Confinement effects in methanol to olefins catalysed by zeolites: A computational review

doi:10.1007/s11705-016-1557-3

Front. Chem. Sci. Eng.

2016, Vol. 10

Issue (1) : 76-89 https://doi.org/10.1007/s11705-016-1557-3

REVIEW ARTICLE

Confinement effects in methanol to olefins catalysed by zeolites: A computational review

German Sastre(

)

Instituto de Tecnologia Quimica U.P.V.-C.S.I.C, Universidad Politecnica de Valencia, Avenida Los Naranjos s/n, 46022 Valencia, Spain

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Abstract

Small pore zeolites, containing 8-rings as the largest, are widely employed as catalysts in the process of methanol-to-olefins (MTO). Reactants and products diffuse with constraints through 8-rings and this is one of the reaction bottlenecks related to zeolite micropore topology. Small pore zeolites and silicon-aluminophosphates(SAPOs) containing cavities, where olefins are mainly formed through the hydrocarbon pool (HP) mechanism, are frequently tested for MTO. Shape selectivity of transition states within the side-chain methylation will be reviewed as this is one of the controlling steps of the MTO process, with particular attention to the role of hexamethylbenzene (HMB) and heptamethylbenzenium cation (HeptaMB⁺), which are the most tipically detected reaction intermediates, common to the paring and side-chain routes within the HP mechanism. The relative stability of these and other species will be reviewed in terms of confinement effects in different cage-based zeolites. The role of the different alkylating agents, methanol, dimethyl ether (DME), and surface methoxy species (SMS) will also be reviewed from the computational viewpoint.

Keywords small pore zeolites SAPOs methanol-to-olefins hydrocarbon pool mechanism alkylation of polymethylbenzenes

Corresponding Author(s): German Sastre

Online First Date: 01 February 2016 Issue Date: 29 February 2016

Cite this article:

German Sastre. Confinement effects in methanol to olefins catalysed by zeolites: A computational review[J]. Front. Chem. Sci. Eng., 2016, 10(1): 76-89.

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https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1557-3
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I1/76

Fig.1 Citation network obtained from the search of {(MTO or “methanol to olefins”) and (zeo* or SAPO*)} in title or keywords or abstract in Scopus, giving 539 papers. The graph shows the number of papers as well as the relative citations between groups through line widths. ‘O’ is University of Oslo, ‘G’ is University of Gent, ‘U’ is Utrecht University, ‘D’ is Dalian Institute of Physical Chemistry, ‘S’ is University of Stuttgart, and ‘B’ is Universidad Politecnica del Pais Vasco (Bilbao)

Fig.2 Scheme of the catalytic properties of CHA zeotype for the MTO process. Left: CHA crystal with cavities sixfold connected, some of them fouled by the presence of coke. Right: Perspective view of cha cavity with the transition state of the concerted methylation of HMB

Fig.3 Simplified scheme of the MTO process through the HP mechanism in small pore zeolites containing cavities. HZ is a zeolite Brønsted site. From the several proposals for the formation of the first C–C bond, this scheme shows a simplified version of that recently suggested in ref. [27]

Fig.4 Simplified scheme showing relevant initial interatomic interactions of three unlikely direct mechanisms (DM) of C–C bond forming in MTO/zeolites discussed in the literature. The carbon atom in the SMS interacts with methanol through an oxygen (DM-1), hydrogen (DM-2) and carbon (DM-3)

Fig.5 Relevant cavities of the zeolites indicated containing the optimised geometry of the transition state of methylation of HMB with methanol. Highlighted r(O–C) distances are 2.22±0.02 Å in all cases; and r(C–C) distances are 2.26±0.01 Å in all cases. Angle(O–C–C) is: 150° (AEI), 177° (AFX), 176° (CHA), 163° (ERI), 125° (LEV), 169° (LTA), 166° (RHO), and 156° (RTH). The Al atom close to the Brønsted site with which methanol interacts is highlighted

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