Advanced Membranes
·
2025
·
IF 9.5
Bingbing Gao,Yiran Peng,Ming Wu,Hua Ma,Jianchao Sun,Peng Zhang,Xingzhong Cao,Like Ouyang,Xiaobin Fu,Chunfang Zhang,Yunxiang Bai,Lijun Liang,Yang Liu,Liangliang Dong
Polyimide membranes have attracted considerable attention for gas separation applications; however, achieving efficient helium (He) separation remains a significant challenge due to the low fractional free volume ( FFV ) and poorly controlled pore size distribution. Here, we report a novel three-in-one polyimide-based blended membrane constructed from a polymer (6FDA-TFMB) and alkynyl-based polyimide (EBPA-TB) matrix via thermal crosslinking. By carefully designing membrane synthesis and structure, the resulting membrane achieves the “1+1>2” effect: (i) high He selectivity derived from reinforced interphase adhesion and size-sieving ability due to the hydrogen bonding and similar structure between 6FDA-TFMB and EBPA-TB; (ii) high He permeability derived from the rigid cross-linked network distorting the EBPA-TB chain packing and generating additional free volume; (iii) high anti-aging performance derived from the thermal crosslinking preventing microstructural rearrangements. The optimal membrane an unprecedented combination of high He permeability (51.24 Barrer), excellent He/N 2 selectivity (146.40) and remarkable aging resistance (less than 3.97 % of permeability decrease over 50 days), outperforming the performance of state-of-the-art polyimide-based blended membranes for He purification. This three-in-one blended membrane construction strategy provides a general toolbox for the development of next-generation, high-performance blended membranes with desirable performance for diverse industrial applications.
研究领域:
材料科学
·
化学工程
·
气体分离技术
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Zhiyuan Liu,Yanni Liu,Haoran Wang,Zhou Qu,Jinpeng Hou,Hong Meng,Hongwei Fan
Metal–organic framework (MOF) membranes have great potential in efficient helium (He) recovery, but it is highly demanded to improve their separation performance by enhancing molecular sieving. Herein, we explored an orifice-modified MOF-on-MOF bilayer membrane prepared by growing an amino-functionalized ZIF-7 layer on a ZIF-90 layer through an aldehyde-amine condensation reaction. Due to the precise docking between the aperture windows of the crystal cells of such two MOFs, the size-sieving effect was intensified for selective He separation. The resultant membrane exhibits significantly increased selectivities for He/N2 and He/CH4 along with a satisfactory He permeance (∼67 × 10–10 mol·m–2·s–1·Pa–1). Specifically, the He/N2 selectivity of the membrane can reach 16.19, which is about 5 times higher than that of the ZIF-90 membrane (3.24), ranking among the reported He-selective MOF membranes. In addition, a continuous operation for 100 h, subjected to a successive test at room temperature and 150 °C indicates that the membrane has excellent stability. The proposed concept of orifice-modified MOF-on-MOF would provide a new idea for the design and development of advanced MOF-based gas separation membranes.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Hua Ma,Haohao Liu,Feng Tian,Bingbing Gao,Lijun Liang,Yang Liu,Peng Gao,Xingzhong Cao,Yunxiang Bai,Chunfang Zhang,Liangliang Dong
Membrane separation technology plays a critical role in the utilization of helium (He) resources. Yet, the performance of current polymer membranes is hindered by a trade-off between permeability and selectivity, as well as by physical aging. Solving these problems is vitally crucial for the industrial application of He separation. This study reported controllable thermal crosslinking of alkynyl-based polyimide membrane (EBPA-TB-TC) to improve He permeability and anti-aging performance. The resulting covalently crosslinked structures conferred thermal and chemical stability to the membranes, as well as increased microporosity. It led to a notable 'anti-trade-off' effect and improved anti-aging characteristics. An optimized EBPA-TB-TC membrane exhibited a superior combination with a He permeability of 61.14 Barrer and an He/N 2 selectivity of 72.78. Crucially, mixed-gas He/N 2 (1:1, 50/50) separation results over 50 days revealed minimal reductions in He permeability (1.34 %) and He/N 2 selectivity (2.95 %), indicating fantastic anti-aging performance. These findings demonstrated the significant potential of thermally cross-linked EBPA-TB-TC membrane in long-term stable helium separation.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Yisa Zhou,Kunyan He,Yutong Lou,Jian Xue,Haihui Wang
Membrane separation offers an efficient and energy-saving process for extracting rare helium from natural gas. Among them, mixed matrix membranes (MMMs) containing two-dimensional (2D) materials are considered potential gas separation membranes. Herein, 2D g-C 3 N 4 nanosheets with nanoporous structure are incorporated into the polyimide (PI) matrix to prepare MMMs for efficient He separation. The incorporated g-C 3 N 4 nanosheets generate additional gas transport and sieving channels in MMMs. As a result, the PI/g-C 3 N 4 MMM comprising 0.5 wt% g-C 3 N 4 nanosheets exhibits a He/CH 4 selectivity of 160.4 with He permeability of 40.7 Barrer, which are 2.0 and 3.2 times higher than the pure PI membrane, respectively. Moreover, the membrane also shows good stability at elevated temperatures or a continuous 150 h long-term operation. Therefore, the remarkable gas separation performance and excellent stability make the membrane promising for gathering helium from natural gas.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2023
·
IF 9.5
Zhenyuan Li,Tianliang Han,Wei Lai,Jie Ma,Yang Zhang,Qi Wu,Can Wang,Chunfa Liao,Shuangjiang Luo
Herein, we develop and investigate the performance of defect-free hollow fiber membranes (HFMs) based on a novel 6FDA-mPDA 0.65 -DABA 0.3 -TFMB 0.05 copolyimide for helium separation from multi-component natural gas. The copolyimide is synthesized using a two-step condensation polymerization, and the hollow fiber membranes are fabricated using a dry-jet/wet-quench spinning approach. Thermal crosslinking of hollow fiber membranes is conducted to enhance plasticization resistance. The crosslinked membranes exhibit improved He selectivity (α(He/CH 4 ) = 259) compared to the pristine hollow fiber membrane (α(He/CH 4 ) = 210). Gas permeation tests are performed on the pristine and crosslinked hollow fiber membranes using pure-gas and mixed-gas at various pressures. The results demonstrate that the crosslinked membranes effectively resist plasticization even under high-pressure gas feeds containing CO 2 , light hydrocarbons, and heavy hydrocarbons. In contrast, the uncrosslinked membranes experience plasticization, dramatically decreasing selectivity. The findings provide valuable insights into the plasticization behavior of different impurity compounds in hollow fiber membranes and highlight the potential of thermal crosslinking as an effective strategy to improve the plasticization resistance of HFMs for He recovery. These defect-free and plasticization-resistant membranes hold promise for efficient He recovery from mixed-gas streams, offering a viable and energy-efficient alternative to traditional separation methods.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Lingyu Liu,Qixuan Li,Luxin Sun,Aqib Riaz,Jianxin Li,Yingge Wang,Ingo Pinnau,Xiaohua Ma
One major challenge of helium recovery from natural gas by membranes is the development of materials offers both high He permeability and He/CH 4 selectivity. Here, ultrahigh performance He separation membranes were achieved by directly fluorination of a carbon molecular sieve (CMS) membrane that derived from pyrolyzing a polyimide at 550 °C. The FCMS550-60, fluorinated for 60 s, showed an unprecedented combination of high He permeability of 3432 Barrer and ultrahigh He/CH 4 selectivity of 5329 that is located far beyond any He/CH 4 trade-off lines. Additionally, it also exhibited outstanding mixed-gas separation properties with a He permeability of 1765 Barrer and He/CH 4 selectivity of 4114 at 20 bar. The largely enhanced He/CH 4 selectivity resulted exclusively from a boost in diffusion selectivity, which is originated from the formation of C–F bonds inside the micropores of the CMS membrane that remarkably enhanced the sieving ability of the FCMS membrane. This work provides a broad prospect for the application of FCMS membranes for He recovery from natural gas and other resources.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2025
·
IF 4.5
Zhenyuan Li,Xing Liu,Ying Sun,Lili Gong,Chunfa Liao,Shuangjiang Luo
Industrial gas separation processes demand membranes with superior separation performance under high feed pressures. Herein, we fabricate defect-free hollow fiber membranes (HFMs) using 6FDA-mPDA 0.9 -TFMB 0.1 copolyimide, achieving both exceptional pressure resistance and excellent gas separation performance. Through a dry-jet/wet-quench spinning approach, we systematically optimize the microstructure of the HFMs by adjusting the dope composition and spinning conditions. The results reveal that polymer concentration, dope-to-bore fluid ratio, and take-up rate have a significant impact on the pressure resistance of HFMs. Under optimized conditions, the fabricated HFMs exhibit a high burst pressure of 10.5 MPa, along with excellent gas separation performance, including a He permeance of 72.1 GPU and a He/CH 4 selectivity of 178. Additionally, mixed-gas permeation experiments conducted at feed pressures up to 750 PSIA demonstrate excellent resistance to heavy hydrocarbons. These ultra-strong, high-performance HFMs show great potential for efficient helium separation from natural gas under high-pressure conditions.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Zhou Qu,Yanni Liu,Haoran Wang,Qianxi Yang,Hongwei Fan,Hong Meng
Hetero-structured nanocomposite membranes have great potential in advanced gas separation due to the synergy of hierarchical pores. Herein, we report a MOF (metal–organic framework)-in-COF (covalent organic framework) layer supported on a polyacrylonitrile (PAN) ultrafiltration substrate prepared by a contra-diffusion reaction of MOF inside a one-dimensional (1D) pore-channels of COF layer. Such 1D confinement-induced membrane features a unique ultramicropore-in-nanopore structure, which intensifies the molecular sieving while preserving high-speed transfer pathways. The prepared ZIF-67-in-TAPB-BPDA-PAN membrane exhibited an excellent helium (He) permeance of ∼1500 GPU together with an enhanced separation selectivities of 3.89 for He/N 2 and 5.38 for He/CH 4 , respectively. The overall performance is competitive among the reported He-selective membranes. A continuous gas permeation test for 100 h indicates good stability. This work would bring insights into the engineering and preparation of nanocomposite functional materials applied in various separation fields.
研究领域:
材料科学
·
化学工程
·
膜技术
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2025
·Vol. 19
·期 10
·1-10
·
IF 4.5
Wang Lu,Li Zhiqiang,He Yangdong,Huang Chenzhi,Chen Shijin,Zhou Xianyun,Fan Xiaosong,Xie Wenjing,Wang Xuerui
Membrane gas separation is an energy-efficient approach to extract helium from natural gas. However, the limited separation performance shown as Robeson’s upper bound has hindered the techno-economic feasibility. This study introduces an advanced copolyimide membrane engineered for He extraction from natural gas. The membranes were facilely achieved by dip-coating the α -alumina substrates in the copolyimide solution followed by in situ thermal rearrangement. In addition to the rigid 5-amino-2-(4-aminobenzene)benzimidazole segments, the active ortho-hydroxyl groups were converted to benzoxazole rings, contributing to extra micropores. The membrane showed an improved mixture selectivity of 120 and He permeance of 23.5 GPU, far surpassing the performance of benchmark membranes for helium separation over CH 4 . The membrane also demonstrated long-term stability as evidenced by the continuous operation over 250 h. Additionally, the membrane exhibited resistance to impurities such as CO 2 and C 2 H 6 , enduring the asymmetric membranes promising for practical helium extraction from natural gas.
研究领域:
材料科学
·
化学工程
·
气体分离技术
✓ 已验证
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Yiqiang Deng,Shengwang Li,Zhuo Yang,Guining Chen,Xiuling Chen,Shuang-Feng Yin,Gongping Liu
The inherent nanochannels of mixed-matrix membranes (MMMs) have demonstrated significant potential in molecular sieving-based separations. However, achieving efficient helium (He) separation and purification remains challenging due to the inherent trade-off between selectivity and permeability. To overcome these limitations, rational design of polymer structures and MOF particle and preparation strategy for MMM is imperative. Herein, we proposed a strategy for constructing novel MOF-802/Mi@6FPZ MMMs for efficient He separation and purification. The design employed a tailored system composed of 6FPZ copolyimide (6FDA/mPDA:PABZ), MOF-802, and the small-molecule modulator 2-methylimidazole (Mi) to MMMs. The presence of hydrogen bonding between Mi and 6FPZ polymer, the formation of Zr–N coordination bonds between Mi and MOF-802 verified by ATR-IR spectroscopy, enabled the MOF-802 particles to be dispersed uniformly within the 6FPZ. Notably, the Zr–N bond formation liberated partial –COOH groups, creating additional nanochannels within the MOF-802/Mi@6FPZ to facilitate gas transport. PAL experiments indicated that the optimized MOF-802(20 %)/Mi(10 %)@6FPZ MMMs possess an average channel size of ≈0.40 nm, ideal for the selective separation of He from CH 4 or N 2 . This small molecule bridged MMMs achieved remarkable He/CH 4 and He/N 2 selectivity values of 429.8 and 174.2, respectively, coupled with a He permeability of 177 Barrer far surpassing the 2016 upper bound. This novel design strategy not only addresses critical challenges in He separation but also presents a versatile platform for developing defect-free, high-performance MMMs for a range of gas separation applications.
研究领域:
材料科学
·
膜分离技术
·
高分子化学
·
气体分离
·
纳米材料
·
能源化工
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）