studied. The best results were obtained with gaseous 1,2-dibromoethane at 140 degrees C for 1 h that gave a membrane with a swelling ratio of 0.66. The sorption reaction of Hg(II) followed a first-order rate law, and the rate-limiting step was shown to be the association of Hg(II) ions with the complexing sites of P(4)VP. Sorption experiments at pH 2.5 showed that the retention ratio could reach 100% under optimized conditions for the initial concentration of Hg(II) and mass of membrane, c(0) = 100 mg L(-1) and m(D) = 100 mg, respectively. The retention ratio was remarkably insensitive to water hardness or the presence of NaCl, suggesting possible use for the purification of real wastewaters. The retention capacity of the membrane was 450 mg g(-1) compared to 311 mg g(-1) reported for the PVA/PEI membrane. Sorption isotherms were determined at various temperatures, according to the Langmuir model, for the determination of the thermodynamical parameters. When T increased, mercury uptake at equilibrium did not change, whereas the sorption coefficient b decreased and the change in free energy DeltaG degrees decreased. This result is probably due to a large favorable entropic effect, ascribed to the displacement of protons from the protonated sites of P(4)VP while they bind with Hg(II) ions. The membrane could be regenerated by 0.5 M nitric acid with less than 3% loss of efficiency. The membrane was used for filtration experiments. The elimination ratio was 99.9% or more for filtration of Hg(II) solutions in the c(0) = 16.6-89.1 mg L(-1) range.