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Carbon Capture Science & Technology · 2023 · IF 0

Ultrathin UiO-66-NH2 polycrystalline membrane for CO2/CH4 separation

Wufeng Wu,Jiang Fan,Dongyue Wang,Yali Zhao,Xinglei Zhao,Yanying Wei

MOF membranes exhibit impressive performance in gas separation due to their large surface area, controllable pore size and unique affinity. Here, the ultrathin UiO-66-NH 2 polycrystalline membranes with thickness of ∼320 nm are successfully prepared within 1 h using a combination of ultrasound-assisted and microwave synthesis strategies. During the reaction, high-density small MOF nuclei are produced by sodium formate ultrasound-assisted, which act as sufficient nucleation sites for heterogeneous nucleation during membrane growth, aiming for development of a continuous MOF membrane on the porous substrate. The obtained UiO-66-NH 2 membrane shows an ideal CO 2 /CH 4 selectivity of 40 due to the enhanced the interaction between CO 2 molecules and the membrane. Moreover, the narrowed pore structure further hinders the diffusion of larger-sized molecules owing to -NH 2 occupying the pore channels, resulting in elevated CO 2 /CH 4 selectivity. Compared to many other MOF membranes, the UiO-66-NH 2 polycrystalline membranes exhibit a well balance of gas permeance and CO 2 /CH 4 selectivity, which presents a new route for CO 2 capture.

研究领域: 材料科学 · 化学工程 · 环境科学
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Solvent-induced microstructure of polyimide membrane to enhance CO2/CH4 separation

Ruoxing Liao,Yumin Guo,Liqiu Yang,Haoli Zhou,Wanqin Jin

Membrane technology , a successful technology for separating gases such as CO 2 /CH 4 mixture, has attracted much attention because of its low energy consumption, and membrane performance is an important factor affecting its industrial application. Herein, the solvent-induced microstructure of a polyimide membrane was employed to enhance its CO2/CH4 separation performance. The effect of solvents on the membrane structure and gas separation performance was investigated by using different solvents (such as tetrahydrofuran, N,N-dimethylacetamide) to dissolve a newly synthesized polyimide polymer, which was fabricated into a membrane. Various characterization methods, such as positron annihilation lifetime spectroscopy (PALs) and X-ray diffractometry (XRD), were conducted to reveal changes in the microstructure of membranes prepared with different solvents. The interaction of solvents with groups of polymer backbones was also analyzed for the explanation of the effect of solvents on the membrane performance for the separation of different gas pairs, such as CO2/CH4 mixture. The results showed that a membrane with optimal separation performance was obtained by optimizing the solvent composition, which exceeded the 2018 mixed-gas CO2/CH4 upper bound. The induced effect of solvents on the polymer membrane structure provides a new research path for the optimization of polymer membranes to enhance separation performance.

研究领域: 材料科学 · 化学工程 · 气体分离技术
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Membranes · 2021 ·Vol. 11 ·期 2 ·118 · IF 4.106

Efficient Facilitated Transport Polymer Membrane for CO2/CH4 Separation from Oilfield Associated Gas

Chunwei Zhang,Menglong Sheng,Yaoqiang Hu,Ye Yuan,Yulong Kang,Xiao Sun,Tao Wang,Qinghua Li,Xisen Zhao,Zhi Wang

CO2enhanced oil recovery (CO2-EOR) technology is a competitive strategy to improve oil field economic returns and reduce greenhouse gas emissions. However, the arbitrary emissions or combustion of the associated gas, which mainly consists of CO2and CH4, will cause the aggravation of the greenhouse effect and a huge waste of resources. In this paper, the high-performance facilitated transport multilayer composite membrane for CO2/CH4separation was prepared by individually adjusting the membrane structure of each layer. The effect of test conditions on the CO2/CH4separation performance was systematically investigated. The membrane exhibits high CO2permeance of 3.451 × 10−7mol·m−2·s−1·Pa−1and CO2/CH4selectivity of 62 at 298 K and 0.15 MPa feed gas pressure. The cost analysis was investigated by simulating the two-stage system. When the recovery rate and purity of CH4are 98%, the minimum specific cost of separating CO2/CH4(45/55 vol%) can be reduced to 0.046$·Nm−3CH4. The excellent short-to-mid-term stability indicates the great potential of large industrial application in the CH4recovery and CO2reinjection from oilfield associated gas.Keywords:oilfield associated gas;CO2capture;multilayer composite membrane;facilitated transport;CO2/CH4separation

研究领域: 化学工程 · 环境科学
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MICROPOROUS AND MESOPOROUS MATERIALS · 2022 · IF 5.876

Highly efficient of CO2/CH4 separation performance via the pebax membranes with multi-functional polymer nanotubes

Yanyong Sun,Minmin Gou

Based on the one-dimensional tubular structure of halloysite nanotubes (HNTs), plant polyphenols and polyamines were used for in situ polymerization on the surface of HNTs to form amino-rich polymers, which were then removed as templates to synthesize polymer nanotubes. These nanotubes were then incorporated into a Pebax matrix to prepare mixed-matrix membranes (MMMs) for CO 2 /CH 4 gas separation. The removal of the HNT template increased the lumen diameter of the filler and significantly improved its gas permeability . And the amino groups on the inner surface of the polymer nanotubes were exposed. Further, the number of CO 2 reaction sites increased, which improved the reaction selectivity of CO 2 . In addition, the presence of amine groups on the inner and outer surfaces of the polymer nanotubes provided various transfer channels for CO 2 , which were conducive for CO 2 gas transfer in the membrane. When the CC-PEINT content was 8 wt%, the CO 2 permeability was 710 Barrer and CO 2 /CH 4 selectivity was 60. The CO 2 permeability and CO 2 /CH 4 selectivity of the Pebax/CC-PEINTs membranes increased by 163% and 132%, respectively, compared with those of the pure Pebax membrane.

CAS / MDL: 120-80-9 9002-98-6
研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

ZIF-301 MOF/6FDA-DAM polyimide mixed-matrix membranes for CO2/CH4 separation

Zhenggang Wang,Jianwei Yuan,Renhao Li,Haipeng Zhu,Jingui Duan,Yanan Guo,Gongping Liu,Wanqin Jin

Compared with traditional separation methods, membrane-based technology shows advantages in energy efficiency for natural gas purification. To overcome the performance trade-off of conventional polymeric membranes, in this study, ZIF-301 MOF was employed as novel filler to fabricate 6FDA-DAM polyimide mixed-matrix membranes (MMMs) for CO 2 /CH 4 separation. A solvent exchange approach was proposed to remove the high-boiling-point solvent used for fabricating the MMMs. The microstructures and physico-chemical properties of the ZIF-301 fillers and ZIF-301/6FDA-DAM MMMs were characterized by SEM, EDX, XRD, IR, TGA, DSC and high-pressure sorption isotherms. The CO 2 /CH 4 transport properties through the MMMs were evaluated by permeation measurement at various feed pressures and analyzed by solution-diffusion model. The results showed that the incorporation of ZIF-301 into 6FDA-DAM enhanced both the CO 2 permeability and CO 2 /CH 4 selectivity, attributing to the preferential CO 2 sorption and aperture molecular sieving effect of the ZIF-301 filler. The MMM with optimal ZIF-301 loading of 20 wt% exhibited CO 2 permeability of 891 barrer and CO 2 /CH 4 of 29.3 that surpassed the 2008 Robeson upper-bound, suggesting that ZIF-301 based membrane could be a potential candidate for natural gas purification.

CAS / MDL: 872-50-4 10196-18-6
研究领域: 材料科学 · 化学工程 · 环境科学
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RSC Advances · 2024 ·Vol. 14 ·期 29 ·21151-21157 · IF 3.9

Rapid synthesis of aminal-linked covalent organic frameworks for CO2/CH4 separation

Jianwei Yang,Xianghao Han,Xiao Feng

As an emerging category of crystalline porous materials, covalent organic frameworks (COFs) are primarily synthesized via solvothermal methods. However, achieving rapid synthesis of COFs through this approach poses a significant challenge. To address the issue of slow synthesis, we studied the crystallization process of aminal-linked COFs via the condensation of a cost-effective aldehyde and secondary amine, and successfully expedited the synthesis of COFs within a one-hour duration. Furthermore, gram-scale aminal-linked COFs with abundant ultra-microporous channels demonstrated promising potential for CO2/CH4 separation. This study enables the rapid synthesis of aminal-linked COFs from cheap raw materials, which lays a foundation for their practical applications.

研究领域: 材料科学 · 化学工程
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SEPARATION SCIENCE AND TECHNOLOGY · 2016 · IF 1.083

Microwave synthesis of tubular zeolitic imidazolate framework ZIF-8 membranes for CO2/CH4 separation

Yaqiong Zhu,Qian Liu,Aisheng Huang

The separation of CO2/CH4 is reported in detail by using zeolitic imidazolate framework (ZIF-8) membrane which was prepared on 3-aminopropyltriethoxysilane modified Al2O3 tube through microwave heating synthesis. Attributed to the preferential adsorption affinity of CO2 over CH4 and a narrow pore window of 0.34 nm, the ZIF-8 membrane shows high separation performances for the separation of CO2/CH4 mixtures. For the separation of equimolar CO2/CH4 mixture at 100°C and 2 bar feed (1 bar permeate) pressure, a CO2 permeance of 1.02 × 10−8 mol/m2· s· Pa and a CO2/CH4 selectivity of 6.8 are obtained, which is promising for CO2 separation.

研究领域: 材料科学 · 环境工程
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JOURNAL OF MEMBRANE SCIENCE · 2018 · IF 6.578

Enhanced CO2/CH4 separation performance of mixed-matrix membranes through dispersion of sorption-selective MOF nanocrystals

Ke Chen,Kai Xu,Long Xiang,Xiao Dong,Yue Han,Chongqing Wang,Lin-Bing Sun,Yichang Pan

Mixed matrix membranes (MMMs) derived from metal-organic frameworks (MOFs) nanocrystals represent a promising alternative for overcoming the trade-off between permeability and selectivity derived from the pristine polymeric membrane . The selection of MOFs fillers are mainly focused on their diffusion-selectivity property for gas-pairs. However, the improvement of both gas-permeability and selectivity through addition of sorption-selective MOFs are rarely reported. Herein, the incorporation of CO 2 -philic KAUST-7 (also referred to as NbOFFIVE-1-Ni) nanocrystals makes the neat 6FDA-Durene polyimide membrane more permeable and more selective, surpassing the state-of-the-art 2008 Robeson upper bound for CO 2 /CH 4 . Nano-sized (~ 80 nm) KAUST-7 crystals with sharp particle size distribution were first fabricated through a co-solvent synthesis method. The explored gas transportation mechanism indicates that the improvement of CO 2 /CH 4 selectivity on MMMs are attributed to the significant raise of the sorption-selectivity rather than the diffusion-selectivity. The favorable interfacial interaction between the imide groups of the 6FDA and the H of the pyrazine in the KAUST-7 enhances plasticization resistance of the neat polymer membrane. The developed MMMs exhibit a promising application in CO 2 capture from natural- and bio-gas.

研究领域: 材料科学 · 化学工程
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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Molecularly Homogenized Composite Membranes Containing Solvent-Soluble Metallocavitands for CO2/CH4 Separation

Tongxin Liu,Ruili Zhang,Guang-Rui Si,Bin Liu,Yabo Xie,Lin-Hua Xie,Jian-Rong Li

The rational design of mixed matrix membranes (MMMs) combining appropriate additives and industrial processable polymers offers a new prospect for highly efficient membrane separations. However, the difficulty in their fabrication due to the lack of processability of most additives and the formation of segregated filler domains in polymer matrices hampers the development and application of MMMs. Herein, we present two new zirconocene-based metallocavitands (ZRA and ZRT) and a series of MMMs fabricated by blending ZRA, ZRT, and MOC-1-NH2 (a zirconocene-based metal–organic cage) with the polyimide (6FDA-DAM), respectively. It was found that ZRA exhibited high thermal stability and good solubility in various solvents, which can be homogeneously mixed with polymers to prepare ZRA-based MMMs without any indication of filler agglomeration. Compared to the pure 6FDA-DAM membrane, a low ZRA-loading MMM (ZRA-2.2%) exhibited better mechanical properties and 50% improved CO2 permeability for CO2/CH4 separation. ZRA-2.2% also exhibited a good performance after 6 months of aging and significantly alleviated the plasticization effect under high pressures. These results suggest the great potential of the ZRA-2.2% for CO2/CH4 separation and that the simple metallocavitands may serve as promising additives in fabricating MMMs for gas separations.

研究领域: 材料科学 · 化学工程 · 气体分离技术
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Veiled metal organic frameworks nanofillers for mixed matrix membranes with enhanced CO2/CH4 separation performance

Ke Chen,Linhan Ni,Hao Zhang,Jia Xie,Xin Yan,Saisai Chen,Junwen Qi,Chaohai Wang,Xiuyun Sun,Jiansheng Li

The interfacial compatibility between fillers and polymers essentially influences the separation performance of mixed matrix membranes (MMMs). In this work, an one-pot synthesized functional layer veiled zeolite imidazolate frameworks-67 (VZIF-67) was used as an efficient nanofillers to fabricate MMMs via physical blending with 6FDA-Durene polyimide. Benefiting from the CO 2 affinity from functional layer and the intrinsic characteristics of porous nanofillers, significant enhancement on separation performance was observed on the resultant MMMs. Specifically, the optimized VZIF-67 MMMs (30 wt% loading) exhibited CO 2 /CH 4 selectivity of 32.5 with CO 2 permeability of 1210 Barrer, which is 1.7 and 1.5 times higher than those of the control membrane, respectively. More importantly, the surface organic attribute and abundant amine groups of VZIF-67 reinforced the interfacial compatibility between the nanofillers and polymer matrix, leading to a doubled CO 2 /CH 4 selectivity compared with the ZIF-67 MMMs. Overall, the performance of the VZIF-67 membrane toward CO 2 /CH 4 separation surpasses the 2008-updated Robeson upper bound. These results indicate the functionalization strategy on porous nanofillers is a promising approach to fabrication of high performance of MMMs.

CAS / MDL: 1107-00-2 3102-87-2
研究领域: 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2025 · IF 9

Amino-functionalized KAUST-7 embedded polymers of intrinsic microporosity membrane with enhanced selectivity for CO2/CH4 separation

Ke Chen,Xin Guo,Linhan Ni,Junwen Qi,Jiansheng Li

Rational design and construction of fillers and polymers are crucial for the development of high-performance mixed matrix membranes (MMMs). In this work, amino-functionalized metal-organic frameworks KAUST-7 (KAUST-7-NH 2 ) with square-shaped sheet morphology were utilized as fillers to fabricate MMMs by physical blending with the polymer of intrinsic microporosity (PIM-1). The square-shaped KAUST-7-NH 2 sheets, prepared via in situ replacement of 2-aminopyrazine into the KAUST-7 framework, exhibited superior separation performance compared to the mono-ligand KAUST-7. Benefiting from the strong CO 2 affinity, high porosity and optimal pore sizes of KAUST-7-NH 2 , the outstanding CO 2 /CH 4 separation performance of the composite membrane was observed. The integration of square-shaped KAUST-7-NH 2 sheets provides a 2.5-fold improvement in CO 2 /CH 4 selectivity together with acceptable gas permeability as compared to the original PIM-1 membrane. Furthermore, a 100-h continuous permeation test validated the stability of the fabricated MMMs. Remarkably, the resulting MMM retained 92% of their initial CO 2 permeability after 150 days (drop of only 249 Barrer), indicating that the reduction in CO 2 permeability was approximately 10-fold lower than that of the pristine PIM-1 membrane. The prepared MMMs exhibit enhanced CO 2 /CH 4 selectivity and long-term stability, making it a highly promising candidate for practical application.

研究领域: 材料科学 · 化学工程
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Incorporating KAUST-7 into PIM-1 towards mixed matrix membranes with long-term stable CO2/CH4 separation performance

Ke Chen,Linhan Ni,Hao Zhang,Chengming Xiao,Li Li,Xin Guo,Junwen Qi,Chaohai Wang,Xiuyun Sun,Jiansheng Li

Rational design of fillers and polymers is of great importance to fabricate mixed matrix membranes (MMMs) with high performance. In this work, fluorinated metal-organic frameworks (KAUST-7 (also referred as NbOFFIVE-1-Ni)) were adopted as nanofillers to prepare MMMs through physically blending into the polymer of intrinsic microporosity (PIM-1). Benefiting from the features of porous KAUST-7, including well CO 2 affinity, distinctive pore characteristics (size, shape, and functionality) and strong intermolecular interactions with PIM-1, the achieved MMMs demonstrated increased CO 2 /CH 4 separation performance and improved anti-physical aging property. Specifically, with the assistance of KAUST-7, the CO 2 permeability and CO 2 /CH 4 (30:70 vol%) selectivity of the optimized MMMs increased up to 5928 Barrer and 23.5, corresponding to improvements of 50% of and 88% of the permeability and selectivity compared with the pristine membranes, respectively. Importantly, 100-h continuous separation test results confirmed the satisfying long-term stability of the prepared MMMs. Notably, the MMMs maintained 91% of the initial CO 2 permeability after 150 days (decreased only 539 Barrer), implying that the CO 2 permeability decrement is about 5-fold lower than that of the control PIM-1 membrane. These results suggest that the fabricated MMMs are promising candidates for CO 2 separation in practical applications.

CAS / MDL: 584-08-7 77-08-7
研究领域: 材料科学 · 环境工程
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