Features of the deactivation of Mg/HZSM-5 catalysts for the synthesis of lower olefins from dimethyl ether in a slurry reactor

A. Stashenko, T. Batova, T. Obukhova, N. Kolesnichenko
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Abstract

In a slurry reactor, the formation of compaction products on Mg/HZSM-5 catalysts, irrespective of the SiO2 /Al2O3 molar ratio in the zeolite, proceeds predominantly on strong acidic sites. The composition of compaction products (mostly trimethyl- and tetramethylbenzenes) virtually does not change with a growth of the molar ratio; however, their amount decreases, which is related to a growth of the mesopore volume with an increase in the SiO2 /Al2O3 ratio. This leads to a decrease in diffusion limitations and contribution of secondary reactions and enhances the removal of coke precursors from the zeolite surface, thus promoting the catalyst activity (the conversion of DME increases twofold). The composition of reaction products changes only slightly with a growth of the SiO2 /Al2O3 molar ratio, the total selectivity to lower olefins is ca. 70 wt.%. A rapid loss of the Mg/HZSM-5 activity with extending the operation time in a slurry reactor is caused not by coking, but rather by «clogging» of the catalyst with decomposition products of the dispersion medium (polydimethylsiloxane).
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浆料反应器中二甲醚合成低烯烃的Mg/HZSM-5催化剂失活特性
在泥浆反应器中,无论沸石中SiO2 /Al2O3的摩尔比如何,Mg/HZSM-5催化剂上的压实产物主要在强酸性部位形成。压实产物(主要是三甲基苯和四甲基苯)的组成几乎不随摩尔比的增长而变化;随着SiO2 /Al2O3比的增大,介孔体积增大,其含量逐渐减少。这降低了扩散限制和二次反应的贡献,增强了焦炭前驱体从沸石表面的去除,从而提高了催化剂的活性(二甲醚的转化率提高了两倍)。随着SiO2 /Al2O3摩尔比的增加,反应产物的组成变化不大,对低烯烃的总选择性约为70 wt.%。随着浆料反应器中操作时间的延长,Mg/HZSM-5活性的快速损失不是由焦化引起的,而是由分散介质(聚二甲基硅氧烷)的分解产物“堵塞”催化剂引起的。
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