Effect of temperature in the conversion of methanol to olefins (MTO) using an extruded SAPO-34 catalyst

doi:10.1007/s11705-018-1709-8

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (2) : 226-238 https://doi.org/10.1007/s11705-018-1709-8

RESEARCH ARTICLE

Effect of temperature in the conversion of methanol to olefins (MTO) using an extruded SAPO-34 catalyst

Ignacio Jorge Castellanos-Beltran, Gnouyaro Palla Assima, Jean-Michel Lavoie(

)

Université de Sherbrooke, Chaire de Recherche Industrielle sur l'Éthanol Cellulosique et les Biocommodities (CRIEC-B), Sherbrooke, QC, Canada, J1L 2Y4

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Abstract

The methanol-to-olefin (MTO) reaction was investigated in a bench-scale, fixed-bed reactor using an extruded catalyst composed of a commercial SAPO-34 (65 weight percentage, wt-%) embedded in an amorphous SiO₂ matrix (35 wt-%). The texture properties, acidity and crystal structure of the pure SAPO-34 and its extruded form (E-SAPO-34) were analyzed and results indicated that the extrusion step did not affect the properties of the catalyst. Subsequently, E-SAPO-34 was tested in a temperature range between 300 and 500 °C, using an aqueous methanol mixture (80 wt-% water content) fed at a weight hour space velocity (WHSV) of 1.21 h⁻¹. At 300 °C, a low conversion was observed combined with catalyst deactivation, which was ascribed to oligomerization and condensation reactions. The coke analysis showed the presence of diamandoid hydrocarbons, which are known to be inactive molecules in the MTO process. At higher temperatures, a quasi-steady state was reached during a 6 h reaction where the optimal temperature was identified at 450 °C, which incidentally led to the lowest coke deposition combined with the highest H/C ratio. Above 450 °C, surges of ethylene and methane were associated to a combination of H-transfer and protolytic cracking reactions. Finally, the present work underscored the convenience of the extrusion technique for testing catalysts at simulated scale-up conditions.

Keywords MTO SAPO-34 temperature extrusion coke light alkanes

Corresponding Author(s): Jean-Michel Lavoie

Just Accepted Date: 30 January 2018 Online First Date: 26 April 2018 Issue Date: 09 May 2018

Cite this article:

Ignacio Jorge Castellanos-Beltran,Gnouyaro Palla Assima,Jean-Michel Lavoie. Effect of temperature in the conversion of methanol to olefins (MTO) using an extruded SAPO-34 catalyst[J]. Front. Chem. Sci. Eng., 2018, 12(2): 226-238.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1709-8
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I2/226

Fig.1 Scanning electron microscope images of (a) P-SAPO-34 (×5 000), (b) E-SAPO-34 (×5 000), and (b-inset) magnified E-SAPO-34 surface (×30 000)

Fig.2 XRD patterns of (a) P-SAPO-34, (b) E-SAPO-34 and (c) SAPO-34 extracted from the IZA database

Tab.1 Crystal properties of the SAPO-34 in powder (P) and extruded (E) form

Tab.2 Physico-chemical properties of SAPO-34 in powder (P) and extruded (E) form

Tab.3 Effect of temperature on the conversion of MCH, products molar distribution and performance parameters computed at 2 and 6 h of time-on-stream

Tab.4 Effect of MTO testing (300-500 °C) on the catalyst texture properties, coke content and H/C ratio, and coke molecule composition

Fig.16 Evolution of the MTO reaction over time at 300 °C: (a) molar distribution of light olefins and large molecules (C_4-6), (b) molar distribution of oxygenated molecules (methanol and DME), (c) MCH and EPR factors, and (d) molar distribution of light alkanes (methane and propane)

Fig.17 Mechanisms reported in the literature for the formation of methane in the MTO reaction. Scheme 1 was adapted from reference [³⁷], while scheme 2 was extracted from reference [³⁸]. Scheme 3 is a more recent mechanisms developed by Wei and co-workers, in which methane was identified as a by-product of the formation of the early molecules containing the first C?C bond [³⁹]

Fig.18 Effect of temperature (350?500 °C) on the molar concentration of (a) methane and (b) propane over time

Fig.19 Scheme of (a) the original mechanism proposed by Haag and Dessau in the protolytic cracking of alkanes [⁴²], and (b) the suggested mechanism including the reaction in scheme 2 and protolytic cracking of alkenes explaining the formation of methane at high temperatures

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