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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2018, Vol. 12 Issue (2): 226-238   https://doi.org/10.1007/s11705-018-1709-8
  本期目录
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.

Key wordsMTO    SAPO-34    temperature    extrusion    coke    light alkanes
收稿日期: 2017-09-14      出版日期: 2018-05-09
Corresponding Author(s): Jean-Michel Lavoie   
 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2018, 12(2): 226-238.
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. Front. Chem. Sci. Eng., 2018, 12(2): 226-238.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-018-1709-8
https://academic.hep.com.cn/fcse/CN/Y2018/V12/I2/226
Fig.1  
Fig.2  
Samples SAPO-34 content /% Relative crystallinity /% Crystallite size /nm
SAPO-34
(P) 100.0 100 41.3
(E) 65.0 68.5 42.0
Tab.1  
Samples Pore volume NH3-TPD
/(cm3?gSAPO-34?1) /(µmol?gSAPO-34?1)
Total VMicro* VMeso* Total Weak Strong
SAPO-34
(P) 0.252 0.252 0.000 1 348 528 820
(E) 0.483 0.237 0.246 1 370 531 839
Tab.2  
time-on-stream
Final (6 h)
Temperature /°C 300 350 380 450 480 500 300 350 380 450 480 500
MCH /% 61.8 74.4 85.6 83.5 83.3 84.9 15.8 72.2 80.2 86.1 89.1 91.5
Product molar distribution /%
Olefins
Ethylene 31.0 37.3 48.3 59.9 66.6 64.4 10.1 38.1 49.2 62.4 67.8 66.4
Propylene 32.8 31.7 29.7 25.1 20.5 16.1 10.7 34.7 31.1 24.7 19.9 17.9
C4-6 15.6 15.1 10.7 6.3 3.5 2.8 3.2 12.5 9.2 4.8 2.9 2.8
Paraffins
Methane 2.0 1.2 1.5 3.3 7.0 14.7 3.1 1.3 1.7 3.6 8.0 10.7
Propane 16.1 14.0 9.0 4.3 1.6 1.1 5.2 12.1 7.8 3.4 1.2 1.2
Oxygenated
MeOH 1.1 0.0 0.1 0.2 0.1 0.2 32.2 0.1 0.1 0.2 0.2 0.2
DME 1.1 0.0 0.0 0.0 0.0 0.0 35.1 0.4 0.0 0.0 0.0 0.0
EPR /mol 0.95 1.18 1.63 2.38 3.25 4.01 0.94 1.10 1.57 2.53 3.55 3.70
Hydrogen transfer index 0.329 0.310 0.233 0.146 0.072 0.063 0.327 0.259 0.201 0.121 0.057 0.063
Δ350-380 Δ380-450 Δ450-480 Δ480-500
ΔR 1.49 1.22 3.14 2.93
Tab.3  
Temperature/°C
300 350 380 450 480 500
Pore volume /(cm3• g SAPO-34-1)
VMicro 0.067 0.135 0.167 0.175 0.144 0.131
Total 0.270 0.343 0.391 0.408 0.380 0.381
Coke content /wt.-% 10.6 6.06 4.17 3.81 5.12 5.55
Coke H/C ratio (atomic) 1.22 1.38 1.71 1.89 1.08 0.95
Coke composition
Adamantanes
PMBs
PCAs
Tab.4  
Fig.16  
Fig.17  
Fig.18  
Fig.19  
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