Catalytic performance of modified kaolinite in pyrolysis of benzyl phenyl ether: A model compound of low rank coal

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A serials of modified kaolinites were prepared by calcination and further acid treatment and characterized by in-situ XRD, N 2 adsorption, NH 3 -TPD, Py-IR and 27 Al MAS-NMR. And their catalytic performance in pyrolysis of methanol/benzyl phenyl ether (MeOH-BPE), a model compound of low-rank coal, were investigated at 400 °C in a fixed-bed reactor to explore the correlation between the structure of modified samples and their catalytic performances. The results show that calcination temperature above 500 °C causes the collapse of kaolinite structure. Further acid leaching facilitates the formation of micropores and mesopores. The calcination of kaolinite leads to the transformation of six-coordinate Al atoms (Al VI ) into four and five coordinate species (Al IV and Al V ), while the subsequent acid treatment increases the contents of Al IV and Al VI and removes Al V . Total acid sites exhibit a first increase and then decrease tendency with the raising calcination temperature. In the presence of the modified kaolinites, BPE conversion significantly enhances and reaches the highest value of 91.41% over K-A-700 prepared by calcination at 700 °C of kaolinite and further acid leaching. Besides, the maximum content of phenol and toluene is also achieved due to the highest acid sites and Al IV content of K-A-700, which favors the generation of ·H, thus resulting in an obvious inhibition of bibenzyl formation but a significant increase of 2-benzylphenol. In-situ pyrolysis by time-of-flight mass spectrometry suggests that the cleavage of C al -O bond of BPE to form phenol radicals and benzyl radicals is the primary way, while insufficient ·H results in the formation of dominant product of 2-benzylphenol. • Modification makes the six-coordinate Al of kaolinite to four and five species. • Modified-kaolinite promotes BPE conversion and the highest appears on K-A-700. • The primary way of BPE pyrolysis is cleavage of C ali -O to form phenoxyl and benzyl radicals. • The mechanism of BPE pyrolysis is revealed by time-of-flight mass spectrometry.