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O—正丁基—N—異丁基硫氨酯在黃銅礦表面的吸附熱力學和動力學

Adsorption thermodynamics and kinetics of O—butyl—N—isobutyl thionocarbamate on chalcopyrite surfaces

  • 摘要: O—正丁基—N—異丁基硫氨酯(NBIB)是一種新型銅硫分離捕收劑。利用紫外?可見分光光度計進行吸附量測定,研究吸附溫度、pH值、時間和捕收劑濃度等對NBIB在黃銅礦表面吸附量的影響,并進行吸附熱力學和動力學研究。純礦物浮選實驗表明,NBIB對黃銅礦具有較強的捕收能力,且受pH影響很小。在溫度分別為288、298、308 K,pH值為6、9、12條件下,NBIB在黃銅礦表面的吸附量隨NBIB濃度的增加而增大,當平衡濃度達到0.5×10?4 mol?L?1,吸附量增加幅度變小。相同pH值時,吸附量隨溫度的升高而增加,推測NBIB捕收劑在黃銅礦表面的吸附為吸熱過程。pH值對吸附量影響不大。將吸附量數據進行Langmuir和Freundlich方程線性擬合,NBIB在黃銅礦表面的吸附過程更符合Langmuir單分子層吸附模型。熱力學計算結果表明,吸附的吉布斯自由能變(?G)均為負值,焓變(?H)和熵變(?S)均為正值,說明黃銅礦吸附NBIB的過程可能為自發進行的、熵驅動的、吸熱的化學吸附。吸附溫度從288 K到308 K,吸附量隨吸附時間和溫度的增加而增大,當吸附時間達到20 min之后,吸附量的增加趨勢變緩。動力學計算表明,二級反應速率方程的線性擬合結果更好,利用二級反應速率方程計算所得的平衡吸附量更接近于實驗平衡吸附量,推測NBIB在黃銅礦表面的吸附符合二級吸附動力學模型。

     

    Abstract: O—butyl—N—isobutyl thionocarbamate (NBIB) is a novel collector for copper sulfur flotation separation. The adsorption capacity of NBIB was measured using a UV–vis spectrophotometer. The effects of the adsorption temperature, pH value, stirring time, and collector concentration on the adsorption capacity of NBIB on chalcopyrite surfaces, as well as its adsorption thermodynamics and kinetics, were investigated. Results of a pure mineral flotation experiment indicate that NBIB has a high recovery rate for chalcopyrite, strong collection capacity, and little influence by pH. The adsorption capacity of NBIB on a chalcopyrite surface increases with an increase in the collector concentration at 288, 298, and 308 K and pH 6, 9, and 12, respectively. When the equilibrium concentration reaches 0.5×10?4 mol?L?1, the adsorption capacity has a small increase range. At the same pH value, the adsorption capacity increases with an increase in the adsorption temperature. It is speculated that NBIB adsorption on a chalcopyrite surface is an endothermic process. At pH 6 and 9, little difference exists in adsorption capacity, which slightly decreases when pH increases to 12. Meanwhile, the pulp pH value has little effect on the adsorption capacity, which is consistent with the flotation test results. The adsorption capacity data were linearly fitted by Langmuir and Freundlich isotherms, and the Langmuir equation has a better correlation coefficient of the fitting curve. The adsorption process of NBIB on the chalcopyrite surface is more consistent with the Langmuir adsorption model, and it is speculated that the adsorption process may be monolayer adsorption. The parameters of the Langmuir equation are considered based on a thermodynamic formula. The results indicate that the linear fitting results are good, ?G is negative, and ?H and ?S are positive. Therefore, the process of chalcopyrite adsorbing NBIB may be spontaneous, entropy-driven, and endothermic chemical adsorption. Meanwhile, the adsorption capacity of NBIB on the chalcopyrite surface increases with an increase in the adsorption time at temperatures from 288 K to 308 K. The increasing trend of adsorption capacity slows down after the adsorption time reaches 20 min. Moreover, the adsorption capacity increases with increasing temperature. Evidently, the adsorption is an endothermic process, which is consistent with the results of the thermodynamic analysis. The kinetic calculation shows that the correlation coefficients of the second-order reaction fitting curve are greater than those of first-order reaction, indicating that the second-order reaction rate equation has a better linear fitting result. The equilibrium adsorption capacity calculated by the second-order reaction rate equation is closer to the experimental equilibrium adsorption capacity. Therefore, it is speculated that the NBIB adsorption on the chalcopyrite surface conforms to the second-order adsorption kinetic model.

     

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