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[石化行业排放的典型挥发性有机化合物在CuCeOx复合氧化物上的氧化行为及动力学]

[Oxidation behavior and kinetics of representative VOCs emitted from petrochemical industry over CuCeOx composite oxides].

作者信息

Chen Chang-Wei, Yu Yan-Ke, Chen Jin-Sheng, He Chi

出版信息

Huan Jing Ke Xue. 2013 Dec;34(12):4724-33.

PMID:24640915
Abstract

CuCeOx composite catalysts were synthesized via coprecipitation (COP-CuCeO,) and incipient impregnation (IMP-CuCeOx) methods, respectively. The physicochemical properties of the samples were characterized by XRD, low-temperature N2 sorption, H2-TPR and O2-TPD. The influences of reactant composition and concentration, reaction space velocity, O2 content, H2O concentration, and catalyst type on the oxidation behaviors of benzene, toluene, and n-hexane emitted from petrochemical industry were systematically investigated. In addition, the related kinetic parameters were model fitted. Compared with IMP-CuCeOx, COP-CuCeOx had well-dispersed active phase, better low-temperature reducibility, and more active surface oxygen species. The increase of reactant concentration was unfavorable for toluene oxidation, while the opposite phenomenon could be observed in n-hexane oxidation. The inlet concentration of benzene was irrelevant to its conversion under high oxidation rate. The introduction of benzene obviously inhibited the oxidation of toluene and n-hexane, while the presence of toluene had a positive effect on beuzene conversion. The presence of n-hexane could promote the oxidation of toluene, while toluene had a negative influence on e-hexane oxidation. Both low space velocity and high oxygen concentration were beneficial for the oxidation process, and the variation of oxygen content had negligible effect on n-hexane and henzene oxidation. The presence of H2O noticeably inhibited the oxidation of toluene, while significantly accelerated the oxidation procedure of henzene and n-hexane. COP-CuCeOx had superior catalytic performance for toluene and benzene oxidation, while IMP-CuCeOx showed higher n-hexane oxidation activity under dry condition. The oxidation behaviors under different conditions could be well fitted and predicted by the pseudo first-order kinetic model.

摘要

分别通过共沉淀法(COP-CuCeO)和初湿浸渍法(IMP-CuCeOx)合成了CuCeOx复合催化剂。采用XRD、低温N2吸附、H2-TPR和O2-TPD对样品的物理化学性质进行了表征。系统研究了反应物组成和浓度、反应空速、O2含量、H2O浓度以及催化剂类型对石化行业排放的苯、甲苯和正己烷氧化行为的影响。此外,对相关动力学参数进行了模型拟合。与IMP-CuCeOx相比,COP-CuCeOx具有活性相分散良好、低温还原性更好以及活性表面氧物种更多的特点。反应物浓度的增加不利于甲苯氧化,而在正己烷氧化中则观察到相反的现象。在高氧化率下,苯的入口浓度与其转化率无关。苯的引入明显抑制了甲苯和正己烷的氧化,而甲苯的存在对苯的转化率有积极影响。正己烷的存在可以促进甲苯的氧化,而甲苯对正己烷氧化有负面影响。低空速和高氧浓度都有利于氧化过程,氧含量的变化对正己烷和苯氧化的影响可忽略不计。H2O的存在明显抑制了甲苯的氧化,而显著加速了苯和正己烷的氧化过程。COP-CuCeOx对甲苯和苯氧化具有优异的催化性能,而IMP-CuCeOx在干燥条件下表现出较高的正己烷氧化活性。不同条件下的氧化行为可以通过准一级动力学模型进行很好的拟合和预测。

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