Abstracts
Résumé
Depuis le milieu du siècle dernier, nous savons que le fer existe à son degré d'oxydation supérieur VI dans l'ion tétraoxoferrate(VI) FeO42-, isostructural de SO42-, CrO42-, MnO42-. Cette espèce mise en solution aqueuse oxyde l'eau en O2, et ce quelque soit le pH de cette solution. La vitesse de cette réaction est très grande en milieu acide, plus lente en milieu alcalin où elle conduit à la précipitation de Fe(OH)3. On peut donc envisager son emploi comme réactif polyfonctionnel : oxydant et floculant, dans le traitement de certaines eaux.
La première partie de ce travail décrit une voie originale de synthèse à l'état solide, à la température ambiante, du sel de formule K2(Fe,S)O4, appelé sulfatoferrate de potassium, qui contient l'entité FeO42-. En effet, jusqu'à ce jour seules des synthèses par voie aqueuse, à rendements très faibles, chimiques ou électrochimiques, ont été utilisées pour obtenir FeO42-.
Dans une seconde partie, nous avons mesuré les propriétés oxydantes et floculantes du sulfatoferrate de potassium agissant sur deux types d'eaux usées urbaines, chargées (MEST=258 mg.L-1, DCO=549 mg.L-1) et peu chargées (MEST=9 mg.L-1, DCO=37 mg.L- 1). Cette étude effectuée en collaboration avec le Centre International de l'Eau de Nancy (NANC.I.E.) nous a permis de préciser les conditions optimales d'emploi de K2(Fe,S)O4 et de comparer ses performances à celles de FeCl3.6H2O et Al2(SO4)3.18H2O.
Sur une eau chargée, l'abattement de la MEST est meilleur avec FeCl3.6H2O et Al2(SO4)3.18H2O, tandis que K2(Fe,S)O4 est plus efficace vis à vis de l'abattement de la DCO.
Sur une eau peu chargée, c'est l'effet bactéricide de K2(Fe,S)O4 qui est le plus remarquable; une dose de 10 mg.L-1 en fer (VI) anéantit 99,70% des coliformes totaux et 99,90% des coliformes fécaux.
Mots-clés:
- Ferrate(VI), , , ,
- bactéricide,
- oxydant,
- coagulant
Abstract
Tetraoxoferrate(VI), FeO42-, possesses properties which make it potentially useful in certain areas of water purification: it is an excellent oxidizing agent, it has a powerful bactericidal action and it spontaneously decomposes over a short period of time. When reduced, the FeO42- ion generates base in solution and a Fe(OH)3 type gel which precipitates and carries down with it other ions (precipitation of hydroxide metal salts). These properties make ferrate(VI) useful in water disinfection and in wastewater treatment because it acts by an oxidation-coagulation-precipitation process.
Iron, in its familiar form exists in the (II) and (III) oxidation states; ferrate(VI) ion has long been known, but, due to its instability and difficulty of preparation, it has not been studied extensively and has not been industrially produced. In this paper, we recommend a method of synthesis of alkali ferrate(VI) salts by a dry powder process, which occurs at room temperature and can be easily used for industrial production of Fe(VI). To minimize ferrate(VI) decomposition, we proceed in a strong alkaline medium (presence of a strong base like potash or caustic soda) where oxidation of an iron (bivalent or trivalent) containing salt becomes easier. By such a synthesis process, we produce stabilized ferrate(VI) which enters a solid solution with the formula:
M2(Fe,X)O4
where M designates Na or K, X is an element whose cation has the electronic structure of a rare gas, e.g. X=S. M2XO4 is an isomorph of K2FeO4 with closed unit cell parameters. The M2(Fe,X)O4 formula has been established by chemical means and by X-ray diffraction; [sup]57Fe Mössbauer spectrometry has been used to monitor the hexavalent iron oxidation state. This paper deals with sulfatoferrate K2(Fe,S)O4 properties for compounds having Fe/S ratios between 1 and 1.5. in aqueous solution, K2(Fe,S)O4 dissolves and gives rise to FeO42- and SO42- anions.
In collaboration with NANC.I.E. (Centre International de l'Eau de Nancy), the effectiveness of K2(Fe,S)O4 in wastewater treatment has been studied. The product exhibits a real bactericidal effect on both coliforms and total bacteria. This bactericidal efficiency is reached in a short period of time with iron starting levels as low as 5-10 mg.L-¹. Comparative coagulation jar-tests were carried out on raw wastewater and on secondary effluent using FeCl3·6 H2O, Al2(SO4)3·18 H2O and K2(Fe[inf]0.54,S[inf]0.46)O4. Total suspended solids (TSS) removal on the raw wastewater was better with Al(III) and Fe(III) than with sulfatoferrate. On the secondary effluent, 40% removal was achieved with sulfatoferrate as well as with Fe(III). For removal of chemical oxygen demand (COD), better results were reached with Fe(VI) than with either Fe(III) or Al(III). The effectiveness of FeO42- after 30 minutes of contact with the bacterial medium (secondary effluent) has also been studied. At pH=8.5, a dose of 10 mg.L-¹ iron(VI) removes 99.70% of the total coliforms and 99.90% of the fecal coliforms.
Keywords:
- Ferrate(VI),
- bactericide,
- oxidizing agent,
- coagulation,
- wastewater