Conversion of methanol to propylene over SAPO-14: Reaction mechanism and deactivation

doi:10.1016/S1872-2067(22)64123-8

Abstract

Abstract:

Methanol to olefins (MTO) reaction as an important non-oil route to produce light olefins has been industrialized, and received over 80% ethylene plus propylene selectivity. However, to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of challenge. Small-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene selectivity. It provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic performance. In this work, a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions, which help to achieve more selectivity data in response to very short catalytic life of SAPO-14. Changes in product distribution, especially during the low activity stage, reflect valuable information on the reaction pathway. Combined with in situ diffuse reflectance infrared Fourier-transform spectroscopy, in situ ultraviolet Raman measurements and ¹²C/¹³C isotopic switch experiments, a reaction pathway evolution from dual cycle to olefins-based cycle dominant was revealed. In addition, the deactivation behaviors of SAPO-14 were also investigated, which revealed that polymethylbenzenes have been the deactivated species in such a situation. This work provides helpful hints on the development of characteristic methanol to propylene (MTP) catalysts.

Key words: Methanol to propylene, SAPO-14 molecular sieve, UV Raman spectroscopy, Dual-cycle mechanism, Deactivation

Ye Wang, Jingfeng Han, Nan Wang, Bing Li, Miao Yang, Yimo Wu, Zixiao Jiang, Yingxu Wei, Peng Tian, Zhongmin Liu. Conversion of methanol to propylene over SAPO-14: Reaction mechanism and deactivation[J]. Chinese Journal of Catalysis, 2022, 43(8): 2259-2269.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64123-8

https://www.cjcatal.com/EN/Y2022/V43/I8/2259

Figures/Tables 6

Fig. 1. The views and sizes of cage-defining rings (red colored) for AEI, LEV, ERI, and AFN topologies.

Fig. 2. Seconds-level MTO product distribution and conversion and selectivity profiles of propylene, ethylene and propylene/ethylene ratios over SAPO-14 (a,b) and SAPO-18 (c,d). Reaction condition: 673 K, weight hourly space velocity: 0.5 h-1, methanol partial pressure: 5 kPa.

Fig. 3. In situ diffuse reflectance infrared Fourier-transform spectra recorded during methanol conversion over SAPO-14 at 673 K. The spectra were recorded from 0 to 20 min.

Fig. 4. Time-resolved UV Raman spectra, the selected typical UV Raman spectra and their peak fittings of SAPO-14 catalyst in 12C-methanol conversion (a?c), and 13C-methanol conversion followed by 12C-methanol switch at a TOS of 6 min (d?f). Reaction condition: 673 K; methanol partial pressure: 5 kPa; ultraviolet excitation line: 244 nm.

Fig. 5. The coke amount as a function of time on stream (a). The micropore volume (blue line) and Brunauer-Emmett-Teller (BET) surface area (black line) of spent SAPO-14 catalysts as functions of coke amount (b).

Fig. 6. Ultraviolet-visible spectra of SAPO-14 at different reaction times (a). Gas chromatography-mass spectrometry chromatograms of organic species in SAPO-14 at different reaction times (b). Matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectra for extracts obtained from SAPO-14 and the deduced possible molecular structure of polycyclic aromatic hydrocarbons (c). The indicated molecular structures are representative examples of possible structures. Reaction conditions: 673 K for 37 min; weight hourly space velocity: 0.5 h?1.

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