氧化镁上乙酸乙酯和乙酸丁酯氧化反应

doi:10.1016/S1872-2067(17)62986-3

摘要/Abstract

摘要：

采用新型无溶剂反应和回流的方法制得锰钾矿型氧化镁（K-OMS-2），同时采用常规方法制得氧化镁，并测试不同催化剂对工业排放气中有机挥发性物质（VOCs）中的模型化合物——乙酸乙酯和乙酸丁酯的催化氧性能.采用N₂吸附-脱附、X射线衍射、扫描电镜、程序升温还原和X射线光电子能谱等技术对催化剂进行了表征.所有氧化镁样品均表现出很高的催化乙酸乙酯和乙酸丁酯氧化生成CO₂的活性，且制备方法对催化剂性能起着重要作用.新型无溶剂法制得的K-OMS-2纳米棒样品比常规的回流法制得样品表现出更好的催化性能，含锰钾矿型氧化镁的样品比常规方法制得样品表现出更高的活性.性能最好的催化剂也表现出较高的稳定性，在213和202℃条件下，可分别使90%的乙酸乙酯和乙酸丁酯转化为CO₂.催化剂性能的显著差异清楚地表明，对于所选VOCs氧化反应，采用新型无溶剂法制得的K-OMS-2纳米棒样品比常规法制备的氧化镁混合物更好，这可能与样品结构中含有更高的Mn平均氧化态有关.本文表明了催化剂性能与其表面化学性质间存在显著的关联，显示了K-OMS-2内在性质决定了其高的催化性能.

关键词: 挥发性有机化合物, 乙酸乙酯, 乙酸丁酯, 氧化镁, 催化氧化

Abstract:

Mangenese oxides were synthesized using two new methods, a novel solvent-free reaction and a reflux technique, that produced cryptomelane-type products (K-OMS-2). Oxides were also synthesized using conventional methods and all specimens were applied to the oxidation of ethyl acetate and butyl acetate, acting as models for the volatile organic compounds found in industrial emissions. The catalysts were also characterized using N₂ adsorption, X-ray diffraction, scanning electron microscopy, temperature programmed reduction and X-ray photoelectron spectroscopy. Each of the manganese oxides was found to be very active during the oxidation of both esters to CO₂, and the synthesis methodology evidently had a significant impact on catalytic performance. The K-OMS-2 nanorods synthesized by the solvent-free method showed higher activity than K-OMS-2 materials prepared by the reflux technique, and samples with cryptomelane were more active than those prepared by the conventional methods. The catalyst with the highest performance also exhibited good stability and allowed 90% conversion of ethyl and butyl acetate to CO₂ at 213 and 202℃, respectively. Significant differences in the catalyst performance were observed, clearly indicating that K-OMS-2 nanorods prepared by the solvent-free reaction were better catalysts for the selected VOC oxidations than the mixtures of manganese oxides traditionally obtained with conventional synthesis methods. The superior performance of the K-OMS-2 catalysts might be related to the increased average oxidation state of the manganese in these structures. Significant correlations between the catalytic performance and the surface chemical properties were also identified, highlighting the K-OMS-2 properties associated with the enhanced catalytic performance of the materials.

Key words: Volatile organic compound, Ethyl acetate, Butyl acetate, Manganese oxide, Catalytic oxidation

Olívia Salomé G. P. Soares, Raquel P. Rocha, José J. M. Órfão, Manuel F. R. Pereira, José L. Figueiredo. 氧化镁上乙酸乙酯和乙酸丁酯氧化反应[J]. 催化学报, DOI: 10.1016/S1872-2067(17)62986-3.

Olívia Salomé G. P. Soares, Raquel P. Rocha, José J. M. Órfão, Manuel F. R. Pereira, José L. Figueiredo. Ethyl and butyl acetate oxidation over manganese oxides[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(17)62986-3.

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