Catalytic Fast Pyrolysis of Kraft Lignin over Hierarchical HZSM-5 and Hβ Zeolites

The hierarchical HZSM-5 and H beta zeolites were prepared by alkaline post-treatment methods adopting Na2CO3, TMAOH/NaOH mixture, and NaOH as desilication sources, respectively. More mesopores are produced over two kinds of zeolites, while the micropores portion is well preserved. The mesopores formed in hierarchical H beta zeolites were directly related to the basicity of the alkaline solution, indicating that H beta zeolite is more sensitive to the alkaline post-treatment. The hierarchical HZSM-5 and H beta zeolites are more active than the parent one for catalytic fast pyrolysis (CFP) of Kraft lignin. Hierarchical zeolites retained the function of acid catalysis, while additionally creating larger mesopores to ensure the entry of bulkier reactant molecules. The increase of the condensable volatiles yield can be attributed to the improvement of the mass transfer performance, which correlates well with the change of mesoporous surface area. In particular, the condensable volatiles yield for the optimized hierarchical H beta reached approximately two times that of the parent H beta zeolites. In contrast to the parent HZSM-5, the optimized hierarchical HZSM-5 zeolite significantly reduced the selectivity of oxygenates from 27.2% to 3.3%.