Glutaraldehyde cross-linked chitosan was loaded with palladium and then reduced by means of an in
situ hydrogen generation procedure (Zn in sulfuric acid solution) to prepare a chitosan-supported palladium
catalyst. This catalyst was successfully used to degrade nitrophenol in dilute solutions in the presence of
sodium formate as the hydrogen donor. The optimum initial pH was below pH 4. The pH strongly increased
during the reaction. The influence of the initial concentration of nitrophenol and sodium formate was
studied in order to determine the minimum molar ratio between these compounds to achieve the complete
conversion of the nitrogenous product. The pseudo-first-order equation was shown to fit degradation kinetics
in most cases; however, in some cases it was necessary to use a variable-order equation in order to model
the kinetics. Decreasing catalyst particle size increased degradation rate; the kinetic parameter varied
linearly with the reciprocal of the diameter, indicating that film diffusion may partially contribute to the
kinetic control of the reaction. The kinetic parameter linearly increased with catalyst dosage, while increasing
the palladium loading in the catalyst slightly increased degradation kinetics but the catalytic activity did
not increase proportionally. Catalytic activity appears to be restricted to external catalyst layers.
Chitosan has proved efficient at removing platinum in dilute effluents. The maximum uptake
capacity reaches 300 mg g-1 (almost 1.5 mmol g-1). The optimum pH for sorption is pH 2. A
glutaraldehyde cross-linking pretreatment is necessary to stabilize the biopolymer in acidic
solutions. Sorption isotherms have been studied as a function of pH, sorbent particle size, and
the cross-linking ratio. Surprisingly, the extent of the cross-linking (determined by the
concentration of the cross-linking agent in the treatment bath) has no significant influence on
uptake capacity. Competitor anions such as chloride or nitrate induce a large decrease in the
sorption efficiency. Sorption kinetics show also that uptake rate is not significantly changed by
increasing either the cross-linking ratio or the particle size of the sorbent. Mass transfer rates
are significantly affected by the initial platinum concentration and by the conditioning of the
biopolymer. Gel-bead conditioning appears to reduce the sorption rate. While for molybdate and
vanadate ions, mass transfer was governed by intraparticle mass transfer, for platinum, both
external and intraparticle diffusion control the uptake rate. In contrast with the former ions,
platinum does not form polynuclear hydrolyzed species, which are responsible for steric hindrance
of diffusion into the polymer network.
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