Stability of Zeolite HZSM-5 in Liquid Phase Dehydration of Methanol to Dimethyl Ether
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Stability of Zeolite HZSM‑5 in Liquid Phase Dehydration of Methanol to Dimethyl Ether Xinde Sun1 · Yue Yang1 · Yanli He1 · Shukui Zhu1 · Zhongmin Liu1 Received: 30 September 2020 / Accepted: 3 November 2020 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract A high performance HZSM-5 catalyst for liquid phase dehydration of methanol to dimethyl ether (DME) was developed by optimizing Si/Al ratio and hydrothermal treatment temperature. During 6788 h long term test, DME selectivity kept above 99.96% and only slight deactivation was observed primarily due to coking and decline of HZSM-5 crystallinity. Graphic Abstract 90
Liquid phase dehydration of MeOH
MeOH Conversion (%)
80 70 60
SDME: >99.96%
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Deactivation: coke + ZSM-5 crystallinity
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Si dissolution 0
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Time on Stream (h)
Keywords Dimethyl ether · Liquid phase dehydration · ZSM-5 · Deactivation · Dissolution Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10562-020-03454-y) contains supplementary material, which is available to authorized users. * Xinde Sun [email protected] * Zhongmin Liu [email protected] Yue Yang [email protected] Yanli He [email protected] Shukui Zhu [email protected] 1
National Engineering Laboratory for Methanol to Olefins, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, People’s Republic of China
1 Introduction Dimethyl ether (DME) is nontoxic, noncorrosive, clean (free of sulfur and nitrogen compounds), safe to store and handle (does not form explosive peroxides), environmentally benign (easy to degrade photochemically), and has high oxygen content and high cetane number [1–3]. It can be used as, (1) substitute for diesel, (2) LPG blend, (3) gas turbine fuel in power generation sector, (4) propellant in aerosol formulations, (5) green refrigerant, and (6) intermediate for producing many other important chemicals [1–6]. It is projected to be one of the fundamental chemical feed stocks in this century [4]. The total worth of DME industry is estimated to reach $ 9.7 billion by 2020 [1]. DME can be derived from a variety of feed-stock including fossil fuels such as natural gas, crude oil, residual oil, coal, and renewable sources such as biomass, agricultural products and
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waste [2, 3, 7]. The synthesis method includes: (1) the indirect route by dehydration of methanol which was produced from syngas (CO, CO2, and H2) separately, and (2) the direct route in which DME is produced from syngas in a single stage over bi-functional catalysts [1, 2]. So far, the most common process is dehydration of methanol which is usually carried out in gas phase [6, 8]. The catalysts [1, 2, 9] includes A l2O3 [4, 10, 11], zeolites [8, 12–15], heteropolyacids [16, 17] and FePO4 [18]. Low energy consuming catalytic distillation process has been proposed for synthesis of DME from methanol dehydration [2,
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