化工学报 ›› 2021, Vol. 72 ›› Issue (7): 3658-3667.DOI: 10.11949/0438-1157.20210050
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
作者简介:
程挥戈(1996—),男,硕士研究生,基金资助:
CHENG Huige(),NIU Wei,TANG Xinglei,YUE Liangxu,KANG Jincan(),ZHANG Qinghong,WANG Ye
Received:
2021-01-09
Revised:
2021-04-12
Online:
2021-07-05
Published:
2021-07-05
Contact:
KANG Jincan
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。
中图分类号:
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.
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.
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)
Fig.2 Effect of contact manner of Mn/CeO2 oxide and H-ZSM-5(25) zeolite on catalytic performances others—C2H4Cl2 and hydrocarbons
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)
Fig.3 Catalytic performances of Mn/CeO2-H-ZSM-5-grind with different mass ratios of Mn/CeO2 oxide to H-ZSM-5 zeolite
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)
Fig.4 Effect of Si/Al ratio of H-ZSM-5 on catalytic performances over Mn/CeO2-H-ZSM-5 bifunctional catalyst
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)
Fig.5 Catalytic performances with time on stream over Mn/CeO2-H-ZSM-5-grindcatalyst
Reaction time/h | Element content/% (mass) | |||
---|---|---|---|---|
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 |
表1 催化剂反应前后的XRF分析结果
Table 1 XRF analysis of Mn/CeO2-H-ZSM-5 before and after catalytic reaction
Reaction time/h | Element content/% (mass) | |||
---|---|---|---|---|
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 |
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