Abstract
A facile method was developed for the synthesis of highly crystallized nano-sized HZSM-5 via adding sodium alginate into zeolite precursor solution. The effects of addition order and dosage of sodium alginate on the physicochemical properties of the catalysts were systematically studied by XRD, FT-IR, TEM, N2 adsorption–desorption, ICP-OES, 27Al MAS-NMR and NH3-TPD. It was found that the addition order and dosage of sodium alginate have strong influences on the crystal sizes and acidic properties of the obtained catalysts. About 100 nm crystals were generated in S-HZSM-5-0.75-p through adding the sodium alginate prior to TEOS, which were smaller than the crystal size of conventional HZSM-5 (200–350 nm). However, this method was unfavorable for the incorporation of Al into the framework of HZSM-5. The low content of framework Al could cause a decrease in acidity and the amount of acid sites was only 0.38 mmol g−1 in S-HZSM-5-0.75-p, which was slightly lower than conventional HZSM-5 (0.42 mmol g−1). In contrast, smaller crystals (50 nm) and more acid amounts (1.24 mmol g−1) could be obtained for the S-HZSM-5-0.75 synthesized by adding the sodium alginate after TEOS. Nevertheless, the crystals could be easily aggregated to a dandelion-like particles and possessed fewer acid sites when the sodium alginate was added excessively. Under the conditions of 0.1 MPa, 400 °C and a WHSV of 0.96 h−1, a desired 35.06% BTX yield with 8.5 h service lifetime in glycerol aromatization was obtained over S-HZSM-5-0.75 comparing with conventional HZSM-5 (22.19% BTX yield and 3.5 h service lifetime). The remarkable improvement in catalytic performance of nano-sized HZSM-5 zeolite was mainly attributed to the more acid amounts and smaller crystal size, which could increase the accessibility to the acid sites and shorten the diffusion path length.
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The authors would like to thank the financial support from Fundamental Research for the National Natural Science Foundation of China (No. 21676054, 2140603), Natural Science foundation of Jiangsu (No. BK20161415), Fundamental Research for the Central Universities (No. 2242018K40041).
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Xu, N., Pan, D., Wu, Y. et al. Preparation of nano-sized HZSM-5 zeolite with sodium alginate for glycerol aromatization. Reac Kinet Mech Cat 127, 449–467 (2019). https://doi.org/10.1007/s11144-019-01566-0
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DOI: https://doi.org/10.1007/s11144-019-01566-0