One-pass conversion of benzene and syngas to alkylbenzenes by ZnAlOx/ZSM-5 composite catalyst
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摘要: 烷基苯是一类重要的有机化工基础原料,通过煤化工路线的苯合成气烷基化技术生产烷基苯,减轻中国对石油的过度依赖。本研究通过机械混合制备了ZnAlOx/ZSM-5复合催化剂用于苯与合成气的烷基化反应,复合催化剂两组分的最佳质量比为1∶1,复合氧化物的锌铝最佳物质的量比为2∶1,苯与合成气串联反应中间体为甲醇/二甲醚,甲醇合成催化中心是ZnO组分上的氧空位,甲醇在Al2O3上可脱水为二甲醚,甲醇/二甲醚进而在ZSM-5上与苯发生烷基化反应。由于ZnAlOx的高温甲醇或二甲醚合成特征,与ZSM-5的苯烷基化反应能够有效匹配,实现了高的反应活性和选择性。Abstract: Alkylbenzenes are important bulky chemicals. The production of alkylbenzenes through benzene and syngas alkylation technology of coal chemical industry can reduce the domestic dependence on petroleum. In this study, mechanical mixture of ZnAlOx and ZSM-5 were used to catalyze the alkylation reaction of benzene and syngas. The results showed that the best performance catalyst was obtained with the 1∶1 mass ratio of the two components and the 2∶1 molar ratio of zinc to aluminum. It was suggested that the main reaction intermediates of methanol and dimethyl are produced on the O vacancy of ZnO and L acidic center of Al2O3 in ZnAlOx. And the alkylated benzenes are formed by the reaction of benzene with the intermediates over ZSM-5. Due to the high temperature property of ZnAlOx for methanol synthesis which can accommodate to the reaction of ZSM-5 for benzene alkylation, the high catalytic activity and selectivity was obtained.
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Key words:
- alkylbenzene /
- benzene /
- syngas /
- ZnO /
- bifunctional catalyst
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表 1 ZnAlOx和ZSM-5的元素组成
Table 1 Elemental composition of ZnAlOx and ZSM-5
Catalyst Zn/Ala ratio Zn/Alb ratio A/(m2·g−1) ZnAlOx Zn/Al=1 Zn/Al=0.69 137.25 ZnAlOx Zn/Al=2 Zn/Al=1.47 108.65 ZnAlOx Zn/Al=3 Zn/Al=2.34 91.89 ZSM-5 SiO2/Al2O3 = 200 Si/Al=86 370.52 ZSM-5: Na 0.43/%; a: raw material feed molar ratio; b: element molar ratio via ICP -
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