Microporous Noria polymer for selective adsorption and separation of xylene isomers

doi:10.11949/0438-1157.20221303

Abstract

Abstract:

The separation of xylene isomers is an important but challenging industrial process, and the development of novel adsorbent materials is the key to achieving efficient separation. Herein,microporous Noria polymer (MNP) with network structure was synthesized by reacting Noria with 2, 3, 5, 6-tetrafluoroterephthalonitrile and explored for the separation of xylene isomers. MNP is microporous and shows high specific surface area, as revealed by nitrogen adsorption and desorption isotherms. The adsorption of xylene isomers on MNP was investigated. The adsorption isotherms fit well to the Langmuir isotherm model and the adsorption kinetics of three xylene isomers can be described by the pseudo second-order kinetics model. We found that MNP shows a selective interaction with o-xylene, with a maximum adsorption capacity of up to 344 mg·g^-1 for o-xylene according to Langmuir adsorption isotherm fitting. The selectivity of o-xylene over p-xylene is about 1.9 in competitive adsorption experiments, while that of o-xylene over m-xylene can reach as high as 2.4. Dynamic breakthrough experiments verify that MNP can effectively separate o-xylene from xylene isomer mixtures. In addition, MNP has an extremely short adsorption equilibrium time and excellent thermal stability, and is a potential adsorbent for the separation of o-xylene.

Key words: polymers, microporous materials, xylene isomers separation, adsorption, selectivity

摘要：

二甲苯异构体的分离是一个非常重要但极具挑战性的工业过程，新型吸附剂材料的开发是实现其高效分离的关键。采用Noria和2,3,5,6-四氟对苯二腈制备了具有高比表面积的微孔Noria聚合物（MNP），并研究了MNP对二甲苯异构体的吸附分离能力。单组分二甲苯异构体在MNP上的吸附动力学及吸附等温线表明，MNP具有邻二甲苯优先吸附能力，Langmuir吸附等温线拟合得到邻二甲苯最大吸附量达344 mg·g^-1。竞争吸附实验也表明MNP是一种邻二甲苯选择性吸附剂，邻二甲苯与间二甲苯的选择性最高可达2.4，邻二甲苯与对二甲苯选择性在1.9左右。动态穿透实验验证了MNP可以有效分离出邻二甲苯。此外，MNP具有极短的吸附平衡时间和优异的热稳定性，是一种具有潜力的邻二甲苯分离吸附剂。

关键词: 聚合物, 微孔材料, 二甲苯异构体分离, 吸附, 选择性

CLC Number:

TQ 317.4

Qingling QIAN, Qing ZHU, Zhengjin YANG, Tongwen XU. Microporous Noria polymer for selective adsorption and separation of xylene isomers[J]. CIESC Journal, 2022, 73(12): 5438-5448.

钱庆玲, 朱晴, 杨正金, 徐铜文. 微孔Noria聚合物用于二甲苯异构体吸附分离研究[J]. 化工学报, 2022, 73(12): 5438-5448.

Figures/Tables 12

Fig.1 Schematic diagram of the synthesis of MNP

Fig.2 (a) FT-IR spectra of TFTPN, Noria and MNP; (b) 13C NMR spectra of TFTPN and Noria, and 13C CP/MAS solid-state NMR spectra of MNP; (c) Powder X-ray diffraction patterns of Noria and MNP; (d) SEM image of MNP

Fig.3 (a) N2 adsorption/desorption isotherms of Noria and MNP at 77 K; (b) The pore size distributions of Noria and MNP using the nonlocal density functional theory method

Fig.4 Thermogravimetric analysis curves of Noria and MNP in N2 atmosphere

Fig.5 (a) Time-dependent adsorption of single-xylene isomer on MNP; (b) Fitting the adsorption of xylene isomers on MNP to pseudo second-order kinetic model

Table 1 Kinetic fitting results of xylene isomers adsorption on MNP

二甲苯	C₀/ (mol·L^-1)	准一级动力学模型			准二级动力学模型			颗粒内扩散模型
二甲苯	C₀/ (mol·L^-1)	k₁/ (g·mg^-1·h^-1)	Q_e/ (mg·g^-1)	R²	k₂/ (g·mg^-1·h^-1)	Q_e / (mg·g^-1)	R²	k₃/ (g·mg^-1·h^-1)	R²
OX	0.1	0.96	54.1	0.6020	1.31	53.9	0.9999	2.50	0.7511
PX	0.1	0.68	31.0	0.5597	0.90	30.8	0.9989	3.61	0.9004
MX	0.1	0.67	24.8	0.6382	0.56	24.5	0.9980	2.41	0.8033

Fig.6 (a) Single-xylene isomer adsorption isotherms on MNP at 25℃; (b) Langmuir isotherms of single-xylene isomer adsorption on MNP at 25℃; (c) The effect of temperature on single-xylene isomer adsorption on MNP

Table 2 Parameters from fitting the adsorption isotherms of single-xylene isomer on MNP to Langmuir adsorption model and Freundlich adsorption model

二甲苯	温度/℃	Langmuir 吸附等温线			Freundlich 吸附等温线
二甲苯	温度/℃	Q_m/ (mg·g^-1)	K_L/ (L·mg^-1)	R²	K_F/ (mg·g^-1·(L·mol^-1)^1/ⁿ )	1/n	R²
OX	25	344	2.60	0.9925	279.8	0.57	0.9799
PX	25	131	7.93	0.9951	131.4	0.36	0.8851
MX	25	118	18.00	0.9956	116.0	0.13	0.6579

Fig.7 (a) Competitive batch adsorption experiments on MNP conducted with a binary mixture of OX and PX at 25℃; (b) Competitive batch adsorption experiments on MNP conducted with a binary mixture of OX and MX at 25℃; (c) The adsorption capacity of each isomer on MNP in the competitive batch adsorption experiments conducted with a ternary mixture of PX, OX and MX at 25℃; (d) OX/PX and OX/MX selectivity in the ternary competitive batch adsorption experiments

Fig.8 (a) Schematic representation of a homemade column separation device; (b) Breakthrough curves on MNP in the column adsorption experiment conducted with a ternary mixture of PX, OX and MX at 25℃

Fig.9 FT-IR spectra of MNP before and after adsorption of xylene isomers

Table 3 Properties of xylene isomers

二甲苯	动力学尺寸/Å	分子尺寸/Å			z/x
二甲苯	动力学尺寸/Å	x	y	z	z/x
PX	6.7	6.62	3.81	9.15	1.38
OX	7.4	7.27	3.83	7.83	1.08
MX	7.1	7.32	3.95	8.99	1.23

References 21

22	Zhang G W, Emwas A H, Shahul Hameed U F, et al. Shape-induced selective separation of ortho-substituted benzene isomers enabled by cucurbit[7]uril host macrocycles[J]. Chem, 2020, 6(5): 1082-1096.
23	Sun N, Wang S Q, Zou R Q, et al. Benchmark selectivity p-xylene separation by a non-porous molecular solid through liquid or vapor extraction[J]. Chemical Science, 2019, 10(38): 8850-8854.
24	Moosa B, Alimi L O, Shkurenko A, et al. A polymorphic azobenzene cage for energy-efficient and highly selective p-xylene separation[J]. Angewandte Chemie International Edition, 2020, 59(48): 21367-21371.
25	Du Plessis M, Nikolayenko V I, Barbour L J. Record-setting selectivity for p-xylene by an intrinsically porous zero-dimensional metallocycle[J]. Journal of the American Chemical Society, 2020, 142(10): 4529-4533.
26	Lee J S M, Briggs M E, Hasell T, et al. Hyperporous carbons from hypercrosslinked polymers[J]. Advanced Materials, 2016, 28(44): 9804-9810.
27	Alsbaiee A, Smith B J, Xiao L L, et al. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer[J]. Nature, 2016, 529(7585): 190-194.
28	He Y, Zhu X, Li Y K, et al. Efficient CO₂ capture by triptycene-based microporous organic polymer with functionalized modification[J]. Microporous and Mesoporous Materials, 2015, 214: 181-187.
29	Wang H, Liu C Z, Ma X F, et al. Porous multifunctional phenylcarbamoylated-β-cyclodextrin polymers for rapid removal of aromatic organic pollutants[J]. Environmental Science and Pollution Research, 2022, 29(10): 13893-13904.
30	Tan H L, Chen Q B, Chen T T, et al. Selective adsorption and separation of xylene isomers and benzene/cyclohexane with microporous organic polymers POP-1[J]. ACS Applied Materials & Interfaces, 2018, 10(38): 32717-32725.
31	Li L Y, Guo L D, Olson D H, et al. Discrimination of xylene isomers in a stacked coordination polymer[J]. Science, 2022, 377(6603): 335-339.
32	Kudo H, Hayashi R, Mitani K, et al. Molecular waterwheel (Noria) from a simple condensation of resorcinol and an alkanedial[J]. Angewandte Chemie International Edition, 2006, 45(47): 7948-7952.
33	Giri A, Patil N N, Patra A. Porous noria polymer: a cage-to-network approach toward a robust catalyst for CO₂ fixation and nitroarene reduction[J]. Chemical Communications, 2021, 57(36): 4404-4407.
1	Yang Y X, Bai P, Guo X H. Separation of xylene isomers: a review of recent advances in materials[J]. Industrial & Engineering Chemistry Research, 2017, 56(50): 14725-14753.
2	殷梦凡, 唐政, 张睿, 等. 离子液体液液萃取分离正辛烷/邻二甲苯[J]. 化工学报, 2021, 72(12): 6282-6290.
	Yin M F, Tang Z, Zhang R, et al. Separation of n-octane and o-xylene by liquid-liquid extraction with ionic liquids[J]. CIESC Journal, 2021, 72(12): 6282-6290.
3	Sholl D S, Lively R P. Seven chemical separations to change the world[J]. Nature, 2016, 532(7600): 435-437.
4	Lusi M, Barbour L J. Solid-vapor sorption of xylenes: prioritized selectivity as a means of separating all three isomers using a single substrate[J]. Angewandte Chemie International Edition, 2012, 51(16): 3928-3931.
5	Torres-Knoop A, Krishna R, Dubbeldam D. Separating xylene isomers by commensurate stacking of p-xylene within channels of MAF-X8[J]. Angewandte Chemie International Edition, 2014, 53(30): 7774-7778.
6	陈亮, 肖剑, 谢在库, 等. 对二甲苯悬浮熔融结晶动力学[J]. 化工学报, 2009, 60(11): 2787-2791.
	Chen L, Xiao J, Xie Z K, et al. Suspension melt crystallization kinetics of p-xylene[J]. CIESC Journal, 2009, 60(11): 2787-2791.
7	杨明磊, 魏民, 胡蓉, 等. 二甲苯模拟移动床分离过程建模与仿真[J]. 化工学报, 2013, 64(12): 4335-4341.
	Yang M L, Wei M, Hu R, et al. Modeling of simulated moving bed for xylene separation[J]. CIESC Journal, 2013, 64(12): 4335-4341.
8	Zhang G W, Hua B, Dey A, et al. Intrinsically porous molecular materials (IPMs) for natural gas and benzene derivatives separations[J]. Accounts of Chemical Research, 2021, 54(1): 155-168.
9	Santacesaria E, Morbidelli M, Danise P, et al. Separation of xylenes on Y zeolites(1): Delermination of the adsorption equilibrium parameters, selectivities, and mass-transfer coefficients through finite bath experiments[J]. Industrial & Engineering Chemistry Process Design and Development, 1982, 21(3): 440-445.
34	Rasouli M, Yaghobi N, Chitsazan S, et al. Influence of monovalent cations ion-exchange on zeolite ZSM-5 in separation of para-xylene from xylene mixture[J]. Microporous and Mesoporous Materials, 2012, 150: 47-54.
35	Jiang J W, Sandler S I. Shape versus inverse-shape selective adsorption of alkane isomers in carbon nanotubes[J]. The Journal of Chemical Physics, 2006, 124(2): 024717.
10	Minceva M, Rodrigues A E. Understanding and revamping of industrial scale SMB units for p-xylene separation[J]. AIChE Journal, 2007, 53(1): 138-149.
11	Rasouli M, Yaghobi N, Chitsazan S, et al. Effect of nanocrystalline zeolite NaY on meta-xylene separation[J]. Microporous and Mesoporous Materials, 2012, 152: 141-147.
12	Zhao Y J, Zhao H F, Liu D H. Selective adsorption and separation of o-xylene using an aluminum-based metal-organic framework[J]. Industrial & Engineering Chemistry Research, 2021, 60(47): 17143-17149.
13	Yang L P, Liu H B, Xing J C, et al. Separation of xylene isomers in the anion-pillared square grid material SIFSIX-1-Cu[J]. Chemistry—a European Journal, 2021, 27(20): 6187-6190.
14	Li X L, Wang J H, Bai N N, et al. Refinement of pore size at sub-angstrom precision in robust metal-organic frameworks for separation of xylenes[J]. Nature Communications, 2020, 11: 4280.
15	He Z J, Yang Y X, Bai P, et al. Metal-organic framework MIL-53(Cr) as a superior adsorbent: highly efficient separation of xylene isomers in liquid phase[J]. Journal of Industrial and Engineering Chemistry, 2019, 77: 262-272.
16	Mukherjee S, Joarder B, Manna B, et al. Framework-flexibility driven selective sorption of p-xylene over other isomers by a dynamic metal-organic framework[J]. Scientific Reports, 2014, 4: 5761.
17	Huang W, Jiang J, Wu D Y, et al. A highly stable nanotubular MOF rotator for selective adsorption of benzene and separation of xylene isomers[J]. Inorganic Chemistry, 2015, 54(22): 10524-10526.
18	Duan L H, Dong X Y, Wu Y Y, et al. Adsorption and diffusion properties of xylene isomers and ethylbenzene in metal-organic framework MIL-53(Al)[J]. Journal of Porous Materials, 2013, 20(2): 431-440.
19	Vermoortele F, Maes M, Moghadam P Z, et al. p-Xylene-selective metal-organic frameworks: a case of topology-directed selectivity[J]. Journal of the American Chemical Society, 2011, 133(46): 18526-18529.
20	Lennox M J, Düren T. Understanding the kinetic and thermodynamic origins of xylene separation in UiO-66(Zr) via molecular simulation[J]. The Journal of Physical Chemistry C, 2016, 120(33): 18651-18658.
21	Jie K C, Liu M, Zhou Y J, et al. Near-ideal xylene selectivity in adaptive molecular pillar[n]arene crystals[J]. Journal of the American Chemical Society, 2018, 140(22): 6921-6930.

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