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Green Chemistry
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ARTICLE
Journal Name
DOI: 10.1039/C7GC00659D
Scheme 2 Proposed mechanism over microporous zeolites
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and ethanol.
According to the control experiments, the process of
etherification of EG with methanol were proposed as in Scheme 2.
It can be found that the kinetic diameter of methanol is smaller and
matching with pore structure of SAPO-34, can enter into the pores
of SAPO-34 and then activate by the inside acid site of catalyst. The
entered EG could not form the 1, 4-dioxane due to the pore size of
SAPO-34. The activated methanol molecule attacked the EG
molecules via SN2 substitution to first give 2-methoxyethanol. And
such activated methanol attacks another side OH in EG to give the
final desired product of dimethoxyethane. For the larger pore size
zeolite, such as HY, EG was easily accessed into its pores and rapidly
activated to generate 1,4-dioxane, decreased the selectivity of
desired product. It can be learned from the discussion that
efficiently limiting the formation of 1,4-dioxane by pore size control
is an effective method to improve the desired products selectivity.
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In summary, an efficient microporous zeolite has been developed to
achieve high selectivity of dimethoxyethane via etherification of
crude ethylene glycol with methanol, using fixed bed reactor. SAPO-
34 was the most appropriate catalyst for such etherification, which
could realize the selectivity of dimethoxyethane up to 79.4% with
around 96.7% of conversion. To the best of our knowledge, the
selectivity of dimethoxyethane in this report is much higher than
the data reported in the literature. Further study reveals that the
pore structure of SAPO-34 could effectively limit the formation of
1,4-dioxane from ethylene glycol and enhanced the activated
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methanol and water, which provide
a green route for
dimethoxyethane producing and could expand its application.
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Acknowledgements
This work was supported by the National Natural Science
20.
Foundation of China (projects 21233008, 91545102, 21473188) and 21.
the Strategic Priority Research Program of Chinese Academy of
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Sciences (XDB17020300)
Notes and references
6 | J. Name., 2012, 00, 1-3
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