化工学报 ›› 2021, Vol. 72 ›› Issue (7): 3658-3667.doi: 10.11949/0438-1157.20210050

• 催化、动力学与反应器 • 上一篇    下一篇

乙烷与苯经接力催化路线制备乙苯

程挥戈(),牛韦,汤兴蕾,岳亮旭,康金灿(),张庆红,王野   

  1. 厦门大学化学化工学院，醇醚酯化工清洁生产国家工程实验室，福建 厦门 361005
  • 收稿日期:2021-01-09 修回日期:2021-04-12 出版日期:2021-07-05 发布日期:2021-07-05
  • 通讯作者: 康金灿 E-mail:hgcheng@stu.xmu.edu.cn;kangjc@xmu.edu.cn
  • 作者简介:程挥戈（1996—），男，硕士研究生，hgcheng@stu.xmu.edu.cn
  • 基金资助:
    国家自然科学基金项目(21872112)

Synthesis of ethylbenzene from ethane and benzene by tandem catalysis

CHENG Huige(),NIU Wei,TANG Xinglei,YUE Liangxu,KANG Jincan(),ZHANG Qinghong,WANG Ye   

  1. National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
  • Received:2021-01-09 Revised:2021-04-12 Published:2021-07-05 Online:2021-07-05
  • Contact: KANG Jincan E-mail:hgcheng@stu.xmu.edu.cn;kangjc@xmu.edu.cn

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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

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

中图分类号: 

  • TQ 028.8

图1

乙烷氯氧化、乙烯与苯烷基化的催化反应性能"

图2

Mn/CeO2氧化物与H-ZSM-5(25)分子筛的耦合方式对反应性能的影响（反应条件：W(Mn/CeO2) = 0.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5, Mn/CeO2∶H-ZSM-5= 1∶2）"

图3

Mn/CeO2氧化物与H-ZSM-5分子筛的质量比对催化性能的影响（反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5）"

图4

H-ZSM-5分子筛硅铝比对双功能催化剂反应性能的影响（反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, Mn/CeO2∶H-ZSM-5 = 1∶2, time on stream 2.5 h, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5）"

图5

Mn/CeO2-H-ZSM-5(38)- grind催化剂上反应性能随时间变化(反应条件：W = 1.5 g, T = 450℃, P = 0.1 MPa, F(total) = 40 ml/min, C2H6/benzene/HCl/O2/N2/He = 1/3.2/3/1/1.5/3.5)"

图6

Mn负载前后CeO2的XRD谱图"

图7

Mn/CeO2、H-ZSM-5及其复合物的XRD谱图"

图8

Mn/CeO2纳米棒的TEM图"

图9

Mn/CeO2与H-ZSM-5分子筛研磨复合后的TEM图"

表1

催化剂反应前后的XRF分析结果"

Reaction time/hElement content/% (mass)
CeMnAlSi
015.862.160.8434.3
2.515.912.070.8134.0
3516.431.620.7539.7

图10

不同硅铝比的H-ZSM-5分子筛的NH3-TPD图"

图11

Mn/CeO2-H-ZSM-5-grind催化剂反应前后NH3-TPD图"

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