Rh/Al2O3-Cr2O3整体式催化剂的制备和二氯甲烷催化氧化性能

doi:10.7503/cjcu20160843

摘要/Abstract

摘要：

以粉末Al₂O₃为载体, 通过浸渍Rh(NO₃)₃制备Rh/Al₂O₃催化剂; 再以Rh/Al₂O₃、粉末Cr₂O₃和铝胶经过研磨混合制得催化剂活性浆料; 将催化剂活性浆料涂覆到堇青石蜂窝陶瓷载体表面, 经烘干, 焙烧制得不同Rh含量的Rh/Al₂O₃-Cr₂O₃系列整体式催化剂. 研究了该类催化剂的二氯甲烷催化氧化性能, 发现Rh负载量为0.4 g/L的Rh/Al₂O₃-Cr₂O₃催化剂活性最佳, 且未生成含氯中间产物. 结合催化剂的表征结果发现, Rh的添加可增加催化剂的表面酸性和氧化还原性能, 二者的协同作用提高了催化剂活性; 而Cr₂O₃的存在有利于CH₃Cl中间体的进一步氧化, 从而提高了催化剂的选择性.

关键词: 整体式催化剂, 二氯甲烷, 催化燃烧, 表面酸性, 可还原性

Abstract:

A series of Rh catalysts supported on Al₂O₃ powder was prepared by impregnation method. Then a series of Rh/Al₂O₃-Cr₂O₃ monolithic catalysts was prepared by coating method, different proportions of Rh/Al₂O₃, Cr₂O₃ and aluminum gel were mixed into a homogeneous slurry, and then was coated onto the cordierite honeycomb ceramic. These catalysts with different Rh contents were tested for catalytic combustion of dichloromethane. It was found that the 0.4 Rh/Al₂O₃-Cr₂O₃(Rh contents: 0.4 g/L) had the highest activity and no chlorine-containing by-products were formed. The catalysts were characterized by various techniques such as XRD, H₂-TPR, NH₃-TPD and BET. The results showed that the addition of Rh can improve the surface acidity and redox performance of the catalyst, and further improve the activity of the catalyst. It was believed that the activity of the catalyst was closely related to its reducibility and surface acidity. Moreover, the addition of Cr₂O₃ is beneficial to the further oxidation of CH₃Cl intermediate and thus improve the selectivity.

Key words: Monolithic catalyst, Dichloromethane, Catalytic combustion, Surface acidity, Reducibility

中图分类号:

O643

TrendMD:

陈文亚, 朱丽, 何军, 谢云龙, 鲁继青, 罗孟飞. Rh/Al₂O₃-Cr₂O₃整体式催化剂的制备和二氯甲烷催化氧化性能. 高等学校化学学报, 2017, 38(4): 606.

CHEN Wenya, ZHU Li, HE Jun, XIE Yunlong, LU Jiqing, LUO Mengfei. Preparation of Rh/Al₂O₃-Cr₂O₃ Monolithic Catalysts for Dichloromethane Combustion^†. Chem. J. Chinese Universities, 2017, 38(4): 606.

图/表 8

Table 1 SBET, H2 consumption and surface acidity data of catalysts

Catalyst	S_BET/(m²·g^-1)	H₂ consumption/(mmol·g^-1)	Surface acidity/(μmol·g^-1)
0.4Rh/Al₂O₃-Cr₂O₃	137	1.93	1150
Al₂O₃-Cr₂O₃	122	1.54	580
0.4Rh/Cr₂O₃	47	1.09	270
Cr₂O₃	31	0.65	280
0.4Rh/Al₂O₃	210	0.39	2180
Al₂O₃	207	0.11	1043

Fig.1 XRD patterns of the various catalystsa. 0.4Rh/Al2O3-Cr2O3; b. Al2O3-Cr2O3; c. 0.4Rh/Cr2O3; d. Cr2O3; e. 0.4Rh/Al2O3; f. Al2O3.

Fig.2 H2-TPR profiles and H2 consumption of various catalystsa. 0.4Rh/Al2O3-Cr2O3; b. Cr2O3; c. Al2O3-Cr2O3; d. 0.4Rh/Cr2O3; e. 0.4Rh/Al2O3; f. Al2O3.

Fig.3 NH3-TPD profiles of various catalystsa. 0.4Rh/Al2O3; b.Al2O3; c. Cr2O3; d. Al2O3-Cr2O3; e. 0.4Rh/Al2O3-Cr2O3; f. 0.4Rh/Cr2O3.

Fig.4 Catalysis performance of CH2Cl2 on various Rh/Al2O3-Cr2O3 catalysts a. 0.4Rh/Al2O3-Cr2O3; b. Al2O3; c. 0.4Rh/Al2O3; d. Al2O3-Cr2O3; e. 0.4Rh/Cr2O3; f. Cr2O3.

Fig.5 Catalytic performance of xRh/Al2O3-Cr2O3 catalysts a. 0.4Rh/Al2O3-Cr2O3; b. 0.3Rh/Al2O3-Cr2O3; c. 0.2Rh/Al2O3-Cr2O3; d. 0.5Rh/Al2O3-Cr2O3; e. Al2O3-Cr2O3.

Fig.6 Catalysts selectivity to CH3Cl in CH2Cl2 destruction on various catalysts

Fig.7 Relationship between H2 consumption, surface acidity and the reaction rate at 340 ℃ of catalysts

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Rh/Al₂O₃-Cr₂O₃整体式催化剂的制备和二氯甲烷催化氧化性能

Preparation of Rh/Al₂O₃-Cr₂O₃ Monolithic Catalysts for Dichloromethane Combustion^†

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