Benzene alkylation with CO2/H2 is
a doubly
beneficial option to upgrade benzene toward valuable products, in
which benzene can be converted into valuable toluene and xylene, while
CO2 can be utilized as an alkylation reagent to mitigate
the greenhouse effect. It is quite challenging to ascertain the critical
rule of zeolite regulation for the synergistic effect in oxide-zeolite
composite (OXZEO) catalysts, a series of bifunctional catalysts were
investigated in this work, consisting of ZnZrO
x
solid solution and nano-sized HZSM-5 with uniform size distribution
and distinct acid properties. Key parameters affecting the catalyst
performance were analyzed and optimized in this tandem reaction, namely,
the mass ratio of two components, the SiO2/Al2O3 ratio of HZSM-5, and the proximity between ZnZrO
x
and HZSM-5. Due to the increased active
site accessibility originating from nano-sized HZSM-5, the combined
selectivity of toluene and xylene reaches 94.6% at 31.3% benzene conversion,
respectively. Moreover, low ethylbenzene selectivity (<1%) has
been achieved. It is worth noting that the long-term stability test
indicates a faster deactivation in the nano-sized HZSM-5 system as
compared with the micro-sized counterpart. Based on EDS mappings,
it is found that nano-sized HZSM-5 experiences a more severe metal
migration issue, resulting in lower catalyst stability. The reaction
mechanism with formate-methoxy intermediates and the synergistic effect
of CO2 hydrogenation-alkylation were further confirmed
by in situ diffuse reflectance infrared Fourier transformations
spectroscopy and gas chromatography–mass spectrometry. By correlating
zeolite size and acidity with catalytic performances, these findings
could facilitate the further rational design of OXZEO catalysts toward
CO2 catalytic conversions.