Evaluation of Anionic Eco-Friendly Flocculants Prepared from Eucalyptus Pulps with Diverse Lignin Contents for Application in Effluent Treatment.

Modification of cellulosic-rich materials for the production of cellulose-based polyelectrolytes (PELs) can bring several benefits, such as high biodegradability and low or no toxicity, for numerous applications, when compared with the use of traditional, synthetic PELs. Moreover, cellulose-based PELs originating from wood wastes, contribute to the valorisation of such wastes. In this work, Eucalyptus pulps with diverse lignin contents, extracted from Eucalyptus wood wastes, were anionized by a two-step reaction procedure (periodate oxidation followed by sulfonation). Applying different reaction times (24-144 h) in the sulfonation step allowed for producing a range of cellulose-based anionic polyelectrolytes with different characteristics. PELs obtained after 24 and 72 h of sulfonation were thoroughly characterized (Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies, zeta potential and degree of substitution (elemental analysis) and hydrodynamic diameter (dynamic light scattering)) and subsequently evaluated as flocculants in decolouration processes of model effluents (Methylene Blue and Crystal Violet) and an industrial effluent from a textile industry. Furthermore, possible flocculation mechanisms induced by the use of the various PELs are discussed. Results are compared with those obtained with a commonly applied, synthetic flocculant (polyacrylamide). It is demonstrated that it was possible to obtain water-soluble lignocellulosic PELs starting from raw materials with different degrees of purity and that those PELs are promising eco-friendly alternative flocculation agents for the decolouration of effluents.

Evaluation of Anionic and Cationic Pulp-Based Flocculants With Diverse Lignin Contents for Application in Effluent Treatment From the Textile Industry: Flocculation Monitoring.

In wastewater treatment, flocculation is a widely used solid/liquid separation technique, which typically employs a charged polymer, a polyelectrolyte (PEL). Polyelectrolytes features, such as charge type, charge density and molecular weight, are essential parameters affecting the mechanism of flocculation and subsequent floc sedimentation. The effectiveness of the process is also influenced by the characteristics of the system (e.g., type, size, and available surface area of suspended particles, pH of the medium, charge of suspended particles). Thus, a good understanding of the flocculation kinetics, involved mechanisms and flocs structure is essential in identifying the most adequate treatment conditions, having also into consideration possible subsequent treatments. In this study, Eucalyptus bleached pulp and a cellulosic pulp with high lignin content (~4.5 wt%) obtained from Eucalyptus wood waste were used for bio-PELs production. Firstly, a pre-treatment with sodium periodate increased the pulps reactivity. To produce cationic cellulose the oxidation step was followed by the introduction of cationic groups in the cellulose chains, through reaction with Girard's reagent T. Applying different molar ratios (0.975 and 3.9) of Girard's reagent T to aldehyde groups led to cationic PELs with diverse charge density. On the other hand, to obtain anionic cellulose a sulfonation reaction with sodium metabisulfite was applied to the intermediate dialdehyde cellulose-based products, during 24 or 72 h, and anionic-PELs with diverse features were obtained. The developed water soluble, anionic and cationic bio-PELs were characterized and tested as flocculation agents for a textile industry effluent treatment. Initially, jar-tests were used to tune the most effective flocculation procedure (pH, flocculant dosage, etc.). Flocculation using these conditions was then monitored continuously, over time, using laser diffraction spectroscopy (LDS). Due to the small size of the dyes molecules, a dual system with an inorganic complexation agent (bentonite) was essential for effective decolouration of the effluent. Performance in the treatment was monitored first by turbidity removal evaluation (75-88% with cationic-PELs, 75-81% with anionic-PELs) and COD reduction evaluation (79-81% with cationic-PELs, 63-77% with anionic-PELs) in the jar tests. Additionally, the evolution of flocs characteristics (structure and size) during their growth and the flocculation kinetics, were studied using the LDS technique, applying the different PELs produced and for a range of PEL concentration. The results obtained through this monitoring procedure allowed to discuss the possible flocculation mechanisms involved in the process. The results obtained with the bio-PELs were compared with those obtained using synthetic PELs, commonly applied in effluents treatment, polyacrylamides. The developed bio-PELs can be competitive, eco-friendly flocculation agents for effluents treatment from several industries, when compared to traditional synthetic flocculants with a significant environmental footprint. Moreover, LDS proved to be a feasible technique to monitor flocculation processes, even when a real industrial effluent is being tested.

Up-scaling of tannin-based coagulants for wastewater treatment: performance in a water treatment plant.

Tannin extracts from the bark of Acacia mearnsii and wood of Schinopsis balansae, commonly known as Quebracho, were employed. These were modified at laboratory sale via the Mannich aminomethylation with formaldehyde and dimethylamine hydrochloride. Some reaction conditions were varied, namely the formaldehyde dosage and reaction time, while keeping the Mannich solution activation time constant, and their influence on the shear viscosity of the created bio-coagulants was evaluated. The effect of the final pH of the products on their shear viscosity was also analyzed. Up-scaling of the Mannich reaction for tannin from South Africa was performed and the procedure developed at 1-L scale was reproducible in upscaled conditions. One example of a modified South Africa tannin and the modified Quebracho tannin was subsequently selected for the treatment of an industrial wastewater and tested for color and turbidity reduction in jar tests. The effluent treatment was carried out in a single and dual system with cationic synthetic flocculation agents of different charge degree. Good turbidity and decoloration results (93 and 89% reduction, respectively) were obtained with the simultaneous introduction of a cationic, 40% charged polyacrylamide, with minimal dosage (5 ppm) of the latter additive. The tannin-based coagulant from Acacia mearnsii was successfully applied in dual system with cationic polyacrylamide flocculant for industrial wastewater treatment at pilot plant scale. It was shown to satisfactorily treat the water and generate less sludge.

Cationization of Eucalyptus wood waste pulps with diverse lignin contents for potential application in colored wastewater treatment.

Modification of cellulosic-rich materials such as Eucalyptus wood waste and production of cellulose-based polyelectrolytes (PELs) presents several advantages for a variety of applications, when compared to the utilization of synthetic PELs, due to the nature, availability, high biodegradability and low or no toxicity of cellulosic materials. Moreover, valorization of the cellulosic waste itself to provide end products with higher added value is also an important aspect. In the present work, the objective was to evaluate the possibility of cationizing more complex and heterogeneous chemical pulps, obtained from Eucalyptus wood waste, with different cellulose purity and a relatively high lignin content (up to 4.5%). A two-step reaction (with sodium periodate and Girard's reagent T) was employed and a range of cellulose-based cationic polyelectrolytes were produced with different degrees of substitution. The final products were characterized by several analytical techniques and the bio-PELs with the highest and the lowest substitution degree by cationic groups were evaluated in a new application, as flocculants in the decoloration of model effluents, bentonite having been used as an inorganic aid. Also, possible mechanisms of flocculation were discussed and the results compared with those of a synthetic flocculant, often used in these treatments, cationic polyacrylamide. Lignocellulosic-PELs proved to be very favorable eco-friendly flocculation agents for the decoloration of dye-containing waters with potential application in several industries.

Environmentally friendly cellulose-based polyelectrolytes in wastewater treatment.

Natural-based polyelectrolytes (PELs), with all the advantages coming from being produced from renewable and biodegradable sources, are a potential solution for the removal of dyes from wastewater. In this work, surplus Eucalyptus bleached cellulose fibres from a paper mill were modified to increase the charge and solubility of cellulose. First, reactive aldehyde groups were introduced in the cellulose backbone by periodate oxidation of cellulose. Further modification with alkylammonium produced positively charged cellulose-based PELs. The final products were characterized by several analytical techniques. The PEL with the highest substitution degree of cationic groups was evaluated for its performance in decolouration processes, bentonite being used as aid. This was found to be effective for colour removal of either anionic or cationic dyes. Bio-PELs can thus be considered as very favourable eco-friendly flocculation agents for decolouration of harsh effluents from several industries, considering their biodegradable nature and thus the ability to produce less sludge.

Gastro retention using polymer cocoons.

A gastro-retentive capsule has been prepared which is retained in the stomach for a period of 24h, providing a vehicle for the controlled delivery to the upper intestines. These "gastro cocoons" can resist passage through the sphincter of the stomach, and can retain a high drug payload (30%). They are made from oppositely charged polyelectrolytes and can swell to twice their initial volume. They are strong and also can resist 550 N of compressive force. They are based on filled pharmaceutical capsules which are visible to X-rays. Using ambroxol hydrochloride as a model drug linear, zero-order, release curves were obtained.