密胺苯二醛多孔聚合物/聚二甲基硅氧烷混合基质膜的制备及气体分离性能

以溶液复合成膜法制备了密胺苯二醛多孔聚合物(MA)/聚二甲基硅氧烷(PDMS)混合基质膜,利用扫描电镜(SEM)表征了混合基质膜的形貌。考察了不同MA用量下MA/PDMS混合基质膜的气体分离性能,结果表明,MA的加入可以在提高PDMS膜渗透系数的同时提高CO_2气体分离选择性;随着混合基质膜中MA含量的增加,混合基质膜的渗透系数均明显提高,气体分离选择性则先增大后减小。双组分混合气体分离测试结果表明,MA/PDMS(1.2%(w,质量分数))混合基质膜对CO_2/N_2和CO_2/CH_4的分离选择性分别是19.2和6.0,CO_2的渗透系数达到8100Barrer,均高于纯PDMS膜。MA/PDMS(1.2%(w))混合基质膜对CO_2/N_2混合气的分离性能突破了Robeson上限。     

CO2捕集膜分离的Pebax基材料研究进展

膜分离CO₂技术是实现“双碳”目标的关键技术手段之一,而膜材料的性能对膜分离效果具有重要影响.聚醚嵌段聚酰胺(Pebax)对CO₂具有较高的渗透性和选择性,其自身具有高机械强度和良好的化学稳定性,且价廉易得,是一种极具潜力的聚合物气体分离膜材料.本综述介绍了用于CO₂捕集的Pebax基膜材料的特征及其气体分离性能的影响因素,重点概述了Pebax制备工艺优化、促进传递膜、交联和共混四种Pebax超薄复合膜的优化方式,并综述了Pebax基混合基质膜及填料功能化的研究进展.针对目前Pebax基材料存在渗透性和选择性权衡的问题,对Pebax基膜材料未来的优化方向作出了展望.     

多孔材料表面修饰聚酰亚胺非对称混合基质膜对CO2/N2和CO2/CH4的气体分离

兼具高通量和高选择性的气体分离膜是研究膜分离材料的目标.采用相转化法制备了聚酰亚胺非对称膜,并将其作为基底膜材料,分别在其表面修饰掺有金属有机框架材料Cu₃(BTC)₂ (1, 3, 5-均苯三甲酸合铜),沸石咪唑酯骨架材料ZIF-8以及镁铝水滑石MgAl-LDHs的聚酰胺酸溶液,经热亚胺化后制成非对称混合基质膜.研究了该系列非对称混合基质膜的结构特性和对CO₂、CH₄和N₂气体分离性能;考察了ZIF-8的掺杂量对非对称混合基质膜透气性能的影响.结果表明非对称聚酰亚胺膜的表面修饰可有效地改变膜的表面性质,掺杂ZIF-8的非对称混合基质膜气体的透气性能和选择性都增加,且掺杂量为5% (w)时CO₂/N₂和CO₂/CH₄的理想选择性分别高达24和83,为合成高效的CO₂分离膜提供了借鉴.     

共轭微孔聚合物膜的制备策略及其分离应用

降低工业分离过程的能耗为缓解全球能源紧缺问题提供了有效途径. 相比传统工业分离技术, 膜分离技术能耗低、经济效益高, 开发高效的膜材料是提升膜分离性能的重要手段. 共轭微孔聚合物(CMP)膜具有刚性永久超微孔道、高孔隙率、孔结构及化学环境可调控、交联骨架稳定性好等优势, 在分离领域具有良好的应用前景. 概述了近年来CMP膜的制备方法并简要对比了其优缺点, 阐述了CMP膜在气体分离、有机溶剂纳滤、离子筛分和手性分离等领域的分离机理和研究进展, 为开发新型具有良好分离性能的CMP膜材料提供研究思路.     

纤维素醋酸丁酸酯/碳纳米管混合基质膜的气体分离性能

通过溶液复合-溶液成膜的方法,制备了一系列纤维素醋酸丁酸酯(CAB)/多壁碳纳米管(MWCNTs)的新型混合基质膜.表征了CAB/MWCNTs膜材料的形貌、结构与力学性能.结果表明,MWCNTs与CAB界面未见明显缺陷存在,混合基质膜材料具有良好的力学性能.进一步考察了不同MWCNTs含量(2 wt%~30wt%)对CAB/MWCNTs混合基质膜材料的气体分离性能的影响.发现,随着混合基质膜中MWCNTs含量的增加,其对几种测试气体(O2、N2、CH4、CO和CO2)的渗透系数均明显提高,尤其是常见气体对中的"快气"——O2和CO2的渗透系数提高显著:当MWCNTs含量为30 wt%时,所制备的混合基质膜对O2和CO2渗透系数分别达到40.24和180.20 Barrer,比纯CAB膜分别提高了约300%和260%;同时,混合基质膜对多种气体对均表现出优异的分离效果.     

活性炭材料吸附CO_2的研究进展

CO_2排放引起了诸多环境问题,从混合气体中分离、利用CO_2,是近期的研究热点.目前的CO_2捕集和分离技术,大都由于费用高、能耗大等问题难以得到推广.利用多孔材料吸附分离CO_2的方法,因其高效、低能耗、低成本、易再生、易回收等特点得到广泛关注.在实际应用中多孔材料不仅要具备较高的CO_2吸附量、选择性,还要有较好的疏水性能.因此,活性炭被认为是最适合的材料之一.其具有优异的疏水性能,在常压和高压下均呈现出很高的CO_2吸附量,并且容易再生.综述了活性炭材料作为CO_2吸附剂的最新进展,重点介绍活性炭微结构与CO_2吸附性能之间的关系、活性炭表面官能团与CO_2之间的相互作用,最后探讨了目前的研究中存在的问题,并对今后的CO_2吸附分离研究工作进行了展望.     

气体分离用MOF基混合基质膜的界面构建策略

混合基质膜结合多孔填料优异的气体分离性能和聚合物材料良好的加工性能,被认为是最具有应用前景的一种气体分离膜材料。金属-有机框架材料(MOF)由于具有高比表面积和孔隙率、可调节的孔径以及可修饰的表面性能,成为制备混合基质膜的重要多孔材料。本文针对MOF基混合基质膜制备中所面临的主要挑战,聚焦于MOF和聚合物界面缺陷问题,分析了界面缺陷的产生原因及其对性能的影响,重点阐述了改善MOF填料和聚合物基质界面相容性的策略,以期为制备具有良好的界面形态和优异的气体分离性能的混合基质膜提供借鉴思路。     

MOF-聚合物混合基质膜的制备、改性及其在渗透汽化中的应用

渗透汽化是一种具有能耗低、操作简便等优点的膜分离技术,目前传统聚合物渗透汽化膜在分离性能和稳定性等方面还有欠缺。金属有机框架(MOF)是由金属离子与有机配体以自组装形式组建而成的晶态多孔材料,具有独特的性质,如对目标分子的选择性吸附和分子筛分效应,近年来许多研究表明将MOF作为填料引入聚合物基质中构筑混合基质膜(MMMs)对其渗透汽化性能有很好的促进作用。本文从MOF的不同系列出发,讨论了适用于渗透汽化混合基质膜的MOF种类,分析了MOF-聚合物混合基质膜的制备方法与改性策略,综述了该类混合基质膜在渗透汽化方面(有机溶剂脱水、从稀溶液中回收有机物、有机混合物的分离)的应用进展,总结了用于渗透汽化的MOF-聚合物混合基质膜研究面临的挑战,并对其未来发展提出展望。     

抗溶胀型聚酰亚胺气体分离膜的制备及其研究进展

膜分离技术具有绿色、高效、低能耗等特点.聚酰亚胺膜具有优异的气体分离性能及机械性能,但在分离高压天然气及生物气时,聚酰亚胺膜易被CO2溶胀塑化,导致膜的选择性下降.近年来,已经报道了多种可用于提高聚酰亚胺膜抗溶胀的技术.本文介绍了由于CO2渗透引起的聚合物膜塑化机理,并详述了热退火、热交联、化学交联、热重排、与纳米材料共混及与聚合物共混等用于抑制聚酰亚胺膜塑化的方法,提出了用于天然气及生物气分离的膜材料,未来的主要研究方向是开发同时具备高气体渗透性及高抗CO2塑化的聚酰亚胺膜材料.     

CO_2捕集炭膜的前驱体结构设计及性能

从分子结构设计出发,合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体,并制备了炭膜.采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律;测试了所制备炭膜的气体分离性能.结果表明,前驱体的自由体积分数显著影响炭膜的气体分离性能;聚合物结构越具刚性,自由体积越大,所得炭膜结构越疏松,极微孔道尺寸越大,越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输.其中,刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积,提高聚合物的自由体积,所形成炭膜的结构较疏松,均表现出优异的气体渗透性和分离选择性,超越了Robeson上限,解决了传统炭膜气体渗透性能低的问题.特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时,CO_2气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10-18m2·s-1·Pa-1),可实现对CO_2的有效分离和捕集,展现出良好的商业化应用前景.     

Hydrate capture CO2 from shifted synthesis gas,flue gas and sour natural gas or biogas

CO₂ capture by hydrate formation is a novel gas separation technology, by which CO₂ is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO₂ and other gases. However, rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO₂ capture. In this paper, the key problems in CO₂ capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas (CO₂/CH₄ system), the bottleneck is how to enhance the selectivity of CO₂ hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO₂ separation from shifted synthesis gas, flue gas and sour natural gas or biogas.     

Amine‐Appended Hierarchical Ca‐A Zeolite for Enhancing CO2/CH4 Selectivity of Mixed‐Matrix Membranes

An amine‐appended hierarchical Ca‐A zeolite that can selectively capture CO₂ was synthesized and incorporated into inexpensive membrane polymers, in particular polyethylene oxide and Matrimid, to design mixed‐matrix membranes with high CO₂/CH₄ selectivities. Binary mixture permeation testing reveals that amine‐appended mesoporous Ca‐A is highly effective in improving CO₂/CH₄ selectivity of polymeric membranes. In particular, the CO₂/CH₄ selectivity of the polyethylene oxide membrane increases from 15 to 23 by incorporating 20 wt % amine‐appended Ca‐A zeolite. Furthermore, the formation of filler/polymer interfacial defects, which is typically found in glassy polymer‐zeolite pairs, is inhibited owing to the interaction between the amine groups on the external surface of zeolites and polymer chains. Our results suggest that the amine‐appended hierarchial Ca‐A, which was utilized in membrane fabrication for the first time, is a good filler material for fabricating a CO₂‐selective mixed‐matrix membrane with defect‐free morphology.     

Pebax‐Based Membrane Filled with Two‐Dimensional Mxene Nanosheets for Efficient CO2 Capture

Mixed matrix membranes (MMMs) made from inorganic fillers and polymers is a kind of promising candidate for gas separation. In this work, two‐dimensional MXene nanosheets were synthesized and incorporated into a polyether‐polyamide block copolymer (Pebax) matrix to fabricate MMM for CO₂ capture. The physicochemical properties of MXene nanosheets and MXene/Pebax membranes were studied systematically. The introduction of MXene nanosheets provided additional molecular transport channels and meanwhile enhanced the CO₂ adsorption capacity, thereby enhancing both the CO₂ peremance and CO₂/N₂ selectivity of Pebax membrane. The optimized MXene/Pebax membrane with a MXene loading of 0.15 wt % displayed a high separation performance with a CO₂ permeance of 21.6 GPU and a CO₂/N₂ selectivity of 72.5, showing potential application in CO₂ capture.     

The beneficial impacts of functional groups of CNT on structure and gas separation properties of PEBA mixed matrix membranes

Incompatibility between filler and polymer chains accompanied by particle agglomeration has a detrimental effect on the performance of mixed matrix membranes (MMMs). To obviate intermolecular forces of different additives, functional groups (-COOH, –NCO, and –NH₂) were grafted on the surface of multi-walled carbon nanotubes (MWCNTs) which were then incorporated as fillers in the poly(ether-block-amide) (PEBA) polymeric matrix in the range of 0.1–1 wt% loading. CO₂ permeability and ideal CO₂/N₂ and CO₂/CH₄ selectivity of MMMs was compared with the neat membrane, and the results revealed favorable enhancement and surpassed CO₂/N₂ Robeson's upper bound under 4–10 bar in the range of 15–55 °C. Mixed gas separation performance of MMMs, which is of vital importance in industrial applications, was also investigated. The results indicate that MWCNT-NCO created superior grafts with the polymer chains, and MMMs with this additive had a better gas separation performance with high mechanical and thermal stability.     

Enhanced CO2-selective behavior of Pebax-1657: A comparative study between the influence of graphene-based fillers

Mixed matrix membranes (MMMs) containing graphene-based fillers have attracted considerable attention in the field of gas separation. In this study, two types of graphene derivatives (Graphene (G) and Graphene Oxide (GO)) were embedded into the poly-ether-block-amide (Pebax) based MMM to investigate and compare CO₂/N₂ separation at various filler loadings (0.3–1 wt%). The morphologies of the prepared neat Pebax and MMMs were characterized by SEM, XRD, FTIR and DSC. Compared with the neat Pebax, the permeability of all gases was increased by adding filler content in the MMMs due to the crystallinity decrement of the polyamide (PA) segment. The best separation performance of the Pebax/G MMMs occurred at 0.7 wt%, where the CO₂ permeability increased from 26.51 to 44.78 Barrer (~1.7 times). Also, for the Pebax/GO MMMs, the CO₂ permeability was increased up to 58.96 Barrer (~2.2 times) by adding 0.5 wt% filler. This further gas permeation increment for the Pebax/GO sample was attributed to the higher affinity of GO nanosheets to CO₂ sorption, which can facilitate CO₂ gas transition through the membrane matrix. Moreover, the CO₂/N₂ ideal selectivity increased from 74.26 for the neat Pebax to 111.95 (~1.5 times) and 120.72 (~1.62 times) by adding 0.7 wt% G (Pebax/G-0.7) and 1 wt% GO (Pebax/GO-1) into Pebax, respectively. As a consequence, graphene derivatives can be recognized as a promising developer of permselectivity (permeability and selectivity) of the MMMs.     

A parametric study of CO2/N2 gas separation membrane processes for post-combustion capture

Capture of CO₂ from flue gases produced by the combustion of fossil fuels and biomass in air is referred to as post-combustion capture. Chemisorbent processes are considered to be the most feasible method and are already at an advanced stage of development, but gas separation membranes are attracting more and more attention as a possible alternative. This paper describes a detailed parametric study of mass and energy balances for a simulated single membrane process. Typical operating conditions (CO₂ concentration in the flue gas, pressure and temperature, etc.) together with the influence of the membrane quality (permeability, selectivity) and membrane area on membrane performance (CO₂ separation degree and CO₂ purity) are simulated over a wide range of parameters.     

Ultrapermeable Gel Membranes Enabling Superior Carbon Capture

Membrane technology is rapidly gaining broad attraction as a viable alternative for carbon capture to mitigate increasingly severe global warming. Emerging CO₂-philic membranes have become crucial players in efficiently separating CO₂ from light gases, leveraging their exceptional solubility-selectivity characteristics. However, economic and widespread deployment is greatly dependent on the boosted performance of advanced membrane materials for carbon capture. Here, we design a unique gel membrane composed of CO₂-philic molecules for accelerating CO₂ transportation over other gases for ultrapermeable carbon capture. The molecular design of such soft membranes amalgamates the advantageous traits of augmented permeation akin to liquid membranes and operational stability akin to solid membranes, effectively altering the membrane's free volume characteristics validated by both experiments and molecular dynamics simulation. Surprisingly, gas diffusion through the free-volume-tuned gel membrane undergoes a 9-fold improvement without compromising the separation factor for the superior solubility selectivity of CO₂-philic materials, and CO₂ permeability achieves a groundbreaking record of 5608 Barrer surpassing the capabilities of nonfacilitated CO₂ separation materials and exceeding the upper bound line established in 2019 even by leading-edge porous polymer materials. Our designed gel membrane can maintain exceptional separation performance during prolonged operation, enabling the unparalleled potential of solubility-selective next-generation materials towards sustainable carbon capture.     

Molecularly engineering polymeric membranes for H2/CO2 separation at 100–300 °C

Over the last two decades, polymers with superior H₂/CO₂ separation properties at 100–300 °C have gathered significant interest for H₂ purification and CO₂ capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H₂/CO₂ separation and the advantages of high-temperature operation (such as improved solubility selectivity and absence of CO₂ plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H₂ and CO₂, including functional polymers (such as polybenzimidazole) and engineered polymers by cross-linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size-sieving or H₂-sorptive nanofillers with attractive H₂/CO₂ separation properties.     

Uniformly Distributed Mixed Matrix Membranes via a Solution Processable Strategy for Propylene/Propane Separation

Aggregation of filler particles during the formation of mixed matrix membranes is difficult to avoid when filler loadings exceed a 10–15 wt %. Such agglomeration usually leads to poor membrane performance. In this work, using a ZIF-67 metal–organic framework (MOF) as filler along with surface modification of Ag₄tz₄ to improve processability and selective olefin adsorption, we demonstrate that highly loaded with a very low agglomeration degree membranes can be synthesized displaying unmatched separation selectivity (39) for C₃H₆/C₃H₈ mixtures and high permeability rates (99 Barrer), far surpassing previous reports in the literature. Through molecular dynamics simulation, the enhanced compatibility between ZIF-67 and polymer matrix with adding Ag₄tz₄ was proven and the tendency in gas permeability and C₃H₆ selectivity in the mixed matrix membranes (MMMs) were well explained. More importantly, the membrane showed a wide range of pressure and temperature resistance, together with remarkable long-term stability (>900 h). The modification method might help solve interface issues in MMMs and can be extended to the fabrication of other fillers to achieve high performance MMMs for gas separation.     

Insights on Cryogenic Distillation Technology for Simultaneous CO2 and H2S Removal for Sour Gas Fields

Natural gas demand has dramatically increased due to the emerging growth of the world economy and industry. Presently, CO₂ and H₂S content in gas fields accounts for up to 90% and 15%, respectively. Apart from fulfilling the market demand, CO₂ and H₂S removal from natural gas is critical due to their corrosive natures, the low heating value of natural gas and the greenhouse gas effect. To date, several gas fields have remained unexplored due to limited technologies to monetize the highly sour natural gas. A variety of conventional technologies have been implemented to purify natural gas such as absorption, adsorption and membrane and cryogenic separation. The application of these technologies in natural gas upgrading are also presented. Among these commercial technologies, cryogenic technology has advanced rapidly in gas separation and proven ideally suitable for bulk CO₂ removal due to its independence from absorbents or adsorbents, which require a larger footprint, weight and energy. Present work comprehensively reviews the mechanisms and potential of the advanced nonconventional cryogenic separation technologies for processing of natural gas streams with high CO₂ and H₂S content. Moreover, the prospects of emerging cryogenic technologies for future commercialization exploitation are highlighted.