氦气分离聚合物膜

doi:10.11949/0438-1157.20241214

摘要/Abstract

摘要：

氦气作为一种不可再生的稀有气体，在科学研究、工业生产等领域发挥着至关重要的作用，高效、经济地分离纯化氦气具有重要的科研和应用价值。膜分离技术以其能耗低、操作简便等优势，成为氦气分离领域的研究热点。聚合物膜因其优异的柔韧性、成膜性以及良好的气体分离性能而备受关注。介绍了近年来聚酰亚胺、自聚微孔聚合物和含氟聚合物等氦气分离膜材料的最新研究进展，重点综述氦气分离膜材料的可加工性、放大生产以及长期稳定性（如塑化和物理老化）等问题，并对未来氦气分离聚合物膜材料的开发及未来发展趋势进行了展望。

关键词: 氦气, 膜, 聚合物, 分离, 稳定性

Abstract:

Helium, as a non-renewable noble gas, plays a vital role in scientific research and industrial production. Therefore, efficient and economical separation and purification of helium has significant research and application value. Membrane separation technology has emerged as a promising approach for helium purification owing to its low energy consumption and operational simplicity. Polymeric membranes, in particular, have garnered considerable interest due to their excellent flexibility, membrane-forming properties, and gas separation performance. This review summarizes the latest research progress of helium separation membrane materials such as polyimide, self-polymerized microporous polymer and fluorinated polymer in recent years, focusing on the processability, scale-up production and long-term stability (such as plasticization and physical aging) of helium separation membrane materials, and prospects for the development of helium separation polymer membrane materials and future development trends.

Key words: helium, membrane, polymer, separation, stability

中图分类号:

TQ 028.8

高冰冰, 许诺, 白云翔, 张春芳, 杨永强, 董亮亮. 氦气分离聚合物膜[J]. 化工学报, 2025, 76(5): 2119-2135.

Bingbing GAO, Nuo XU, Yunxiang BAI, Chunfang ZHANG, Yongqiang YANG, Liangliang DONG. Polymeric membranes for helium separation[J]. CIESC Journal, 2025, 76(5): 2119-2135.

图/表 14

表1 富He天然气田列表及成分［9］

Table 1 List of He-rich natural gas fields and composition［9］

天然气田	含量/%(摩尔)
天然气田	He	CH₄	N₂	CO₂	C₂₊
美国新墨西哥州	4.05	49	45	0.9	1.05
美国阿拉斯加州	2.54	90.2	6.8	0.3	—
美国得克萨斯州	1.17	66.2	31.1	0.1	1.43
加拿大艾伯塔省	0.53	93	6	0.5	—
波兰奥斯特罗	0.4	56	46	0.3	0.3
卡塔尔北场	0.03	79.5	5.19	3.68	8.85
澳大利亚棕榈谷	0.21	97.5	2.3	0.1	—

图1 膜分离与其他天然气提He技术比较[17]

Fig.1 Comparison of membrane separation with other He extraction technologies from natural gas[17]

表2 典型的He分离聚合物膜及性能

Table 2 Typical polymeric membranes for He separation and performances

膜名称	厚度/nm	He渗透系数/GPU^①	选择性		文献
膜名称	厚度/nm	He渗透系数/GPU^①	He/N₂	He/CH₄	文献
醋酸纤维素	130	106	34	31	[18]
Udel^® P1700 (聚砜)	50~100	200	100	100	[19]
BPDA-TMPD (聚酰亚胺)	约1000	360	12	11	[19]
Matrimid 5218 (聚酰亚胺)	约300	87	—	197	[19]
P84^® (聚酰亚胺)	500	33	6.3	5	[19]

图2 常见He分离聚合物膜材料

Fig.2 Common polymeric membrane materials for He separation

表3 常见聚酰亚胺膜的He气体分离性能

Table 3 He separation properties of common polyimide membranes

膜名称	温度/℃	压力/atm^①	He渗透系数/Barrer^②	选择性		文献
膜名称	温度/℃	压力/atm^①	He渗透系数/Barrer^②	He/N₂	He/CH₄	文献
P84^®	35	1	9	120	106	[21]
Matrimid^® 5218	35	5	23.1	98.6	131.1	[22]
6FDA-mPDA	35	7	80.46	92.3	229.4	[23]
6FDA-DAM:DABA	35	7	195.91	27.8	30.1	[23]
6FDA-DAM	35	7	533.21	9.7	11.4	[24]
6FDA-TFMB	35	4	73	247	—	[25]
PI-TB	35	1	376	19	13.92	[28]
MPAP-6FDA	35	4	26.03	11.31	—	[29]
TC-EBPA-TB	35	1	61.14	72.78	—	[32]
Ac-CoPI-TBs	35	1	540	16.36	16.36	[33]
PI-TB-N	35	1	531	13.61	13.97	[33]
6FDA-terphenyl	35	10	43.01	42.16	57.58	[34]
6FDA-biphenyl	35	10	37.59	61.02	105	[34]
6FDA-phenyl	35	10	36.45	59.17	103.25	[34]
6FDA-BAPB	36	6	38.2	81.27	82.3	[35]
6FDA-durene	35	4	358.4	9.46	11.06	[36]
6FDA-Durene/CARDO(OH)	25	35	285	13.7	21.4	[37]
6FDA-DAM	22	7	332	9.48	13.66	[38]
6FDA-DAM/6FDA-CARDO	22	7	139	14.04	21.82	[38]
6FDA-6FpDA	35	1	114	45.6	88.37	[39]
6FDA-OFB	35	1	220	22.68	42.31	[39]
6FD-PP	30	4	31.8	53.99	219.31	[40]
40%-PI	35	7	76.2	50.46	89.4	[41]
TBDA1-6FDA-PI	35	1	199	30.62	60.3	[42]
TB-PIMPIs	35	1	198	21.75	34.74	[43]

表4 常见自聚微孔聚合物膜的He气体分离性能

Table 4 He separation properties of common polymers of intrinsic microporosity membranes

膜名称	温度/℃	压力/atm	He渗透系数/Barrer	选择性		文献
膜名称	温度/℃	压力/atm	He渗透系数/Barrer	He/N₂	He/CH₄	文献
CPIM	35	3	153	6.3	—	[49]
FPIM-1	35	1	824	420	1004.87	[50]
PIM-F-30	22	1	710	229.03	443.75	[51]
ITB-DM	35	2	32	229	246	[52]
ITB-OT	35	2	83	184	198	[52]
ITB-Trip	35	2	3698	4.8	4.9	[52]
PIM-PI-TB-2	35	1	300	7.14	6.82	[53]
PIM-Trip-TB	35	2	2500	3.97	2.76	[54]
CCS-PIM	25	2	745.5	26.3	21.67	[55]

表5 常见全氟聚合物膜的He气体分离性能

Table 5 He separation properties of common perfluorinated polymeric membranes

膜名称	温度/℃	压力/atm	He渗透系数/Barrer	选择性		文献
膜名称	温度/℃	压力/atm	He渗透系数/Barrer	He/N₂	He/CH₄	文献
Teflon AF2400	22	1	2740	5.71	7.03	[58]
Teflon AF1600	22	1	830	15.09	20.24	[58]
Cytop	22	1	170	34	85	[58]
Nafion	35	1	40.9	227.22	511.25	[59]
Aquivion	35	1	27.5	161.76	316.09	[60]
Poly(PFMMD)	35	10	560	72	280	[61]
Poly(PFMD)	35	10	210	295.77	1615.38	[61]
Homo AF	22	3	3600	4.34	5.22	[63]
Hyflon AD	25	1	340	8.95	17	[64]
Polyperfluoropropylene	22	1	597	12.44	24.88	[65]
Poly(perfluropropyl vinyl ether)	22	1	357	17.5	31.59	[66]
Copoly(HFP-TFE)	22	1	533	19.89	46.75	[67]
Polyperfluoro(2-methyl-2- ethyl-1,3-dioxole)	35	1	2180	6.81	9.08	[68]

图3 聚合物膜对He/N2和He/CH4的分离性能与Robeson上限（1991年[75]、2008年[76]、2019年[77]）的比较

Fig. 3 Comparison of separation performance of polymeric membranes for He/N2 and He/CH4 with the Robeson upper bounds (1991[75], 2008[76], 2019[77])

图4 非对称膜的制备方法：（a）界面聚合；（b）浸没沉淀相转化[98,101]

Fig.4 Preparation methods for asymmetric membranes: (a) interfacial polymerization; (b) immersion-precipitation phase inversion [98,101]

图5 对称膜的制备方法:（a）在玻璃板上旋涂；（b）刮涂；（c）静电纺丝[104-105]

Fig.5 Preparation method of symmetric membrane: (a) spin coating; (b) blade coating; (c) electrospinning[104-105]

图6 （a）PIM-1膜和TFC膜的制备工艺；（b）旋涂法制备TFC PIM-1膜的工艺示意图；（c）中空纤维纺丝装置原理图；(d)引入Matrimid 5218的PIM-1 TFC膜的制备工艺[114-117]

Fig.6 (a) Process of PIM-based bulk membrane and TFC membrane preparation; (b) Schematic illustration of preparation process for TFC PIM-1 membranes via spin coating; (c) Schematic diagram of spinning device; （d）PIMs-based TFC membrane with introduction of Matrimid 5218[114-117]

图7 几种常见He分离聚合物材料多维度工业分析的五边形雷达图

Fig.7 A pentagonal radar chart for a multi-dimensional industrial analysis of several common He-selective polymer materials

图8 膜分离机制示意图[125]

Fig.8 Membrane separation mechanisms[125]

图9 非全氟聚合物膜和全氟聚合物膜用于He与其他气体分离的上限：(a) He/N2；(b) He/CH4；(c) He/CO2；(d) He/H2[125]

Fig. 9 Upper bounds of nonperfluoropolymer and perfluoropolymer membranes for He separation from other gases: (a) He/N2;(b) He/CH4; (c) He/CO2; (d) He/H2[125]

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