Elucidating the dominant reaction mechanism of methanol-to-olefins conversion in H-SAPO-18: A first-principles study

• Published in: Chinese journal of catalysis Vol. 39; no. 7; pp. 1272 - 1279
• Main Authors: Wang, Chuan-Ming, Wang, Yang-Dong, Xie, Zai-Ku
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.07.2018
• Subjects: Density functional theory; H-SAPO-18 zeotype; Hydrocarbon pool reaction mechanism; Methanol-to-olefins conversion; Olefin-based hydrocarbon pool; Density functional theory; Methanol-to-olefins conversion; Olefin-based hydrocarbon pool; H-SAPO-18 zeotype; Hydrocarbon pool reaction mechanism
• ISSN: 1872-2067; 1872-2067
• DOI: 10.1016/S1872-2067(18)63064-5

The reaction mechanism of zeolite- or zeotype-catalyzed methanol-to-olefins (MTO) conversion is still a subject of debate. Employing periodic density functional theory calculations, the olefin-based cycle was studied using tetramethylethene (TME) as a representative olefinic hydrocarbon pool in H-SAPO-18 zeotype. The overall free energy barrier at 673 K was calculated and found to be less than 150 kJ/mol in the TME-based cycle, much lower than those in the aromatic-based cycle (> 200 kJ/mol), indicating that olefins themselves are the dominant active hydrocarbon pool species in H-SAPO-18. The similarity of the intermediates involved between the aromatic-based cycle and the olefin-based cycle was also highlighted, revealing that both cycles were pattern-consistent. The selectivity related to the distribution of cracking precursors, such as higher olefins or carbenium ions, as a result of the olefin-based cycle for the MTO conversion. The enthalpy barrier of the cracking step scaled linearly with the number of carbon atoms of cracking precursors to produce ethene or propene with ethene being much less favored than propene for cracking of C7 and higher precursors. This work highlighted the importance of the olefin-based cycle in H-SAPO-18 for the MTO conversion and established the similarity between the olefin-based and aromatic-based cycles. The olefins were calculated to be the dominant hydrocarbon pool for MTO conversion in H-SAPO-18. The enthalpy barrier of the cracking step linearly relates to the size of cracking precursors.