高渗透支撑SBS膜制备与CH<sub>4</sub>/N<sub>2</sub>分离性能

徐靖凯; 高倩; 肖伟; 张登华; 张辉; 张柳杰

高渗透支撑SBS膜制备与CH₄/N₂分离性能

辽宁石油化工大学　石油化工学院, 抚顺 113001

基金项目: 辽宁省自然科学基金(2022-KF-13-05)

详细信息

通讯作者:
肖伟，博士，教授，硕士生导师，研究方向为电池隔膜材料、分离纯化用膜材料　E-mail：nuaaxiaowei@163.com

中图分类号: TQ028.8；TD712.67；TB332
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- 文章访问数: 56
- HTML全文浏览量: 23
- 被引次数: 0
出版历程
- 收稿日期: 2024-06-06
- 修回日期: 2024-08-28
- 录用日期: 2024-09-07
- 网络出版日期: 2024-09-21

Preparation and CH₄/N₂ separation performance of high permeability supported SBS membrane

College of Petroleum and Chemical Engineering, Liaoning Petrochemical University, Fushun 113001

Funds: Natural Science Foundation of Liaoning Province (2022-KF-13-05)

摘要

摘要: SBS嵌段树脂具有软硬段互相结合的独特结构，可通过挤压实现对气体分子的分离。本研究以多孔α-Al₂O₃陶瓷管为载体，利用一系列x-SBS/四氢呋喃(THF)树脂溶液制备了相应的SMS-x分离膜。FT-IR、XRD、SEM等表征测试结果表明，SBS树脂与载体之间可较好结合，分离膜厚度均小于50 μm。气体测试表明，在0.05 - 0.3 MPa压力范围内，SMS-20分离膜CH₄/N₂气体选择性最优，在0.1 MPa时，α(CH₄/N₂) =3.81，CH₄的摩尔通量为1.41×10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹。在0.3 MPa，SMS-10的CH₄摩尔通量最大，可达3.47×10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹。此外，通过不同比例混合气体的测试验证了本文制备的分离膜同样可胜任相应的分离工作。本文制备的所有分离膜在0.1 MPa压差下可稳定分离气体长达7 d，具有良好的性能稳定性。因此，多孔α-Al₂O₃支撑型SBS分离膜可兼备优异的渗透通量及气体选择性，在煤层气CH₄的富集方面提供有利选择。
- 气体分离膜 /
- 嵌段聚合物 /
- 支撑体 /
- 渗透通量 /
- CH₄/N₂选择性
Abstract: SBS block resin has a unique structure in which soft and hard segments are combined with each other, and gas molecules can be separated by extrusion. In this study, a series of x-SBS/Tetrahydrofuran (THF) resin solutions were used to prepare the corresponding SMS-x separation membranes with porous α-Al₂O₃ ceramics tubes as the carrier. FT-IR, XRD, SEM and other characterization test results show that the SBS resin can be well combined with the carrier, and the thickness of the separation membrane is less than 50 μm. The gas test shows that the SMS-20 separation membrane has the best CH₄/N₂ gas selectivity in the pressure range of 0.05-0.3 MPa. At 0.1 MPa, α(CH₄/N₂) =3.81, and the molar flux of CH₄ is 1.41×10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹. At 0.3 MPa, the CH₄ molar flux of SMS-10 is the largest, which can reach 3.47×10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹. In addition, the test of different proportions of mixed gas verifies that the separation membrane prepared in this paper can also be competent for the corresponding separation work. All the separation membranes prepared in this paper can stably separate gas for up to 7 days at a pressure difference of 0.1 MPa, and have good performance stability. Therefore, the porous α-Al₂O₃ substrate SBS separation membrane can have both excellent permeation flux and gas selectivity, and provide a favorable choice for the enrichment of coalbed methane CH₄.
- Separation Membrane /
- Block Polymer /
- Supporting /
- Permeation Flux /
- CH₄/N₂ Selectivity

HTML全文

图 1 SBS树脂分子链段结构示意图

Figure 1. Schematic diagram of molecular chain segment structure of SBS resin

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图 2 α-Al₂O₃支撑体SBS膜制备工艺示意图

Figure 2. Schematic diagram of preparation process of SBS membrane on α-Al₂O₃ substrate

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图 3 气体渗透性测试装置示意图

Figure 3. Gas permeability test device schematic diagram

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图 4 (a) 5-SBS/(四氢呋喃)THF (b) 10-SBS/THF (c) 15-SBS/THF (d) 20-SBS/THF的SBS粒径尺寸分布图

Figure 4. The SBS particle size distribution of (a) 5-SBS/Tetrahydrofuran (THF) (b) 10-SBS/THF (c) 15-SBS/THF (d) 20-SBS/THF

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图 5 α-Al₂O₃支撑体SBS膜的(a) FT-IR与(b) XRD谱图

Figure 5. (a) FT-IR and (b) XRD patterns of α-Al₂O₃ substrate SBS membrane

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图 6 不同分离膜(a,e) Al₂O₃载体 (b,f) SMS-10 (c,g) SMS-15 (d,h) SMS-20的表面SEM图像

Figure 6. (a,e) blank α-Al₂O₃ substrate (b,f) SMS-10 (c,g) SMS-15 (d,h) SMS-20 SEM images of the surface of different separation membranes

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图 7 不同分离膜(a) Al₂O₃载体 (b) SMS-10 (c) SMS-15 (d) SMS-20的截面SEM图像

Figure 7. (a) blank Al₂O₃ substrate (b) SMS-10 (c)SMS-15 (d) SMS-20 SEM images of cross-section of different separation membranes

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图 8 载体表面成膜 (a)示意图 (b)SEM照片

Figure 8. The membrane-forming schematic on the substrate surface (a)Schema (b)SEM

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图 9 不同分离膜在25℃不同压差下单组份气体(a)N₂渗透性 (b)CH₄渗透性 (c)CH₄/N₂选择性

Figure 9. The single component gas separation performance curves of different separation membranes at 25℃ and different pressure differences (a)N₂ permeability (b)CH₄ permeability (c)CH₄/N₂ selectivity

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图 10 不同分离膜在25℃，0.1 MPa压差下(a) CH₄∶N₂=50∶50 vol% (b) CH₄∶N₂=15∶85 vol%混合气体分离性能

Figure 10. The Data change trend diagram of (a) CH₄∶N₂=50∶50 vol% (b) CH₄∶N₂=15∶85 vol% mixed gas separation performance of different separation membranes at 25℃ and 0.1 MPa pressure difference

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图 11 不同分离膜在25℃，0.1 MPa压差下(a) N₂ (b) CH₄的4 h性能稳定性曲线

Figure 11. Performance stability curves of different separation membranes at 25℃ and 0.1 MPa pressure difference for 4 h (a) N₂ permeability stability (b) CH₄ permeability stability

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图 12 不同分离膜在25℃，0.1 MPa压差下(a) N₂ (b)CH₄的7 d性能稳定性曲线

Figure 12. Performance stability curves of different separation membranes at 25℃ and 0.1 MPa pressure difference for 7 d (a)N₂ permeability stability (b) CH₄ permeability stability

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表 1 不同分离膜的溶解系数与渗透系数

Table 1. Dissolution coefficient and permeability coefficient of different separation membranes

Sample	D(CH₄)^a	D(N₂)^a	S(CH₄)^b	S(N₂)^b
SMS-10	35.32	9.71	0.86	0.98
SMS-15	34.98	9.65	0.84	1.01
SMS-20	35.25	9.69	0.86	0.99
Notes: a：Diffusivity coefficient 10⁸ (cm² ·s⁻¹); b：Solubility coefficient [cm³(STP)/cm³·atm]

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表 2 本研究与相关文献报道性能对比

Table 2. Performance comparison between this study and related literature reports

Membrane material	P(CH₄)^a	P(N₂)^b	α(CH₄/N₂)	Operational condition^c	Ref.
Pebax^®	31	9.8	3.16	25℃，pure gas	[4]
Pebax^®	37	13	2.85	35℃，pure gas	[4]
SBS/Pebax^®	43.5	15.8	2.75	25℃，pure gas	[4]
SBS/Pebax^®	61.4	26.8	2.29	35℃，pure gas	[4]
SBS	37	12.5	2.96	25℃，pure gas，1 atm	[9]
SBS	50	16	3.13	35℃，pure gas，1 atm	[9]
SBS/PDMS-co-PHMS	440	140	3.14	25℃，pure gas	[19]
SBS/PDMS-co-PHMS	510	170	3.00	35℃，pure gas	[19]
Matrimid^®	310	180	1.72	25℃，pure gas	[24]
PI	0.0042^d	0.0087^d	0.48	25℃，pure gas	[25]
PIM-1	310	180	1.70	25℃，pure gas	[26]
SBS/α-Al₂O₃	14.1^e	3.71^e	3.81	25℃，pure gas，0.1 MPa	This work
SBS/α-Al₂O₃	34.7^e	11..21^e	2.87	25℃，pure gas，0.3 MPa	This work
Notes: a ,b：1 Barrer = 10⁻¹⁰ cm³ (STP) ·cm·cm⁻² ·s⁻¹·cmHg⁻¹ ; c：1 atm=0.1 MPa; d：GPU [10⁻⁶ m³ ·cm⁻² ·s⁻¹·cmHg⁻¹]; e：Permeation flux [10⁻⁶ mol·m⁻²·s⁻¹·Pa⁻¹] SBS is the Poly (styrene-b-butadiene-b-styrene); Pebax^® is the trade name of poly(ether-block-amide); PDMS-co-PHMS is the Trimethylsilyl terminated poly(dimethylsiloxane-co-methylhydrosiloxane); Matrimid^® is the trade name of PI (polyimide); PIM-1 is a novel polymer of intrinsic microporosity.

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