Communication
ChemComm
external surface of zeolite during the carbonylation reaction. Dr Guohui Yang thanks the financial support from the National
The internal zeolite pores and channels were not affected at all. Natural Science Foundation of China (91645113 and U1510110)
The coke deposition mechanism on this HEU-12 zeolite is and the Key Research Program of Frontier Sciences, CAS, Grant
completely different from that known for other zeolite catalysts. No. QYZDB-SSW-JSC043.
The coke formation on zeolites such as MOR and ZSM-35 in the
carbonylation reaction usually occurs inside the zeolite pores
and channels, resulting in their quick deactivation. Therefore,
the specific coke formation mechanism of HEU-12 was favour-
Conflicts of interest
There are no conflicts to declare.
able for its excellent stability. To further analyze the cause of
deactivation, coke species over the spent zeolite was identified
by GC-MS (Fig. S11, ESI†). The coke extracted from the spent
HEU-12 consisted mainly of single-ring aromatics with two or
more aliphatic branches. Besides, traces of compounds with
two-ring aromatics were also identified. Based on the above
results, a deduced model of coke formation on HEU-12 during
DME carbonylation reaction was proposed (Scheme S1, ESI†).
To investigate the potential commercial application of
EU-12, the spent catalyst after 50 h reaction was regenerated. XRD
patterns indicated that the crystallinity of regenerated HEU-12
catalyst was retained well. The NH3-TPD analysis of the regen-
erated HEU-12 catalyst revealed that the total acid amount
can be recovered to a comparative level as that of fresh zeolite
(Fig. S12a, ESI†). It can be observed that the catalytic activity of
spent HEU-12 could be recovered after first and second regen-
erations. The MA selectivity of regenerated HEU-12 catalyst was
almost the same as that of fresh HEU-12 zeolite (Fig. S12b, ESI†).
Furthermore, based on the proposed reaction mechanism, the
catalytic activity and MA selectivity over HEU-12 could be
improved facilely by decreasing the diffusion path or tuning
the amount of Brønsted and Lewis acid sites with metals.15
A Cu/EU-12 (Cu: 0.8 wt%, measured by XRF) sample prepared by
Notes and references
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This work was financially supported by ACT-C (JPMJCR12YT),
CREST (17-141003297) of Japan Science and Technology Agency.
Financial aid from JST-SATREPS project is also greatly appreciated.
Chem. Commun.
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