A descriptor for the relative propagation of the aromatic- and olefin-based cycles in methanol-to-hydrocarbons conversion on H-ZSM-5

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• 作者：Samia Ilias^a ; ^{ilias003@umn.edu} ; Rachit Khare^a ; ^{khare014@umn.edu} ; Andre Malek^b ; ^{AMalek@dow.com} ; Aditya Bhan^a ; ^{abhan@umn.edu}
• 关键词：Methanol-to-hydrocarbons ; Methanol-to-olefins ; Zeolite ; Hydrocarbon pool ; Olefin and aromatic methylation ; HZSM-5 ; Selectivity
• 刊名：Journal of Catalysis
• 出版年：2013
• 出版时间：July, 2013
• 年：2013
• 卷：303
• 期：Complete
• 页码：135-140
• 全文大小：1352 K

文摘

The observed product distribution in methanol-to-hydrocarbons (MTH) catalysis can be rationalized based on the relative rates of propagation of the aromatic- and olefin-based cycles that operate on the zeolite catalyst. We report that the ratio of ethene to 2-methylbutane + 2-methyl-2-butene (ethene/2MB) yield can be used to describe the propagation of aromatic and olefin methylation/cracking cycles. The co-reaction of ¹²C-ethene with ¹³C-dimethyl ether (DME) shows that the rate of DME conversion (1.62 mol C (mol Al s)^?1) is ¡«20 times faster than ethene conversion (0.08 mol C (mol Al s)^?1), suggesting that ethene can be considered as terminal product for MTH at 623 K. At iso-conversion conditions at 548 K, propene is co-fed with DME to increase propagation of the olefin-based cycle and correspondingly a 1.7-fold decrease in the ethene/2MB yield is observed. Similarly, the co-reaction of toluene with DME increases propagation of the aromatic-based cycle and a 2.1-fold increase in the ethene/2MB yield is observed. The ethene/2MB yield also increased by a factor of 2 as DME conversion increased from 5 % to 62 % , which is consistent with the observed concurrent increase in selectivity to ethene and methylbenzenes. For the reaction of DME alone, increasing the temperature from 548 K to 723 K increases the propagation of the olefin-based cycle and a corresponding decrease in the ethene/2MB yield from 4.7 to 1.3 is also observed. The ethene/2MB yield varies systematically with feed composition, conversion, and temperature, showing that this ratio describes the relative propagation of the aromatic to olefin methylation/cracking cycles in MTH conversion on H-ZSM-5.