电子级CF4中痕量NF3杂质的吸附脱除

doi:10.16085/j.issn.1000-6613.2024-0718

摘要/Abstract

摘要：

高效低成本脱除氟碳合成法制备CF₄中的少量NF₃杂质对电子级CF₄的开发有着重要的应用价值。本文制备了一系列具备高密度开放金属位点的MOF-74材料作为吸附剂，利用一维孔道内活性位点与NF₃的强相互作用，在低分压下实现对NF₃的超高吸附容量（298K和10kPa时最高可达50.3mL/g）及优异NF₃选择性（在NF₃与CF₄摩尔比为0.001时，MOF-74-Mg对NF₃的理想吸附溶液理论选择性可达245.6）。理论计算结果表明，MOF-74孔道内的不饱和金属位点对极性分子NF₃具有强的吸附作用力；固定床穿透实验则进一步验证了材料能够在动态条件下捕获CF₄中的痕量NF₃。以上结果证实了这类基于开放金属位点的MOFs材料能够作为一种高效经济型的吸附剂，为分离纯化氟碳合成法制备CF₄中的痕量NF₃杂质提供了一种新的策略。

关键词: 开放金属位点, 金属有机骨架, 四氟化碳, 三氟化氮, 电子特气纯化

Abstract:

The efficient and low-cost removal of trace NF₃ impurities in the preparation of CF₄ by fluorocarbon synthesis method has important application value for the development of electronic grade CF₄. In this paper, a series of MOF-74 materials with high density open metal sites were prepared as adsorbents. Based on the strong interaction of active sites on NF₃ inside the one-dimensional channels, the ultra-high adsorption capacity of NF₃ under low partial pressure (up to 50.3mL/g at 298K and 10kPa) and excellent NF₃/CF₄ selectivity (the IAST selectivity of MOF-74-Mg can reach to 245.6 at 0.001 molar ratio of NF₃) were achieved. The theoretical results showed that the unsaturated metal sites in the pores of MOF-74 had stronger affinity for the polar molecule NF₃, and the fixed-bed breakthrough experiment further verified that the materials could capture trace NF₃ in CF₄ under dynamic conditions. In summary, the above results confirmed that MOFs materials with open metal sites could be served as an efficient and economical adsorbent, providing a new strategy for the separation and purification of trace NF₃ impurities in CF₄ prepared by fluorocarbon synthesis.

Key words: opening metal sites, metal organic framework, carbon tetrafluoride, nitrogen trifluoride, electronic special gas purification

中图分类号:

TQ 028.1

傅钰, 李晓宇, 伍岳, 陶春珲, 段然, 张文祥, 马和平. 电子级CF₄中痕量NF₃杂质的吸附脱除[J]. 化工进展, 2025, 44(6): 3570-3578.

FU Yu, LI Xiaoyu, WU Yue, TAO Chunhui, DUAN Ran, ZHANG Wenxiang, MA Heping. Removal of trace NF₃ impurities from electronic grade CF₄ by adsorption[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3570-3578.

图/表 10

表1 CF4和NF3的物理性质对比

气体	沸点/℃	动力学尺寸/Å	极化率/10^-25cm^-3	偶极矩/D
CF₄	-128	4.8	38.4	0
NF₃	-129	4.5	36.2	0.235

图1 高密度开放金属位点的MOF-74-M及其NF3-CF4分离应用示意图

图2 MOF-74-M（M=Co、Ni、Mg）的实验及理论PXRD谱图对比

图3 MOF-74-M（M=Co、Ni、Mg）的红外对比图

图4 MOF-74-Co、MOF-74-Ni和MOF-74-Mg的SEM图

图5 MOF-74-M（M=Co、Ni、Mg）的77K氮气吸附脱附等温线图（实心圆为吸附点；空心圆为脱附点）和孔径分布和累计体积（QSNFT模型）

图6 MOF-74-M（M=Co、Ni、Mg）在298K和273K下的NF3和CF4的吸附脱附等温线（实心圆为吸附等温线；空心圆为脱附等温线；1bar=105Pa）以及IAST选择性

图7 利用Materials Studio优化NF3@MOF-74-M（M=Co、Ni、Mg）和CF4@MOF-74-M（M=Co、Ni、Mg）的几何形状及吸附能

图8 不同压力下MOF-74-M（M=Co、Ni、Mg）三种材料NF3和CF4的模拟平均负载量

图9 固定床穿透装置示意图和MOF-74-M（M=Co、Ni、Mg）的实验穿透曲线

参考文献 29

[1]	CHANG Moo Been, CHANG Jen-Shih. Abatement of PFCs from semiconductor manufacturing processes by nonthermal plasma technologies: A critical review[J]. Industrial & Engineering Chemistry Research, 2006, 45(12): 4101-4109.
[2]	WU Yue, WANG Shanshan, ZHANG Wenxiang, et al. Enhancing perfluorinated electron specialty gases separation selectivity in ultra-microporous metal organic framework[J]. Separation and Purification Technology, 2022, 289: 120739.
[3]	WAN Zhuoyan, YAN Tongan, CHANG Miao, et al. Nickel-based metal-organic framework for efficient capture of CF₄ with a high CF₄/N₂ selectivity[J]. Separation and Purification Technology, 2023, 306: 122617.
[4]	李超楠, 魏磊, 酒坤, 等. MSA在三氟化氮分析检测装置中的应用[J]. 化学推进剂与高分子材料, 2020, 18(4): 67-70.
	LI Chaonan, WEI Lei, Kun JIU, et al. Application of MSA in analysis and detection device for nitrogen trifluoride[J]. Chemical Propellants & Polymeric Materials, 2020, 18(4): 67-70.
[5]	ZHANG Wenxiang, WU Yue, LI Yinhui, et al. Fluorine-functionalized porous organic polymers for durable F-gas capture from semiconductor etching exhaust[J]. Macromolecules, 2022, 55(4): 1435-1444.
[6]	于剑昆. 四氟化碳的合成与开发[J]. 化学推进剂与高分子材料, 2004, 2(3): 14-17.
	YU Jiankun. Synthesis and development of carbon tetrafluoride[J]. Chemical Propellants & Polymeric Materials, 2004, 2(3): 14-17.
[7]	唐忠福. 氟碳合成高纯四氟化碳的工艺技术[J]. 低温与特气, 2013, 31(1): 32-34.
	TANG Zhongfu. The sysnthesis technology of high purity tetrafluoromethane by fluorine and carbon[J]. Low Temperature and Specialty Gases, 2013, 31(1): 32-34.
[8]	VOROTYNTSEV V M, DROZDOV P N, VOROTYNTSEV I V, et al. The physico-chemical bases of separation and high purification of fluorocarbons and simple gases[J]. Petroleum Chemistry, 2011, 51(7): 492-495.
[9]	CHOLACH Alexander, YAKOVIN Dmitri. Removal of CF4 from NF₃ at the phase interface[J]. Journal of the Taiwan Institute of Chemical Engineers, 2022, 131: 104178.
[10]	ZHANG Minhua, LIU Lin, LI Qinghua, et al. Theoretical design of MOFs and PSA process for efficient separation of CF₄/NF₃ [J]. Industrial & Engineering Chemistry Research, 2023, 62(18): 7103-7113.
[11]	阙祥育. 电子级四氟化碳高效节能精馏技术的研究[J]. 当代化工研究, 2022(24): 137-139.
	QUE Xiangyu. Research on high eﬃciency and energy-saving distillation technology of electronic grade carbon tetraﬂuoride[J]. Modern Chemical Research, 2022(24): 137-139.
[12]	林德荣. 四氟化碳中三氟化氮杂质的热分解技术研究[J]. 当代化工研究, 2023(5): 182-184.
	LIN Derong. Research on thermal decomposition technology of nitrogen trifluoride impurity in carbon tetraﬂuoride[J]. Modern Chemical Research, 2023(5): 182-184.
[13]	WANG Chuanjin, LIU Xinlong, YANG Tianhang, et al. An overview of metal-organic frameworks and their magnetic composites for the removal of pollutants[J]. Separation and Purification Technology, 2023, 320: 124144.
[14]	WANG Kecheng, LI Yaping, XIE Linhua, et al. Construction and application of base-stable MOFs: A critical review[J]. Chemical Society Reviews, 2022, 51(15): 6417-6441.
[15]	FURUKAWA Hiroyasu, CORDOVA Kyle E, Michael O’KEEFFE, et al. The chemistry and applications of metal-organic frameworks[J]. Science, 2013, 341(6149): 1230444.
[16]	LI Jianrong, YU Jiamei, LU Weigang, et al. Porous materials with pre-designed single-molecule traps for CO₂ selective adsorption[J]. Nature Communications, 2013, 4(1): 1538.
[17]	AHMED Imteaz, JHUNG Sung Hwa. Applications of metal-organic frameworks in adsorption/separation processes via hydrogen bonding interactions[J]. Chemical Engineering Journal, 2017, 310: 197-215.
[18]	ISLAMOGLU Timur, CHEN Zhijie, WASSON Megan C, et al. Metal-organic frameworks against toxic chemicals[J]. Chemical Reviews, 2020, 120(16): 8130-8160.
[19]	Ülkü KÖKÇAM-DEMIR, GOLDMAN Anna, ESRAFILI Leili, et al. Coordinatively unsaturated metal sites (open metal sites) in metal-organic frameworks: Design and applications[J]. Chemical Society Reviews, 2020, 49(9): 2751-2798.
[20]	ZHAO Xiang, BU Xianhui, ZHAI Quanguo, et al. Pore space partition by symmetry-matching regulated ligand insertion and dramatic tuning on carbon dioxide uptake[J]. Journal of the American Chemical Society, 2015, 137(4): 1396-1399.
[21]	WANG Gangding, LI Yongzhi, ZHANG Wanfang, et al. Acetylene separation by a Ca-MOF containing accessible sites of open metal centers and organic groups[J]. ACS Applied Materials & Interfaces, 2021, 13(49): 58862-58870.
[22]	ZICK Mary E, LEE Jung-Hoon, GONZALEZ Miguel I, et al. Fluoroarene separations in metal-organic frameworks with two proximal Mg²⁺ coordination sites[J]. Journal of the American Chemical Society, 2021, 143(4): 1948-1958.
[23]	MYERS A L, PRAUSNITZ J M. Thermodynamics of mixed-gas adsorption[J]. AIChE Journal, 1965, 11(1): 121-127.
[24]	ZHOU Wei, WU Hui, YILDIRIM Taner. Enhanced H₂adsorption in isostructural metal-organic frameworks with open metal sites: Strong dependence of the binding strength on metal ions[J]. Journal of the American Chemical Society, 2008, 130(46): 15268-15269.
[25]	GEIER Stephen J, MASON Jarad A, BLOCH Eric D, et al. Selective adsorption of ethylene over ethane and propylene over propane in the metal-organic frameworks M₂(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)[J]. Chemical Science, 2013, 4(5): 2054-2061.
[26]	WU Yue, YAN Tong, ZHANG Wenxiang, et al. Adsorption interface-induced H...F charge transfer in ultramicroporous metal-organic frameworks for perfluorinated gas separation[J]. Industrial & Engineering Chemistry Research, 2022, 61(36): 13603-13611.
[27]	QUEEN Wendy L, HUDSON Matthew R, BLOCH Eric D, et al. Comprehensive study of carbon dioxide adsorption in the metal-organic frameworks M₂(dobdc) (M=Mg, Mn, Fe, Co, Ni, Cu, Zn)[J]. Chemical Science, 2014, 5(12): 4569-4581.
[28]	伍岳, 李晓宇, 陶春珲, 等. 离子改性的CON材料用于吸附分离NF₃ [J]. 化工进展, 2023, 42(11): 6076-6085.
	WU Yue, LI Xiaoyu, TAO Chunhui, et al. Adsorptive separation of NF₃ using ion-modified CON material[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 6076-6085.
[29]	陈姝晖, 伍岳, 张文祥, 等. 离子型有机多孔聚合物的制备及其烟气脱硫耦合脱碳性质[J]. 化工进展, 2023, 42(2): 1028-1038.
	CHEN Shuhui, WU Yue, ZHANG Wenxiang, et al. Preparation of ionic organic porous polymer and its coupled desulfurization and decarbonization properties in flue gas[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 1028-1038.

电子级CF₄中痕量NF₃杂质的吸附脱除

Removal of trace NF₃ impurities from electronic grade CF₄ by adsorption

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张新宇, 陶梦滢, 于小婷, 赵钟兴, 赵祯霞. 介孔金属有机骨架固定化漆酶及其活性艳蓝KN-R降解性能[J]. 化工进展, 2025, 44(3): 1758-1767.
[2]	张爱京, 王桢钰, 肖宁宁, 宋艳娜, 李军, 冯江涛, 延卫. 新型汞离子吸附材料研究进展[J]. 化工进展, 2025, 44(2): 899-913.
[3]	王涛, 高翔, 高继峰, 邓海全, 余显涌, 周振华, 唐玲, 吕航. 改性Cu-BTC基混合基质膜在CO₂分离中的应用[J]. 化工进展, 2024, 43(6): 3240-3246.
[4]	苏士焜, 刘唐, 金也, 郑金玉. 氢气纯化吸附材料研究进展[J]. 化工进展, 2024, 43(10): 5612-5632.
[5]	汪尚, 姚瑶, 王佳, 董迪迪, 常刚刚. CoZn-MOF衍生多级孔取向碳载CoP及其析氢性能[J]. 化工进展, 2024, 43(1): 447-454.
[6]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[7]	潘宜昌, 周荣飞, 邢卫红. 高效分离同碳数烃的先进微孔膜：现状与挑战[J]. 化工进展, 2023, 42(8): 3926-3942.
[8]	常晓青, 彭东来, 李东洋, 张延武, 王景, 张亚涛. MOFs基丙烯/丙烷高效分离混合基质膜研究进展[J]. 化工进展, 2023, 42(4): 1961-1973.
[9]	陈飞, 丁玉栋, 马丽娇, 朱恂, 程旻, 廖强. 微波合成MOF-808及其水蒸气捕集特性[J]. 化工进展, 2023, 42(12): 6461-6468.
[10]	伍岳, 李晓宇, 陶春珲, 张莹, 李印辉, 张文祥, 杨伯伦, 马和平. 离子改性的CON材料用于吸附分离NF₃[J]. 化工进展, 2023, 42(11): 6076-6085.
[11]	曹明敏, 韩铖乐, 杨芳, 陈玉焕. 离子液体/金属有机框架复合材料捕集分离CO₂[J]. 化工进展, 2023, 42(11): 5831-5841.
[12]	张金辉, 张焕, 朱新锋, 宋忠贤, 康海彦, 刘红盼, 邓炜, 侯广超, 李桂亭, 黄真真. UiO-66复合材料用于典型有机污染物吸附和光催化氧化的研究进展[J]. 化工进展, 2023, 42(1): 445-456.
[13]	朱晓, 朱军勇, 张亚涛. 金属有机骨架/聚酰胺薄层纳米复合膜的研究进展[J]. 化工进展, 2022, 41(8): 4314-4326.
[14]	张彦, 汪伟, 谢锐, 巨晓洁, 刘壮, 褚良银. 负载酶@ZIF-8复合物的聚合物微颗粒可控制备[J]. 化工进展, 2022, 41(4): 2022-2028.
[15]	陈运涛, 董晓旭, 王洋, 王健男, 崔美, 黄仁亮. 巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用[J]. 化工进展, 2022, 41(2): 854-861.