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

doi:10.11949/0438-1157.20210026

Abstract

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

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

CLC Number:

TQ 028.1

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.

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.

Figures/Tables 10

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

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

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

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

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

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

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

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

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

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

References 46

1	Lashof D A, Ahuja D R. Relative contributions of greenhouse gas emissions to global warming[J]. Nature, 1990, 344(6266): 529-531.
2	Wuebbles D J. Nitrous oxide: no laughing matter[J]. Science, 2009, 326(5949): 56-57.
3	Ravishankara A R, Daniel J S, Portmann R W. Nitrous oxide (N₂O): the dominant ozone-depleting substance emitted in the 21st century[J]. Science, 2009, 326(5949): 123-125.
4	Xiao D J, Bloch E D, Mason J A, et al. Oxidation of ethane to ethanol by N₂ O in a metal-organic framework with coordinatively unsaturated iron(Ⅱ) sites[J]. Nature Chemistry, 2014, 6(7): 590-595.
5	Kay S. Synthetic chemistry with nitrous oxide[J]. Chemical Society Reviews, 2015, 44(17): 6375-6386.
6	Tian H, Xu R, Canadell J G, et al. A comprehensive quantification of global nitrous oxide sources and sinks[J]. Nature, 2020, 586(7828): 248-256.
7	Konsolakis M. Recent advances on nitrous oxide (N₂O) decomposition over non-noble-metal oxide catalysts: catalytic performance, mechanistic considerations, and surface chemistry aspects[J]. ACS Catalysis, 2015, 5(11): 6397-6421.
8	Hamilton S M, Hopkins W S, Harding D J, et al. Infrared induced reactivity on the surface of isolated size-selected clusters: dissociation of N₂O on rhodium clusters[J]. Journal of the American Chemical Society, 2010, 132(5): 1448-1449.
9	Jabłońska M, Palkovits R. It is no laughing matter: nitrous oxide formation in diesel engines and advances in its abatement over rhodium-based catalysts[J]. Catalysis Science & Technology, 2016, 6(21): 7671-7687.
10	Jurado A, Borges A V, Brouyère S. Dynamics and emissions of N₂O in groundwater: a review[J]. Science of the Total Environment, 2017, 584/585: 207-218.
11	Wang L, Zhang F F, Wang C, et al. Ethylenediamine-functionalized metal organic frameworks MIL-100(Cr) for efficient CO₂/N₂O separation[J]. Separation and Purification Technology, 2020, 235: 116219.
12	Chen D L, Wang N W, Wang F F, et al. Utilizing the gate-opening mechanism in ZIF-7 for adsorption discrimination between N₂O and CO₂[J]. The Journal of Physical Chemistry C, 2014, 118(31): 17831-17837.
13	赵铎, 陈聚良, 史红军, 等. 一种己二酸尾气中氮氧化物的脱除装置: 206587600U[P]. 2017-10-27.
	Zhao D, Chen J L, Shi H J, et al. A device and method for removing nitrogen oxides in adipic acid tail gases: 206587600U[P]. 2017-10-27.
14	Tsai M L, Hadt R G, Vanelderen P, et al. [Cu₂O]₂⁺ active site formation in Cu-ZSM-5: geometric and electronic structure requirements for N₂O activation[J]. Journal of the American Chemical Society, 2014, 136(9): 3522-3529.
15	Zhang F M, Chen X, Zhuang J, et al. Direct oxidation of benzene to phenol by N₂O over meso-Fe-ZSM-5 catalysts obtained via alkaline post-treatment[J]. Catalysis Science & Technology, 2011, 1(7): 1250-1255.
16	Zeng R, Feller M, Diskin-Posner Y, et al. CO oxidation by N₂O homogeneously catalyzed by ruthenium hydride pincer complexes indicating a new mechanism[J]. Journal of the American Chemical Society, 2018, 140(23): 7061-7064.
17	Tolman W. Binding and activation of N₂O at transition-metal centers: recent mechanistic insights[J]. Angewandte Chemie International Edition, 2010, 49(6): 1018-1024.
18	Park K S, Ni Z, Côté A P, et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks[J]. Proceedings of the National Academy of Sciences of the United States of America, 2006, 103(27): 10186-10191.
19	Hartmann N J, Wu G, Hayton T W. Synthesis and reactivity of a nickel(Ⅱ) thioperoxide complex: demonstration of sulfide-mediated N₂O reduction[J]. Chemical Science, 2018, 9(31): 6580-6588.
20	Perez-Ramirez J, Santiago M. Metal-substituted hexaaluminates for high-temperature N₂O abatement[J]. Chemical Communications, 2007, 38(6): 619-621.
21	周丽, 丁剑木. 空分装置中有害气体的危害与控制[J]. 冶金动力, 2020, 39(5): 30-33.
	Zhou L, Ding J M. The harms and control of harmful gases in air separation unit[J]. Metallurgical Power, 2020, 39(5): 30-33.
22	Harvey M J, Sperlich P, Clough T J, et al. Global research alliance N₂O chamber methodology guidelines: recommendations for air sample collection, storage, and analysis[J]. Journal of Environmental Quality, 2020, 49(5): 1110-1125.
23	Groen J C, Pérez-Ramírez J, Zhu W D. Adsorption of nitrous oxide on silicalite-1[J]. Journal of Chemical & Engineering Data, 2002, 47(3): 587-589.
24	Saha D, Bao Z B, Jia F, et al. Adsorption of CO₂, CH₄, N₂O, and N₂ on MOF-5, MOF-177, and zeolite 5A[J]. Environmental Science & Technology, 2010, 44(5): 1820-1826.
25	Li L B, Lin R B, Krishna R, et al. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites[J]. Science, 2018, 362(6413): 443-446.
26	Lin R B, Xiang S C, Xing H B, et al. Exploration of porous metal-organic frameworks for gas separation and purification[J]. Coordination Chemistry Reviews, 2019, 378: 87-103.
27	Li J R, Kuppler R J, Zhou H C. Selective gas adsorption and separation in metal-organic frameworks[J]. Chemical Society Reviews, 2009, 38(5): 1477.
28	杨江峰, 欧阳坤, 张倬铭, 等. 脱氧剂Fe-MOF-74的制备及氧气吸附失活规律[J]. 化工学报, 2015, 66(8): 3262-3267.
	Yang J F, Ouyang K, Zhang Z M, et al. Preparation and oxygen adsorption of deoxidation agent Fe-MOF-74 and its deactivation[J]. CIESC Journal, 2015, 66(8): 3262-3267.
29	Jiang J, Furukawa H, Zhang Y B, et al. High methane storage working capacity in metal-organic frameworks with acrylate links[J]. Journal of the American Chemical Society, 2016, 138(32): 10244-10251.
30	张倬铭, 杨江峰, 陈杨, 等. 一维直孔道MOFs对CH₄/N₂和CO₂/CH₄的分离[J]. 化工学报, 2015, 66(9): 3549-3555.
	Zhang Z M, Yang J F, Chen Y, et al. Separation of CH₄/N₂ and CO₂/CH₄ mixtures in one dimension channel MOFs[J]. CIESC Journal, 2015, 66(9): 3549-3555.
31	Yang J F, Wang Y, Li L B, et al. Protection of open-metal V(Ⅲ) sites and their associated CO₂/CH₄/N₂/O₂/H₂O adsorption properties in mesoporous V-MOFs[J]. Journal of Colloid and Interface Science, 2015, 456: 197-205.
32	Kloutse F A, Gauthier W, Hourri A, et al. Study of competitive adsorption of the N₂O-CO₂-CH₄-N₂ quaternary mixture on CuBTC[J]. Separation and Purification Technology, 2020, 235: 116211.
33	Saha D, Deng S G. Adsorption equilibrium, kinetics, and enthalpy of N₂O on zeolite 4A and 13X[J]. Journal of Chemical & Engineering Data, 2010, 55(9): 3312-3317.
34	Zhang X P, Chen W J, Shi W, et al. Highly selective sorption of CO₂ and N₂O and strong gas-framework interactions in a nickel(ⅱ) organic material[J]. Journal of Materials Chemistry A, 2016, 4(41): 16198-16204.
35	Yang J F, Du B J, Liu J Q, et al. MIL-100Cr with open Cr sites for a record N₂O capture[J]. Chemical Communications, 2018, 54(100): 14061-14064.
36	Hamon L, Serre C, Devic T, et al. Comparative study of hydrogen sulfide adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal-organic frameworks at room temperature[J]. Journal of the American Chemical Society, 2009, 131(25): 8775-8777.
37	Férey G, Mellot-Draznieks C, Serre C, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area[J]. Science, 2005, 309(5743): 2040-2042.
38	Malouche A, Blanita G, Dan L P, et al. Hydrogen absorption in 1 nm Pd clusters confined in MIL-101(Cr)[J]. Journal of Materials Chemistry A, 2017, 5(44): 23043-23052.
39	Myers A L, Prausnitz J M. Thermodynamics of mixed-gas adsorption[J]. AIChE Journal, 1965, 11(1): 121-127.
40	Kumar K V, Gadipelli S, Wood B, et al. Characterization of the adsorption site energies and heterogeneous surfaces of porous materials[J]. Journal of Materials Chemistry A, 2019, 7(17): 10104-10137.
41	Yang J F, Bai H H, Shang H, et al. Experimental and simulation study on efficient CH₄/N₂ separation by pressure swing adsorption on silicalite-1 pellets[J]. Chemical Engineering Journal, 2020, 388: 124222.
42	Xu M, Deng S G. Efficient screening of novel adsorbents for coalbed methane recovery[J]. Journal of Colloid and Interface Science, 2020, 565: 131-141.
43	Berdonosova E A, Kovalenko K A, Polyakova E V, et al. Influence of anion composition on gas sorption features of Cr-MIL-101 metal-organic framework[J]. The Journal of Physical Chemistry C, 2015, 119(23): 13098-13104.
44	Zhao M, Yuan K, Wang Y, et al. Metal-organic frameworks as selectivity regulators for hydrogenation reactions[J]. Nature, 2016, 539(7627): 76-80.
45	Yoon J W, Chang H, Lee S J, et al. Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites[J]. Nature Materials, 2017, 16(5): 526-531.
46	尚华, 白洪灏, 刘佳奇, 等. CH₄-N₂在自支撑颗粒型Silicalite-1上的吸附分离及PSA模拟[J]. 化工学报, 2020, 71(5): 2088-2098.
	Shang H, Bai H H, Liu J Q, et al. PSA simulation and adsorption separation of CH₄-N₂ by self-supporting pellets Silicalite-1[J]. CIESC Journal, 2020, 71(5): 2088-2098.

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

MIL-101Cr-F/Cl用于N₂O的捕集研究

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