Catalytic fast pyrolysis of cellulose in a microreactor system using hierarchical zsm-5 zeolites treated with various alkalis

Hierarchical ZSM-5 catalysts were prepared by desilication using NaOH, Na2CO3 and TPAOH with different concentrations under the same treatment conditions. Their structures and acidities were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), N2 adsorption and desorption (N2-BET) and ammonia temperature-programmed desorption (NH3-TPD). The catalytic fast pyrolysis (CFP) of cellulose to produce aromatics over the hierarchical ZSM-5 catalysts prepared using different alkali treatments was investigated. The alkali treatment by Na2CO3 (0.4 ∼ 0.8 M) was much milder than treatment by NaOH, which allowed the desilication process to be highly controllable, resulting in an increase of both the amount and strength of the strong acid sites, and the formation of hierarchical structures combining micro- and mesoporosity. The organic hydroxide TPAOH did not change the pore structure of ZSM-5, but it greatly increased the relative crystallinity. The CFP of cellulose with HZSM-5 produced 35.5% liquid aromatic hydrocarbons and 32.7% coke. The yield of aromatics increased after Na2CO3 treatment but decreased after NaOH treatment. In addition, the yield of coke showed the opposite trend. The highest aromatic yield (38.2%) and lowest coke yield were obtained in the CFP of cellulose with the desilicated zeolite treated with 0.6 M Na2CO3. The increased acidity in hierarchical ZSM-5 treated with Na2CO3 increased the selectivity of highly valuable aromatics, such as benzene, toluene, and xylene, and decreased the selectivity of large aromatics. TPAOH-treated HZSM-5 showed a slightly increased yield of aromatics due to the repair effect of TPAOH, but this treatment did not form a mesoporous structure.