【摘要】 采用化学合成的新生态水合δ-MnO2为氧化剂,研究其对17β-雌二醇(E2)氧化转化的反应动力学,考察相关因素(如pH、δ-MnO2投加量等)对氧化转化的影响,并通过气相色谱质谱联用仪(GC/MS)分析δ-MnO2氧化转化E2的产物,探讨氧化转化的反应机制.结果表明,E2对新生态水合δ-MnO2的氧化作用具有较强的反应感受性,且在pH值一定和δ-MnO2充分过量的条件下,E2氧化转化的反应动力学并不是简单的准一级反应动力学,而是遵循复合的反应动力学.E2的氧化转化速率与δ-MnO2的投加量呈正相关,在δ-MnO2投加量为c(E2)∶c(MnO2)=1∶100时,反应体系中的δ-MnO2已足够,E2浓度在8h内降低了90%以上.E2的氧化转化速率与pH值的增加呈负相关,pH为4.0时,E2在0.25h内去除率达到95%,而在pH为6.8和9.0时,E2在1h内只去除了80%和75%.另外,在反应过程中检测到了2个主要产物,分别为雌酮(E1)和2-羟雌二醇,并在此基础上结合相关文献提出了氧化转化流程.更多还原

【Abstract】 The oxidative transformation of 17β-estradiol（E2） by the δ-MnO₂ was investigated in batch experiments,and the influence of pH and δ-MnO₂ dosage on the reaction process was studied.The results suggested that E2 could be degraded by δ-MnO₂,and the oxidation reaction deviated from the pseudo-first-order kinetics at a constant pH and with an enough excess of δ-MnO₂.δMnO₂ dosage had a positive effect on oxidative transformation of E2.When c（E2）∶c（MnO₂）=1∶100,the δ-MnO₂ dosage was enough for E2 degradation,and the removal rate of E2 was above 90% after 8h reaction.The pH value had a negative effect on E2 degradation.When at pH 4.0,E2 concentration was decreased sharply and removal rate reached 95% after 0.25 h reaction,while E2 was disappeared by 80% at pH 6.8 and by 75% at pH 9.0 even after 1 h reaction.Two products,estrone（E1） and 2-hydroxyestradiol,were detected by gas chromatography coupled with mass spectrometry （GC-MS）,and the probable transformation pathway was proposed.更多还原