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Use of δ-manganese dioxide for the removal of acetaminophen from aquatic environment: Kinetic – thermodynamic analysis and transformation products identification
Journal of Environmental Chemical Engineering ( IF 7.7 ) Pub Date : 2020-10-06 , DOI: 10.1016/j.jece.2020.104565
Tryfon Kekes , Maria-Christina Nika , Fotios Tsopelas , Nikolaos S. Thomaidis , Constantina Tzia

High δ-manganese dioxide’s initial concentration (800 mg/L), temperature (50 °C) and acidic pH (3.0–3.5) were found to be the optimum conditions for the removal of acetaminophen. Additionally, acetaminophen was found to be removed more rapidly at high initial concentrations (70−100 mg/L). The kinetic analysis of the experiments revealed that the two tested kinetic models, the one assuming the electron transfer and the other assuming the complex formation as the rate-limiting step, provided a good fit. The positive value of activation energy estimated by the Arrhenius equation indicated that the reaction is endothermic. The transformation products analysis by means of RPLC-QToF, revealed the formation of acetaminophen’s dimer and trimer in the early stages of the reaction, followed by their complete removal in the latter stages of the reaction. Furthermore, four new compounds were detected. Three isomeric compounds fit the formulas C14H11NO4, attributed to aggregates of 1,4-benzoquinone and N-Acetyl-p-benzoquinone Imine, and one additional transformation product was attributed to C17H8N3O5. The abundance of the isomeric compounds was increasing after 60 min of the reaction, and decreasing during the last stages of the reaction, while the latter’s abundance was increasing during the reaction process.



中文翻译:

δ-二氧化锰在水生环境中对乙酰氨基酚的去除:动力学-热力学分析和转化产物鉴定

发现高δ-二氧化锰的初始浓度(800 mg / L),温度(50°C)和酸性pH(3.0-3.5)是去除对乙酰氨基酚的最佳条件。此外,还发现对乙酰氨基酚在高初始浓度(70-100 mg / L)下可以更快地被去除。实验的动力学分析表明,两个测试的动力学模型提供了很好的拟合,其中一个假定电子转移,另一个假定复合物形成为限速步骤。由Arrhenius方程估算的活化能的正值表明该反应是吸热的。通过RPLC-QToF进行的转化产物分析显示对乙酰氨基酚的二聚体和三聚体在反应的早期形成,然后在反应的后期被完全除去。此外,还检测到四种新化合物。三种异构化合物符合式C14 H 11 NO 4,归因于1,4-苯醌和N-乙酰基-对苯醌亚胺的聚集体,另一种转化产物归因于C 17 H 8 N 3 O 5。反应60分钟后,异构体的丰度增加,而在反应的最后阶段则降低,而在反应过程中后者的丰度则增加。

更新日期:2020-10-11
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