不同硅铝比ZSM-5的合成及其吸附脱除柴油中苯胺和吡啶的性能

洪新; 李云赫; 高畅; 范博; 庞宇莹; 张丹; 唐克

不同硅铝比ZSM-5的合成及其吸附脱除柴油中苯胺和吡啶的性能

辽宁工业大学化学与环境工程学院, 辽宁锦州 121001

基金项目:

辽宁省自然科学基金 20180550639

详细信息

中图分类号: O647
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- 被引次数: 0
出版历程
- 收稿日期: 2018-05-30
- 修回日期: 2018-08-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-10-10

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

School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China

Funds:

the Liaoning Provincial Natural Science Foundation of China 20180550639

More Information

Corresponding author: TANG Ke, E-mail:tangke0001@163.com

摘要

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。
- ZSM-5 /
- 硅铝比 /
- 苯胺 /
- 吡啶 /
- 模拟柴油 /
- 吸附脱氮
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.
- ZSM-5 /
- silica-alumina ratio /
- aniline /
- pyridine /
- model fuel /
- adsorption denitrogenation

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图 1 ZSM-5样品的XRD谱图

Figure 1 XRD patterns of various ZSM-5 samples

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图 3 ZSM-5分子筛的SEM照片(10000倍)

Figure 3 SEM images of various ZSM-5 samples (10000 times)

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图 2 ZSM-5样品的红外光谱谱图

Figure 2 FT-IR spectra of various ZSM-5 samples

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图 4 4 ZSM-5样品的N₂吸附-脱附等温线和BJH孔径分布曲线

Figure 4 N₂ adsorption-desorption isotherms and BJH pore size distribution of various ZSM-5 samples

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图 5 ZSM-5样品的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of various ZSM-5 samples

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图 6 不同硅铝比的ZSM-5吸附脱除模拟柴油中苯胺或吡啶

Figure 6 Adsorption performance for aniline or pyridine in model fuel over various ZSM-5 samples

(adsorption conditions: 15 mL model fuel; 1.5 g adsorbent; 303 K; adsorption for 0.5 h)

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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)

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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)

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图 9 ZSM-5(2)吸附脱除模拟柴油中苯胺或吡啶的再生性能

Figure 9 The effects of regeneration method on the performance of regenerated ZSM-5 (2) in the removal of aniline or pyridine in model fuel by adsorption

: fresh ZSM-5(2); : regeregeneration by calcination; : regeregeneration by alcohol washing

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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
Sample	SiO₂	Al₂O₃	Silica/alumina ratio in synthesis system	Silica/alumina ratio in ZSM-5
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

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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

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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
Adsorbate	Temperature T/K	q_m	K_L×10⁵	R²	n	K_F	R²	q_m	K_a×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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