Avaliação da remoção de hidrocarbonetos aromáticos (BTEX) em águas utilizando materiais nanoestruturados do tipo Ti-MCM-41

Volatile Organic Compounds are pollutants coming mainly from activities that use fossil fuels. Within this class are the BTEX (benzene, toluene, ethylbenzene and xylenes) compounds that are considered hazardous. Among the various existing techniques for degradation of pollutants, there is advanced oxidation using H2O2 generating hidoxil radical ( OH). In this work, the mesoporous material of MCM-41 was synthesized by hydrothermal method and then was used as support, the impregnation of titanium by the method of synthesis with excess solvent to obtain the catalyst Ti-MCM-41. The catalyst was used in the reaction catalyzed removal of BTEX in water using H2O2 as oxidant. The materials were characterized by: XRD, TG/DTG, FTIR, nitrogen adsorption-desorption and FRX-EDX, in order to verify the method of impregnation of the mesoporous titanium support was effective. Catalytic tests were carried out in reactors of 20 mL containing BTEX (100.0 μg/L), H2O2 (2.0 M) and Ti-MCM-41 (2.0 g/L) in acid medium. The reaction occurred for 5 h at 60 °C and analysis were performed by gas chromatography with photoionization detector and static headspace sampler. The characterizations have proven the effectiveness of the synthesis method used and the incorporation of titanium lt in the support. The catalytic tests showed satisfactory results with conversion of more than 95 % for the studied compounds, where the catalyst 48% Ti-MCM-41 showed a higher removal efficiency of the compounds under study

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry

Estudo da eficiência eletroquímica para tratamento de chorume gerado em aterro sanitário brasileiro

This work was performing effluent degradation studies by electrochemical treatment. The electrochemical oxidation (EO) hydroquinone (H2Q) was carried out in acid medium, using PbO2 electrode by galvanostatic electrolysis, applying current densities of 10 and 30 mA/cm2 . The concentration of H2Q was monitored by differential pulse voltammetry (DPV). The experimental results showed that the galvanostatic electrolysis process performance significantly depends on the applied current density, achieving removal efficiencies of 100% and 80 % and 10 applying 30 mA/cm2 , respectively. Furthermore, the electroanalytical technique was effective in H2Q be used as a detection method. In order to test the efficiency of PbO2 electrode, the electrochemical treatment was conducted in an actual effluent, leachate from a landfill. The liquid waste leachate (600ml effluent) was treated in a batch electrochemical cell, with or without addition of NaCl by applying 7 mA/cm2 . The efficiency of EO was assessed against the removal of thermo-tolerant coliforms, total organic carbon (TOC), total phosphorus and metals (copper, cobalt, chromium, iron and nickel). These results showed that efficient removal of coliforms was obtained (100%), and was further decrease the concentration of heavy metals by the cathode processes. However, results were not satisfactory TOC, achieving low total removal of dissolved organic load. Because it is considered an effluent complex were developed other tests with this effluent to monitor a larger number of decontamination parameters (Turbidity, Total Solids, Color, Conductivity, Total Organic Carbon (TOC) and metals (barium, chromium, lithium, manganese and Zinc), comparing the efficiency of this type of electrochemical treatment (EO or electrocoagulation) using a flow cell. In this assay was compared to electro streaming. In the case of the OE, Ti/IrO2-TaO5 was used as the anode, however, the electrocoagulation process, aluminum electrodes were used; applying current densities of 10, 20 and 30 mA/cm2 in the presence and absence of NaCl as an electrolyte. The results showed that EO using Ti/IrO2–TaO5 was anode as efficient when Cl- was present in the effluent. In contrast, the electrocoagulation flow reduces the dissolved organic matter in the effluent, under certain experimental conditions.

Usos de membranas de quitosana na remoção de cobre em águas residuais

In this work a chitosan (CS) ionically crosslinked were manufactured by treatment with sulfuric acid solution for application in the treatment of wastewater from oil industry. Two crosslinking process were developed: homogeneous and heterogeneous. In the homogeneous process the ratio molar of SO42-/ NH3+ (1:6 and 1:4) were the variable analyzed, denominated CS16 and CS14 respectively. In the heterogeneous process the soaking time of the membranes in sulfuric acid solution were the variable studied, being used times of 5 (CS5) and 30 (CS30) minutes. FTIR-ATR results indicated no changes in the characteristics of chitosan after homogeneous crosslinking process, while heterogeneous crosslinking showed formation of ionic bonds between protonated groups from chitosan and the crosslinking agent sulfate ions. TG/DTG and XRD analysis confirmed the formation of these interactions, as also shown the new structure on the surface region of CS5 and CS30 membranes compared to CS, CS16 e CS14. Swelling test in aqueous medium have shown that crosslinking process reduced the membrane sorption capacity. Swelling test in acid medium demonstrated that CS16 and CS14 membranes increasing the adsorption capacity up to a maximum percentage of 140% approximately, whereas the CS5 e CS30 reached a maximum of 60%. The mechanical properties indicated the stiff and ductile behavior of crosslinked membrane. Adsorption experiments of CuCl2 results that CS16 membranes reached the efficiency maximum with 73% of copper removal at pH 5.0 and 87% at pH 4.0. The experiments with CuSO4 also obtained efficiency maximum to the CS16 membrane and 80% to the removal of Cu2+ ions. Also was verified that the increase of concentration and temperature cause a decrease in the adsorption capacity for all membranes. Kinetics study indicated that pseudo-second-order obtained characterized better the membranes. Equilibrium studies demonstrated that the CS, CS16 and CS14 follow the Langmuir model, whereas CS5 and CS30 follows Freundlich model. Filtration experiments results with rejection maximum to the CS16 and CS5 membranes, reaching 92 and 98% respectively.

Usos de membranas de quitosana na remoção de cobre em águas residuais

In this work a chitosan (CS) ionically crosslinked were manufactured by treatment with sulfuric acid solution for application in the treatment of wastewater from oil industry. Two crosslinking process were developed: homogeneous and heterogeneous. In the homogeneous process the ratio molar of SO42-/ NH3+ (1:6 and 1:4) were the variable analyzed, denominated CS16 and CS14 respectively. In the heterogeneous process the soaking time of the membranes in sulfuric acid solution were the variable studied, being used times of 5 (CS5) and 30 (CS30) minutes. FTIR-ATR results indicated no changes in the characteristics of chitosan after homogeneous crosslinking process, while heterogeneous crosslinking showed formation of ionic bonds between protonated groups from chitosan and the crosslinking agent sulfate ions. TG/DTG and XRD analysis confirmed the formation of these interactions, as also shown the new structure on the surface region of CS5 and CS30 membranes compared to CS, CS16 e CS14. Swelling test in aqueous medium have shown that crosslinking process reduced the membrane sorption capacity. Swelling test in acid medium demonstrated that CS16 and CS14 membranes increasing the adsorption capacity up to a maximum percentage of 140% approximately, whereas the CS5 e CS30 reached a maximum of 60%. The mechanical properties indicated the stiff and ductile behavior of crosslinked membrane. Adsorption experiments of CuCl2 results that CS16 membranes reached the efficiency maximum with 73% of copper removal at pH 5.0 and 87% at pH 4.0. The experiments with CuSO4 also obtained efficiency maximum to the CS16 membrane and 80% to the removal of Cu2+ ions. Also was verified that the increase of concentration and temperature cause a decrease in the adsorption capacity for all membranes. Kinetics study indicated that pseudo-second-order obtained characterized better the membranes. Equilibrium studies demonstrated that the CS, CS16 and CS14 follow the Langmuir model, whereas CS5 and CS30 follows Freundlich model. Filtration experiments results with rejection maximum to the CS16 and CS5 membranes, reaching 92 and 98% respectively.