Synthesis of ZSM-5 zeolites with different silica/alumina ratios and their performance in the removal of aniline and pyridine from model fuel through adsorption
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摘要: 合成了一系列不同硅铝比的ZSM-5分子筛,采用XRD、FT-IR、ICP、SEM、NH3-TPD和N2吸附-脱附等方法对其进行了表征,研究了不同硅铝比ZSM-5分子筛对模拟柴油中苯胺和吡啶的吸附脱除性能。结果表明,所合成的ZSM-5分子筛均具有典型MFI结构;与合成原料混合物中的硅铝比相比,实际硅铝比稍有降低。ZSM-5分子筛的酸量随硅铝比的增加而降低,硅铝比较小的ZSM-5(1)和ZSM-5(2)的吸附脱除苯胺或吡啶的效果明显优于其他样品,并且所有样品吸附脱除吡啶的效果均优于苯胺。ZSM-5(2)上苯胺和吡啶的吸附等温线符合Langmuir-Freundlich混合模型。Abstract: A series of ZSM-5 zeolites with different silica/alumina ratios were synthesized and characterized by means of XRD, FT-IR, ICP, SEM, NH3-TPD and N2 sorption; their performance in the removal of aniline and pyridine from a model fuel through adsorption was then investigated. The results indicated that all the as-synthesized ZSM-5 zeolites have the MFI structure, although the actual silica/alumina ratio in the as-synthesized ZSM-5 zeolites is somewhat lower than that in the corresponding synthesis mixture. As expected, the acid amount of ZSM-5 zeolites decreases with the increase of the silica/alumina ratio. The adsorption denitrogenation performance of ZSM-5(1) and ZSM-5(2) with relatively lower silica/alumina ratios is superior to that of other two zeolite samples; meanwhile, the removal efficiency for pyridine over all ZSM-5 samples is higher than that for aniline. Moreover, adsorption isotherms of aniline and pyridine over ZSM-5(2) accord with the Langmuir-Freundlich adsorption model.
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Key words:
- ZSM-5 /
- silica-alumina ratio /
- aniline /
- pyridine /
- model fuel /
- adsorption denitrogenation
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图 7 ZSM-5(2)对模拟柴油中苯胺的吸附等温线及其各等温吸附模型的拟合曲线
Figure 7 Adsorption isotherms of aniline over ZSM-5(2) (a) and those fitted with Langmuir, Freundlich and Langmuir-Freundlich adsorption models at 303 K (b), 323 K (c) and 343 K (d)
(adsorption conditions: 15 mL model fuel; 1.5 g adsorbent; 303, 323 or 343 K; 0.5 h)
图 8 ZSM-5(2)对模拟柴油中吡啶的吸附等温线及其各等温吸附模型的拟合曲线
Figure 8 Adsorption isotherms of pyridine over ZSM-5(2) (a) and those fitted with Langmuir, Freundlich and Langmuir-Freundlich adsorption models at 303 K (b), 323 K (c) and 343 K (d)
(adsorption conditions: 15 mL model fuel; 1.5 g adsorbent; 303, 323 or 343 K; 0.5 h)
表 1 ZSM-5样品的ICP测试结果
Table 1 ICP results of the ZSM-5 samples
Sample Content w/% Silica/alumina ratio in synthesis system Silica/alumina ratio in ZSM-5 SiO2 Al2O3 ZSM-5(1) 92.28 7.47 25 21 ZSM-5(2) 96.26 3.88 50 42 ZSM-5(3) 97.36 2.43 75 68 ZSM-5(4) 98.75 0.98 200 172 表 2 ZSM-5样品的孔结构参数
Table 2 Textural properties of the ZSM-5 samples
Sample BET surface area A/(m2·g-1) Total pore volume v/(cm3·g-1) Average pore diameter d/nm ZSM-5(1) 463 0.224 1.965 ZSM-5(2) 448 0.218 1.946 ZSM-5(3) 377 0.276 2.929 ZSM-5(4) 460 0.237 2.061 表 3 Langmuir,Freundlich和Langmuir-Freundlich等温吸附模型拟合的相关参数
Table 3 Regression coefficients for the adsorption of aniline and pyridine on ZSM-5(2) with various adsorption models
Adsorbate Temperature T/K Langmuir Freundlich Langmuir-Freundlich qm KL×105 R2 n KF R2 qm Ka×105 n R2 Aniline 303 140.7 8.966 0.986 2.172 0.893 0.941 122.9 11.95 1.251 0.989 323 189.6 5.647 0.973 1.830 0.425 0.975 212.9 1.734 0.744 0.976 343 153.0 8.338 0.971 2.116 0.838 0.949 156.8 7.876 0.971 0.969 Pyridine 303 276.2 4.614 0.991 1.443 0.142 0.976 184.8 9.589 1.345 0.995 323 284.4 4.329 0.992 1.580 0.241 0.973 223.7 6.964 1.229 0.995 343 338.9 3.661 0.994 1.498 0.186 0.977 246.0 6.753 1.292 0.998 -
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