Melanoidin is responsible for the dark brown color of distillery wastewater. Discharge of colored wastewater has a major environmental impact on the biota of the receiving water body. Consequently, this study explores the removal of melanodin from aqueous solution. The equilibrium, kinetics and thermodynamics of melanoidin sorption are studied by varying initial solution pH, initial concentration, adsorbent dose and temperature. Kinetically, the melanoidin removal from solution by a surfactant modified zeolite is rapid and the amount adsorbed is dependent on pH, initial concentration, adsorbent dose and temperature. The equilibrium sorption data are fitted to the Freundlich and Langmuir models while the sorption kinetics are described by the Ho pseudo-second order and Elovich models. The thermodynamic analysis indicates that the sorption is spontaneous and endothermic in nature. The FTIR spectra analyses show no new peaks or shift in peaks after sorption indicating that the melanoidin sorption may have occurred by a physical process. The results from desorption studies showed that melanoidin eluted back easily to the solution using distilled water which corroborates the physical sorption mechanism.

Melanoidin, a high molecular-weight heterogeneous pollutant in the effluents of molasses-using industries, poses a significant threat to the environment due to its non-biodegradability, unpleasant odour, and harmful effect. Various advanced oxidation processes (AOPs) that produce reactive oxygen species (ROS) are used for the degradation of melanoidins. Heterogeneous photo-Fenton process has emerged as a promising alternative approach in wastewater treatment owing to its enhanced catalytic activity, lower hydrogen peroxide (H2O2) consumption, and reusability of the catalyst. In this work, we investigated the photo-Fenton oxidation of melanoidins using heterogeneous catalyst ZnO@SnOx@nZVI supported on a flexible substrate. The effects of reaction pH, amount of catalyst and H2O2 on color and chemical oxygen demand (COD) removal, as well as the removal kinetics, were studied. It is found that the developed heterogeneous catalyst can lead to 97.3% decolorization of melanoidin (7000 COD) after 4 hours irradiation of simulated sunlight at pH 6 with a much lower dosage of H2O2 than the stoichiometric ratio with respect to COD. The generation of ·OH free radicals and residual H2O2 were monitored to understand the mechanism of melanoidin degradation at near-neutral pH with insufficient H2O2. The findings of this work have significant implications in treatment of non-biodegradable organic pollutants, owing to the advantages in avoiding low pH treatment condition, reducing the cost of H2O2, and enhanced chemical stability of photo-Fenton catalyst. / Melanoidin, en heterogen förorening med hög molekylvikt i avloppsvatten från industrier som använder melass, utgör ett betydande hot mot miljön på grund av dess icke-biologiska nedbrytbarhet, obehagliga lukt och skadliga effekt. Olika avancerade oxidationsprocesser (AOP) som producerar reaktiva syreföreningar (ROS) används för nedbrytning av melanoidiner. Heterogen foto-Fenton-process har framstått som ett lovande alternativ för avloppsrening på grund av dess förbättrade katalytiska aktivitet, lägre väteperoxid (H2O2) förbrukning och återanvändbarhet av katalysatorn. I detta arbete undersökte vi foto-Fenton-oxidationen av melanoidiner med hjälp av heterogen katalysator ZnO@SnOx@nZVI som stöds på ett flexibelt substrat. Effekterna av reaktionens pH, mängden katalysator och H2O2 på färg och avlägsnande av kemisk syreförbrukning (COD), liksom avlägsnandets kinetik, studerades. Det visade sig att den utvecklade heterogena katalysatorn kan leda till 97,3% avfärgning av melanoidin (7000 COD) efter 4 timmars bestrålning av simulerat solljus vid pH 6 med en mycket lågre dosering av H2O2 än det stökiometriska förhållandet med avseende på COD. Generering av ·OH fria radikaler och kvarvarande H2O2 övervakades för att förstå mekanismen för nedbrytning av melanoidin vid nära neutralt pH med otillräcklig H2O2. Resultaten av detta arbete har betydande konsekvenser vid behandling av icke- biologiskt nedbrytbara organiska föroreningar, på grund av fördelarna med att undvika behandlingsförhållanden med lågt pH, minska kostnaden för H2O2 och förbättrad kemiska stabilitet hos foto-Fenton-katalysatorn.

La vinasse est un effluent aqueux issu des distilleries d'éthanol produit à partir de mélasse de canne à sucre, caractérisé par une couleur intense, une forte Demande Chimique en Oxygène (DCO) et un faible Demande Biologique en Oxygène (DBO). Le traitement de ce type d'effluent par Oxydation en Voie Humide (OVH) a fait l'objet d'une étude sur catalyseurs métaux nobles supportés sur TiO2 ou ZrO2 à 190-210°C sous 50-70 bar d'air. L'addition de catalyseurs au Ru permet la minéralisation complète de la partie carbone des polluants modèles (saccharose, polyéthylène glycol, mélanoïdine) ou des effluents réels (vinasse de Cognac et vinasse de canne); les catalyseurs au Pt sont également très efficaces, mais ne convertissent que très peu l'acide acétique formé intermédiairement. Dans ces conditions, l'azote sous forme organique est converti en ammonium. Alors qu'en l'absence de catalyseur, les ions ammonium sont stables, l'addition d'un catalyseur est capable de convertir l'ammonium en diazote et nitrate. Les sélectivités relatives en N2 et NO3 - dépendent des conditions oxydantes de la réaction (quantité d'azote à traiter par rapport à la quantité de métal actif). De manière générale, le platine se révèle plus sélectif en diazote. Une lixiviation des métaux a été détectée au démarrage des réactions d'OVHC des effluents à cause de l'azote sous forme organique ; elle diminue et disparaît au fur et à mesure de la minéralisation de l'azote et le métal se redépose sur le solide catalytique. Les essais en réacteur continu confirment les observations en réacteur batch / Vinasse is an aqueous effluent originating from ethanol production process from sugarcane. It is a dark brown effluent with an extremely high COD and a low BOD. The treatment of this type of effluent by wet air oxidation (WAO) was the subject of this study using noble metal catalysts supported on TiO2 and ZrO2 at 190-210 ° C under 50-70 bar air. The addition of Ru catalysts allowed the complete mineralization of the organic model pollutants (sucrose, polyethylene glycol, melanoidin) or the real effluents (cognac vinasse and cane vinasse); the Pt catalysts were also very effective, but acetic acid was formed as an intermediate which was difficult to be converted. Under these conditions, the organic nitrogen was converted to ammonium. Whereas in the absence of catalyst, the ammonium ions were stable, the addition of a catalyst was capable of converting ammonium to dinitrogen and nitrate. The selectivity to N2 and NO3 - depended on the oxidizing reaction conditions (molar ratio nitrogen/metal). In general, platinum proved to be more selective to dinitrogen. Metal leaching was detected upon CWAO of effluents containing organic nitrogen. The leaching decreased and disappeared as nitrogen was mineralised and the dissolved metal redeposited on the solid catalyst. The continuous reactor tests confirmed the observations in the batch reactor