Élimination des cations métalliques divalents : complexation par l'alginate de sodium et ultrafiltration Removal of divalent metallic cations: complexation by sodium alginate and ultrafiltration

Résumé

Depuis quelques années la pollution par les métaux lourds et devenue un problème important pour la protection de l'environnement et de nombreuses méthodes ont été développées pour éliminer les métaux toxiques présents dans l'eau.

Parmi les différents procédés utilisés, la complexation-ultrafiltration est bien connue et de nombreuses études sur ce sujet sont décrites dans la littérature. Cependant, le choix de nouveaux macroligands hydrosolubles demeure important pour développer cette technologie.

L'un des objectifs de ce travail était de montrer que dans ce procédé un biopolymère peut remplacer un macroligand de synthèse. Les expériences ont été menées avec de l'alginate de sodium, polysaccharide extrait des algues brunes, et porteur de groupements carboxyliques et hydroxydes capables de complexer les cations.

Notre étude se divise en trois parties. Après avoir décrit, dans la première, le matériau et les méthodes utilisées, nous étudions dans la seconde les conditions de l'ultrafiltration (seuil de coupure, pression appliquée, pH, concentration ), avant de discuter dans la troisième les résultats obtenus dans le traitement de solutions contenant Cd²⁺, Cu²⁺, Mn²⁺ and Pb²⁺.

Mots-clés:

• Ultrafiltration,
• complexation,
• alginate de sodium,
• cations métalliques

Abstract

For some years past, pollution by heavy metals has become one of the main problems for environmental protection. A number of methods have been developed to remove toxic metals from water. Among the various processes used, complexation-ultrafiltration is well known and numerous studies on this subject are described in the literature. However, the choice of new water-soluble macroligands remains important for developing this technology.

One aim of the present work was to prove that biopolymers can replace synthetic macroligands in the process. The experiments have been conducted with sodium alginate, a polysaccharide extracted from brown seaweeds and containing carboxylic and hydroxyl groups able to complex heavy cations. Filtration experiments were performed with a frontal system, equipped with a polysulfone membrane with a 20000 Daltons cut-off . The solutions studied were prepared by diluting in demineralized water either sodium alginate or "Titrisol Merck" for cations. Before filtration the two solutions were mixed and stirred for 20 min. The pH of the feed solutions was adjusted with HCl (or HNO3 for Pb) or NaOH and determined accurately using a calibrated probe.

The molecular weight of sodium alginate was determined by liquid chromatography and the viscosity was measured with either a viscosimeter for low values or a capillary method for concentrated solutions. Cation concentrations were measured by atomic absorption spectrophotometryBoth permeate and retentate macroligands concentrations were estimated from measurements of total organic carbon (TOC). Following each experiment, chemical cleaning was performed by filtration of HCl, NaOH and water. This procedure was followed by demineralized water filtration, to ensure that the initial permeability was restored.

In the first part of the work the ultrafiltration of sodium alginate solutions for different concentrations and various pressures was studied. Experimental results for macroligand retention, deduced from the TOC values, show a total rejection. All the curves, permeate flux versus time, present the same profile which indicates a significant concentration polarization. According to the obtained results we chose the value of 5 10^-2 g L^-1 for the ligand concentration and one bar for the applied pressure.

In the second part of the study, the retention of cations (Cd²⁺, Cu²⁺, Mn²⁺ and Pb²⁺) was investigated. The observed results show that the removal rates are close to 100%. These values depend both on the total concentration of cation and on the pH value. The retention of cations is shown to depend strongly on pH: a variation of pH between 3 and 5 leads to changes in retention efficiency from 0 to 100%. This can be explained by the dissociation of alginic acid as a function of pH. For lower pH values the macroligand is in a molecular form and the metallic cation remains free; for higher values metal complexation is possible, increasing the rejection. If coordination number, rejection rate and pH are known, the various association constants can be determined using a graphical method. It can be seen from the results that the stability of the complexes formed decreases in the sequence Pb>Cu>Mn>Cd.

In order to investigate the retention of these cations in a fresh water, the influence of calcium hardness was studied. The results indicate that cation removal decreases when the calcium concentration increases. This observation is an important restriction for fresh water treatment but does not affect the elimination of metals from a solution or an industrial waste containing cations.

Keywords:

• Ultrafiltration,
• complexation,
• sodium alginate,
• metallic cations