氨基功能化的金属有机框架与模型燃油中含氮化合物的结合作用

王蕾; 赵新华; 熊振湖; 张金苗; 李晨; 武春生

氨基功能化的金属有机框架与模型燃油中含氮化合物的结合作用

王蕾^{1, 2, ,},
赵新华¹,
熊振湖²,
张金苗²,
李晨²,
武春生²

1.
天津大学环境科学与工程学院, 天津 300072
2.
天津城建大学环境与市政工程学院, 天津 300384

基金项目:

国家自然科学基金 50878138

详细信息

通讯作者:
王蕾, Tel: 13820677407, E-mail: zhenhu.xiong@126.com, wangl1026@tcu.edu.cn

中图分类号: TE99
计量
- 文章访问数: 70
- HTML全文浏览量: 37
- PDF下载量: 6
- 被引次数: 0
出版历程
- 收稿日期: 2016-03-16
- 修回日期: 2016-05-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-09-10

Combination of amino functionalized metal organic framework with nitrogenous compounds in model fuel

1.
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China
2.
School of Environmental and Municipal Engineering, Tianjin Chengjian University, Tianjin 300384, China

Funds:

the National Natural Science Foundation of China 50878138

摘要

摘要: 合成了金属有机骨架MIL-53（Al）和MIL-53（Al）-NH₂，并且将其作为吸附剂去除油品中的含氮化合物（喹啉和吡咯）。采用X射线衍射（XRD）、扫描电镜（SEM）、FT-IR光谱以及热重分析等对两种吸附剂进行了表征。结果表明，MIL-53（Al）-NH₂能够快速地吸附油品中的喹啉/吡咯并且显示了较高的吸附容量，但MIL-53（Al）对喹啉/吡咯的吸附容量较低，原因是MIL-53（Al）-NH₂和喹啉之间存在有利的氢键结合，但MIL-53（Al）-NH₂与吡咯的氢键作用相对较低。研究了影响吸附容量的因素，包括吸附时间和温度。采用准一级和准二级动力学模型拟合了喹啉和吡咯的吸附数据，研究了MIL-53（Al）-NH₂对喹啉和吡咯的吸附等温线和吸附热力学。通过简单的溶剂洗涤使得MIL-53（Al）-NH₂再生，并重新用于吸附过程。
- MIL-53(Al)-NH₂ /
- 含氮化合物 /
- 吸附脱氮 /
- 模型燃油 /
- 氢键作用
Abstract: The metal-organic frameworks, MIL-53 (Al)-NH₂ and MIL-53 (Al), were synthesized and used as the adsorbents for the removal of nitrogen-containing compounds (quinoline and pyrrole) from model fuel. The adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR spectroscopy, and thermogravimetric analysis. Compared with the adsorption capacity of MIL-53 (Al), MIL-53(Al)-NH₂ possesses a higher adsorption capacity for quinoline and pyrrole in the model fuel due to the hydrogen bonding interaction between MIL-53(Al)-NH₂ and the nitrogen-containing compounds. The factors affecting the adsorption capacity are the adsorptive time and temperature. Furthermore, the pseudo-first-order and pseudo-second-order adsorption kinetics models were tested. It is found that the pseudo-second-order kinetics model is preferable to characterize the adsorption process. The adsorption isotherms and adsorption thermodynamics of quinoline and pyrrole on the MIL-53(Al)-NH₂ were also evaluated. The calculation of separation factor R_L and thermodynamic parameters (ΔG⁰, ΔH⁰和ΔS⁰) show that the adsorption of quinoline/pyrrole on the MIL-53(Al)-NH₂ is a spontaneous and exothermic process. The used MIL-53 (Al)-NH₂ could be regenerated by simple solvent washing with ethanol and reused in the adsorption process.
- MIL-53(Al)-NH₂ /
- nitrogen-containing compounds /
- adsorptive denitrogenation /
- model fuel /
- hydrogen bonding interaction

HTML全文

图 1 MIL-53(Al) 和MIL-53(Al)-NH₂的光谱谱图

Figure 1 FT-IR spectra (a) and XRD pattern (b) of MIL-53(Al) and MIL-53(Al)-NH₂, and the isotherms of adsorption-desorption on MIL-53(Al) (c) and MIL-53(Al)-NH₂(d)

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图 2 MIL-53(Al) (a) 和MIL-53(Al)-NH₂(b) 的SEM照片和热重曲线(c)

Figure 2 SEM micrographs of MIL-53(Al) (a) and MIL-53(Al)-NH₂ (b) and TGA curves (c)

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图 3 在15 ℃下接触时间对喹啉(a), 吡咯(b) 在MIL-53(Al)-NH₂和MIL-53(Al) 上的吸附

Figure 3 Effect of contact time on the adsorption of quinoline (a) and pyrrole (b) on MIL-53(Al)-NH₂ and MIL-53(Al) at 15 ℃

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图 4 10 ℃下喹啉(a) 和吡咯(b) 在MIL-53(Al)-NH₂和MIL-53(Al) 上的吸附等温线

Figure 4 Adsorption isotherms for quinoline (a) and pyrrole (b) over MIL-53(Al)-NH₂ and MIL-53(Al) at 10 ℃

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图 5 在10 ℃下MIL-53(Al)-NH₂吸附喹啉和吡咯的分离因子R_L

Figure 5 Separation factors (R_L) of quinoline and pyrrole adsorption over MIL-53(Al)-NH₂ at 10 ℃

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图 6 喹啉在MIL-53(Al)-NH₂上吸附可能的机理

Figure 6 Possible mechanism of quinoline adsorption on MIL-53(Al)-NH₂

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图 7 MIL-53(Al)-NH₂循环次数对喹啉和吡咯吸附容量的影响

(15 ℃，C₀=100 mg/L，m=10 mg，V=10 mL，contact time=180 min)

Figure 7 Effect of recycle numbers of MIL-53(Al)-NH₂ on the adsorption capacity of quinoline and pyrrole

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表 1 MIL-53(Al) 和MIL-53(Al)-NH₂的比表面积、孔径和孔容

Table 1 BET analysis data of MIL-53(Al) and MIL-53(Al)-NH₂ samples

Adsorbent	BET surface area A/(m²·g^-1)	Tolal pore volume v/(cm³·g^-1)	Average pore diameter d/nm
MIL-53(Al)	1 328.28	0.785	2.36
MIL-53(Al)-NH₂	767.93	0.409	2.13

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表 2 MIL-53(Al)-NH₂吸附喹啉和吡咯的动力学参数

Table 2 Kinetic parameters of pseudo-first-order and -second-order models for the adsorption of quinoline and pyrrole on the MIL-53(Al)-NH₂

Chemical	Pseudo first-order rate model				Pseudo second-order rate model
Chemical	q_e(expt.) /(mg·g^-1)	q_e(cal.) /(mg·g^-1)	K₁ /(min^-1)	R²	q_e(expt.) /(mg·g^-1)	q_e(cal.) /(mg·g^-1)	K₂ /(g·mg^-1·min^-1)	R²
Quinoline	28.74	11.25	0.035 22	0.816 6	28.74	29.25	0.010 99	0.999 8
Pyrrole	12.85	7.31	0.025 95	0.868 3	12.85	13.31	0.010 26	0.999 7

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表 3 在不同温度下由Langmuir模型和Freundlich模型拟合的MIL-53(Al)-NH₂吸附喹啉/吡咯的等温线模型参数

Table 3 Adsorption parameters based on Langmuir model and Freundlich model at different temperatures

Chemical	Temp t/℃	Langmuir model			Freundlich model
Chemical	Temp t/℃	q_m /(mg·g^-1)	b /(L·mg^-1)	R²	K_F /(mg·g^-1)	n /(g·L^-1)	R²
Quinoline	10	139.53	0.152 5	0.997 6	2.304	1.471	0.967 7
	25	120.38	0.115 5	0.997 2	1.925	1.468	0.964 0
	40	108.62	0.046 9	0.979 6	1.507	1.419	0.943 6
Pyrrole	10	31.399	0.149 8	0.994 3	0.685	1.594	0.952 8
	25	30.152	0.001 1	0.998 8	0.414	1.469	0.974 2
	40	26.240	0.001 0	0.998 0	0.250	1.391	0.981 5

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表 4 喹啉和吡咯在MIL-53(Al)-NH₂上吸附的热力学参数

Table 4 Thermodynamic parameters of the adsorption of quinoline and pyrrole on the MIL-53(Al)-NH₂

	ΔH⁰ /(kJ·mol^-1)	ΔS⁰ /(J·mol^-1·K^-1)	ΔG⁰/(kJ·mol^-1)
	ΔH⁰ /(kJ·mol^-1)	ΔS⁰ /(J·mol^-1·K^-1)	10 ℃	25 ℃	40 ℃
Quinoline	-4.999	-12.99	-1.320	-1.125	-0.930
Pyrrole	-2.253	-6.652	-0.408	-0.310	-0.212

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