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that the HB(12) composed of nanoparticles had a higher external surface area and mesopore volume (Figure 2, Table 1) which are beneficial to the products’ diffusion. Therefore, we concluded that the poor catalytic performance of HB(12) was mainly related to its acidic properties. Compared to Al-rich HB(12), HB(77) showed high selectivities to propylene and butenes, however, low selectivities to BTX, ethylene, propane and butanes (Figures 13 and 14A) were demonstrated. It could be due to the smaller amount of acid sites, especially the LAS (Table 1, Figures 6 and 8B). Note that, although the HB(77) had superior catalytic stability, the amount of coke formed on the HB(77) (137 mg/g-catalyst at TOS of 210 min) was comparable to that of Al-rich HB(12). As shown in Figures 13 and 14 catalytic stability and propylene selectivity with high n-hexane conversions can be greatly improved by dealumination with acid treatment. Note that crystal morphology and size were almost unchanged and the textural properties remained after the acid treatment (Figure 2, Table 1). The improvement in catalytic performance would be due to a further decrease in the amount of acid sites, especially the LAS (Table 1, Figures 6B and 8B), resulting in suppression of the hydride transfer and coke formation (e.g., 21 mg/g-catalyst at TOS of 210 min for HB(77)-NT(2 M, 16 h)). This conclusion was consistent with our previous work on n-hexane cracking over dealuminated H-MCM-22 zeolites [7]. 2.3.2. Effect of Desilication As shown in Figure 15A, catalytic stability was not improved after 0.05 or 0.1 M NaOH treatment; however, it was slightly improved after 0.2 M NaOH treatment, although the initial n-hexane conversion was slightly decreased. This may be related to the partially destroyed structure (Figures 1B and 5, Table 2). On the other hand, the catalytic stability was remarkably improved after 0.05 M NaOH treatment followed by HNO3 treatment, although the initial n-hexane conversion was slightly decreased (Figure 15B). This may be due to the decrease in the number of acid sites (Table 2, Figure 9), leading to a smaller amount of coke being formed (e.g., 13 mg/g-catalyst at TOS of 210 min for HB(77)-AT(0.05 M)-NT(1 M)). In addition, the increase in the mesopores formed by the subsequent acid treatment would be beneficial to the diffusion of coke precursor (Table 2). As to the products’ distribution, the propylene selectivity was slightly increased after 0.05 M NaOH treatment. Meanwhile, the BTX selectivities were increased while the propane selectivity was decreased (Figure 16B). This fact suggested that the dehydrogenation of propane and subsequent aromatization of olefins were improved by 0.05 M NaOH treatment, due to the increase in the amount of LAS (Figure 9B). Similar results were observed in our work on n-hexane cracking over alkali-treated H-ZSM-5 zeolites [20]. By increasing the NaOH concentration to 0.2 M, the propane selectivity was further decreased. This is due to the further increase in the amount 94PDF Image | Zeolite Catalysis
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