RESUMEN

Organic compounds are employed as additives to increase the dissolution speed of gold, in concentrations around 1 g/L when using cyanidation, thereby forming a residual aqueous effluent with high amounts of free cyanides and organic compounds, which generate metallic complexes difficult to degrade. To increase the photodegradation efficiency, promising niobium and titanium porous materials are proposed as photocatalysts, due to their role in simultaneous oxidation and reduction reactions. In the process of cyanide oxidation, NbO5 0.3H2O was doped with titanium oxalate (IV) of 0.5, 1, and 1.5%; and HTiNbO5 were synthesized, from the mixture of NbO5 with TiO2 Degussa-P25, by coprecipitation, impregnation, and solid state. The determination of its elemental composition, morphological and textural properties were carried out by using various XRD techniques, Raman spectroscopy, SEM/EDS and acidity by pyridine. The experiments of photocatalytic oxidation of cyanide used one semibatch reactor with ultraviolet irradiation 125 W in a pH range of 9.5-12. The catalyst with the highest percentage of degradation was HTiNbO5 93.7%, which is attributed to the microstructure of the double layer and Lewis acidity sites, followed by NbTi-1% 92.9% and the Nb2O5.3H2O 82.4%, being the majority product cyanate, proposing its mechanism of reaction. Characterization experiments indicated Nb-O-Ti bridges that have been associated with the control of redox properties of the niobium species and Ti-O-Nb = O, which could be generating a greater number of e-H +pairs, increasing the photocatalytic activity. It is considered that the method of synthesis has a strong influence in changing the morphology of the particles such as porosity, specific surface and factors such as the acidity of niobium-based catalysts, which are important to achieving efficiency in degradation. Niobium-Titanium photocatalysts proved to be an excellent new breakthrough in Advanced Oxidation Technologies (AOT), to eliminate cyanide in wastewater from mining activities.

RESUMEN

The thermodynamic and kinetic aspects of ethyl carbamate (EC) formation through the reaction between cyanate and ethanol were investigated. The rate constant values for cyanate ion decay and EC formation are (8.0 ± 0.4) × 10(-5) and (8.9 ± 0.4) × 10(-5) s(-1), respectively, at 25 °C in 48% aqueous ethanolic solution at pH 4.5. Under the investigated experimental conditions, the rate constants are independent of the ethanol and cyanate concentrations but increase as the temperature increases (ΔH1(⧧) = 19.4 ± 1 kcal/mol, ΔS1(⧧) = −12.1 ± 1 cal/K, and ΔG1(⧧) = 23.0 ± 1 kcal/mol) and decrease as the solution pH increases. According to molecular modeling (DFT) that was performed to analyze the reaction mechanism, the isocyanic acid (HNCO) is the active EC precursor. The calculated ΔG1(⧧), ΔH1(⧧), and ΔS1(⧧) values are in very good agreement with the experimental ones.

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RESUMEN

UNLABELLED: Based on the fluorescence properties of 2,4-(1H,3H)-quinazolinedione, a product of the reaction between cyanate and 2-aminobenzoic acid, a simple, sensitive, selective, and reproducible method for the cyanate analysis in aqueous ethanolic media is proposed. In this method, λ(exc) and λ(em) are 310 and 410 nm, respectively, and the limits of detection and quantification are 2.2 × 10(-7) and 6.7 × 10(-7) mol/L, respectively. Under optimal conditions (pH = 4.5, 40% ethanol), a concentration of 5.0 × 10(-6) mol/L cyanate can be determined in a single measurement, at a 95% level of confidence, with an uncertainty of ± 0.13 × 10(-6) mol/L. Cyanide, thiocyanate, chloride, nitrate, and sulfate ions, as well as urea and urethane in concentrations 1 × 10(3) higher than that of cyanate do not interfere with the measurement. The methodology was applied to cyanate analyses in the different fractions of the sugarcane distillate and the data strongly suggest a correlation between the presence of urea in wine, and the cyanate and ethyl carbamate concentrations in the spirit. PRACTICAL APPLICATION: Based on the fluorescence properties of the reaction product between cyanate and 2-aminobenzoic acid, a method for assaying cyanate was devised. This procedure applied to the sugarcane distillate showed for the first time a correlation between cyanate presence and ethyl carbamate (EC) formation in the different fractions of the product. Therefore, the proposed methodology can be used to predict in freshly distillate sugar cane spirits the potential total concentration of EC to be formed. Therefore, these data could be used to advise about the necessity of implementing a procedure to reduce spirit EC concentration before the product reaches the market.

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A mixed culture and a pure bacterial strain (BMV8) were isolated from a bioreactor for thiocyanate treatment. Both cultures removed 5 mM of thiocyanate from the medium in 36 hours. The mixed culture was able to tolerate concentrations up to 60 mM. The efficiency of thiocyanate degradation decreased when the cells were immobilized.

Uma cultura mixta e uma linhagem bacteriana pura foram isoladas de um bioreator para tratamento de tiocianato. As culturas removeram 5mM de tiocianato do meio em 36 horas. A cultura mixta foi capaz de tolerar concentrações superiores a 60mM. A eficiência da degradação de tiocianato diminuiu quando as células foram imobilizadas.