MIL-101Cr-F/Cl用于N2O的捕集研究

doi:10.11949/0438-1157.20210026

摘要/Abstract

摘要：

氧化亚氮（N₂O）是仅次于CO₂和CH₄的第三大温室气体，对其捕集具有资源回收和减排温室气体的双重价值。本文通过添加氢氟酸和盐酸合成了末端具有不同阴离子的MIL-101Cr材料：MIL-101（Cr）-F和MIL-101（Cr）-Cl，通过XRD、BET、SEM等对样品进行了表征，测试并分析了两种样品对N₂O和N₂的吸附性能，进行了选择性和吸附热的计算以及混合气体的穿透模拟。研究结果表明，MIL-101（Cr）-Cl拥有目前最高的N₂O吸附容量（6.43 mmol/g，298 K）和N₂O/N₂选择性（267），混合气体（N₂O/N₂=0.1%/99.9%）穿透模拟结果显示MIL-101（Cr）-Cl具有更加优异的微量N₂O捕获能力。

关键词: 氧化亚氮, 氮气, MIL-101Cr, 阴离子, 吸附分离

Abstract:

Nitrous oxide (N₂O) is the third largest greenhouse gas after CO₂ and CH₄, and its capture has the dual value of resource recovery and greenhouse gas emission reduction. In this paper, MIL-101(Cr) with different anion terminals were synthesized by adding hydrofluoric acid and hydrochloric acid separately, named MIL-101(Cr)-F and MIL-101(Cr)-Cl, the synthesized samples were characterized by XRD, BET and SEM, et al. Single component adsorption isotherms of N₂O and N₂ were tested, and the selectivity of N₂O/N₂ and corresponding adsorption heat of gases were also calculated. Additionally, the simulation of mixture (N₂O/N₂=0.1%/99.9%) breakthrough were carried out. As the result, MIL-101(Cr)-Cl with the highest N₂O adsorption capacity (6.43 mmol/g, 298 K) and N₂O/N₂ selectivity (267) were reported. Furthermore, the simulation result confirmed that MIL-101(Cr)-Cl has great potential to capture trace amount of N₂O.

Key words: nitrous oxide, nitrogen, MIL-101Cr, anion, adsorption and separation

中图分类号:

TQ 028.1

李媛, 张飞飞, 王丽, 杨江峰, 李立博, 李晋平. MIL-101Cr-F/Cl用于N₂O的捕集研究[J]. 化工学报, 2021, 72(9): 4759-4767.

Yuan LI, Feifei ZHANG, Li WANG, Jiangfeng YANG, Libo LI, Jinping LI. Study on the capture of N₂O by MIL-101Cr-F/Cl[J]. CIESC Journal, 2021, 72(9): 4759-4767.

图/表 10

图1 MIL-101(Cr)的结构(a)和两种不同阴离子(b)的示意图

Fig.1 Schematic diagram of the structure (a) and two different anions (b) of MIL-101(Cr)

图2 MIL-101(Cr)-F/Cl的XRD谱图(a)；77 K下的N2吸脱附等温线(b)和孔径分布 (c)

Fig.2 XRD pattern (a)； N2 adsorption-desorption isotherms(b) and pore size distribution (c) at 77 K of MIL-101(Cr)-F/Cl

图3 MIL-101(Cr)-F/Cl的SEM图[（a）、（b）]和MIL-101(Cr)-Cl的EDX元素分布(c)

Fig.3 SEM images [(a),(b)] of MIL-101(Cr)-F/Cl and EDX mapping images (c) of MIL-101(Cr)-Cl

图4 MIL-101(Cr)-F/Cl的热失重曲线

Fig.4 TG curves of MIL-101(Cr)-F/Cl

图5 MIL-101(Cr)-F/Cl在423 K、523 K活化下的N2O和N2吸附等温线

Fig.5 Adsorption isotherms of N2O and N2 on MIL-101(Cr)-F/Cl activated at 423 K and 523 K

表1 298 K、1 bar下N2O在多孔材料上的吸附容量

Table 1 N2O adsorption capacity on several porous materials at 298 K， 1 bar

吸附剂	N₂O吸附量/（mmol/g）	温度/K	文献
Silicalite-1	1.75	298	[23]
Zeolite-5A	4.10	298	[24]
MOF-5	0.90	298	[24]
ZIF-7	2.50	298	[12]
Ni-MOF	2.81	298	[34]
MIL-100Cr	5.78	298	[35]
ED-MIL-100Cr	2.14	298	[11]
MIL-101Cr-F	3.26	298	本文
MIL-101Cr-Cl	6.43	298	本文

图6 MIL-101(Cr)-F/Cl在298 K下N2O和N2的吸附热

Fig.6 Adsorption heats of N2O and N2 at 298 K of MIL-101(Cr)-F/Cl

图7 MIL-101(Cr)-F/Cl对298 K下N2O和N2吸附等温线的拟合

Fig.7 Fitting curves of the N2O and N2 adsorption isotherms at 298 K of MIL-101(Cr)-F/Cl

图8 298 K下N2O和N2的选择性(a)及穿透模拟[(b)、(c)]

Fig.8 Selectivity (a) and breakthrough simulation[(b),(c)] of N2O and N2 at 298 K

表2 吸附剂及吸附床参数设置

Table 2 Parameter setting of adsorbent and adsorption bed

参数	数值
孔隙率	0.53
堆积密度/(kg/m³)	233
吸附剂半径/m	1×10^-5
床层空隙率	0.2
床层高度/m	0.16
床层半径/m	4×10^-3
传质系数(N₂O)	0.02
传质系数(N₂)	0.03

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MIL-101Cr-F/Cl用于N₂O的捕集研究

Study on the capture of N₂O by MIL-101Cr-F/Cl

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