Synthesis of ethylbenzene from ethane and benzene by tandem catalysis

doi:10.11949/0438-1157.20210050

Abstract

Abstract:

This work designs a tandem route for the production of ethylbenzene (EB) directly from ethane and benzene via the ethylene intermediate. The tandem reaction consists of chlorine oxidation of ethane to form ethylene and the alkylation reaction between ethylene and benzene. In this paper, cerium-based oxide was selected as the catalyst for activating ethane to produce ethylene, and the H-ZSM-5 zeolite was used to be further alkylated with benzene to produce ethylbenzene. We investigate the optimization of the selected oxides, and the effects of the ratio of oxides and zeolites, acidity of zeolite on catalytic performances of tandem reaction over Mn/CeO₂-H-ZSM-5 bifunctional catalyst. The stability of catalyst is also investigated. Combining X-ray diffraction (XRD), NH₃ temperature programmed desorption (NH₃-TPD), transmission electron microscopy (TEM), and X-ray fluorescence spectroscopy (XRF) techniques, the structure of catalyst and the relationship of structure and performances are further studied. The research suggests that the key to subsequent catalyst research lies in the improvement of zeolite alkylation ability and anti-loss ability.

Key words: ethylbenzene, ethane, benzene, tandem catalysis, zeolite, cerium oxide

摘要：

设计乙烷经氯氧化制备乙烯再与苯烷基化一步法制备乙苯的接力催化路线。研制铈基氧化物作为活化乙烷生成中间产物乙烯的催化剂，并耦合H-ZSM-5沸石分子筛与苯进一步烷基化生成乙苯。在Mn/CeO₂氧化物与H-ZSM-5沸石分子筛以研磨混合形成的双功能催化剂上，实现了乙烷与苯催化制备乙苯的可控接力催化。考察了氧化物的组成、氧化物与沸石分子筛的耦合方式与最适质量配比、沸石分子筛的硅铝比对接力催化反应的影响，并进行了催化剂稳定性研究。结合X射线衍射（XRD）、NH₃程序升温脱附（NH₃-TPD）、透射电子显微镜（TEM）、X射线荧光光谱分析（XRF）等表征手段分析了催化剂结构及其与催化性能的构效关系。提出后续催化剂研究的关键在于分子筛烷基化能力以及抗流失能力的提高。

关键词: 乙苯, 乙烷, 苯, 接力催化, 分子筛, 氧化铈

CLC Number:

TQ 028.8

CHENG Huige, NIU Wei, TANG Xinglei, YUE Liangxu, KANG Jincan, ZHANG Qinghong, WANG Ye. Synthesis of ethylbenzene from ethane and benzene by tandem catalysis[J]. CIESC Journal, 2021, 72(7): 3658-3667.

程挥戈, 牛韦, 汤兴蕾, 岳亮旭, 康金灿, 张庆红, 王野. 乙烷与苯经接力催化路线制备乙苯[J]. 化工学报, 2021, 72(7): 3658-3667.

Figures/Tables 12

Fig.1 Catalytic performances of chlorine oxidation of ethane and alkylation reaction of ethylene and benzene

Fig.2 Effect of contact manner of Mn/CeO2 oxide and H-ZSM-5(25) zeolite on catalytic performances others—C2H4Cl2 and hydrocarbons

Fig.3 Catalytic performances of Mn/CeO2-H-ZSM-5-grind with different mass ratios of Mn/CeO2 oxide to H-ZSM-5 zeolite

Fig.4 Effect of Si/Al ratio of H-ZSM-5 on catalytic performances over Mn/CeO2-H-ZSM-5 bifunctional catalyst

Fig.5 Catalytic performances with time on stream over Mn/CeO2-H-ZSM-5-grindcatalyst

Fig.6 XRD patterns of CeO2 and Mn/CeO2

Fig.7 XRD patterns of Mn/CeO2, H-ZSM-5 and Mn/CeO2-H-ZSM-5

Fig.8 TEM images of Mn/CeO2 nanorods

Fig.9 TEM images of Mn/CeO2-H-ZSM-5 catalysts

Table 1 XRF analysis of Mn/CeO2-H-ZSM-5 before and after catalytic reaction

Reaction time/h	Element content/% (mass)
Reaction time/h	Ce	Mn	Al	Si
0	15.86	2.16	0.84	34.3
2.5	15.91	2.07	0.81	34.0
35	16.43	1.62	0.75	39.7

Fig.10 NH3-TPD profiles of H-ZSM-5 with different Si/Al ratio

Fig.11 NH3-TPD patterns of Mn/CeO2-H-ZSM-5-grind catalyst before and after reaction

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