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.     

含四芳基咪唑结构的热重排气体分离膜的制备与性能研究

合成了一种新型含四芳基咪唑结构的二胺单体4,4’-(4,5-二苯基-(3-羟基-4-氨基苯氧基)苯基)咪唑(PMAPPP),然后分别与5种二酐单体聚合,经热酰亚胺化处理得到含羟基聚酰亚胺(HPI)薄膜.接着,对这些薄膜进行450℃热处理,得到相应的热重排(TR)膜材料,并对薄膜进行了结构与性能表征.结果表明,刚性大体积四芳基咪唑结构的引入使HPI膜表现出优异的热性能和力学性能,玻璃化转变温度在263～361℃,拉伸强度在98.4～118.3 MPa.热重排后,TR膜的气体分离性能得到了显著提高.其中,TR(PMAPPP-6FDA)的气体渗透性能最佳,即H₂ (269.31 Barrer)、CO₂ (284.25 Barrer)、O₂ (62.75 Barrer)和N₂(10.67 Barrer),CO₂/N₂和O₂/N₂的理想选择性分别为25.24和5.88,且O₂/N₂     

多孔玻璃载体自转晶B-Al-MFI型沸石膜的原位合成

在乙胺和水的混合蒸汽相中,首次通过载体自转晶,在多孔玻璃表面原位合成了B-Al-MFI型沸石膜。X射线衍射和扫描电镜观察证明,膜中沸石晶体的取向是随机的。晶体尺寸约为15～25μm,单层晶体厚的膜约为10～20μm。在焙作去有机模板剂后的沸石膜上,O~2和N~2的透过性分别为0.095×10^-^8和0.15×10^-^8mol/(m^2·s·Pa)。计算的O~2/N~2的理想选择值(0.63)明显低于诺森扩散的理想选择性值(0.94)和透过原载体的理想选择性值(0.91)。     

含叔丁基聚酰亚胺均质膜的气体分离性能

采用高温“一步法”缩聚合成了一系列含叔丁基的可溶性芳香聚酰亚胺树脂, 然后通过溶液浇注法制得相应均质薄膜, 并对其气体分离性能进行了测试, 同时研究了二酐结构和温度对聚酰亚胺均质膜气体分离性能的影响. 结果表明, 对于H₂, N₂, O₂, CO₂和CH₄ 等5种气体, 含叔丁基聚酰亚胺均质膜不仅表现出良好的透气性, 而且具有较高的气体透过选择性, 4,4'-(六氟异丙烯)二酞酸酐(6FDA)和均苯四甲酸二酐(PMDA)两类聚酰亚胺均质膜的气体分离性能最佳. 除CO₂外, 这两类聚酰亚胺均质膜的气体渗透系数随温度升高而升高, 而所有测试气体在这两种均质膜中的扩散系数和溶解度系数均随温度升高而增大.     

燃煤烟气中共存杂质对膜分离CO2性能影响的实验研究

利用自行搭建的膜分离实验台,考察了共存气态组分以及颗粒物对于聚二甲基硅氧烷/聚砜(PDMS-PSF)复合膜分离CO₂性能的影响.结果表明,共存气态组分中O₂对于膜分离CO₂有抑制作用;由于SO₂浓度显著低于CO₂,在短时间内对膜分离CO₂没影响;水汽可以促进CO₂的分离;燃煤飞灰细颗粒在分离膜表面沉积会导致膜性能的恶化.在此基础上,采用模拟湿法烟气脱硫系统装置,进行了燃煤湿法脱硫净烟气环境下的膜分离CO₂实验;在测试的50 h以内,水汽、SO₂和O₂的共同作用导致膜分离性能在前期有一定的提高,随着运行时间的延长,细颗粒物对膜的影响程度加大,导致PDMS-PSF复合膜的分离性能逐渐恶化,最终导致膜的CO₂/N₂分离因子和CO₂渗透速率分别下降了17.91%和28.21%.     

MFI型分子膜的制备与H2S/CH4分离性能

采用二次生长法在多孔α-Al₂O₃载体上制备MFI型（ZSM-5和silicate-1）分子筛膜;通过XRD和SEM检测,证明所合成的分子筛膜为致密、交联和无取向的MFI型分子筛膜,厚度为5 μm;单组分气体渗透实验检测中,所制备样品膜的N₂渗透量均小于10^-11 mol/（m²·s·Pa）,可认为其无缺陷;同时,考察了样品分子筛膜对H₂S/CH₄混合气的分离效果,在渗透压分别为0.3和0.5 MPa时,silicate-1分子筛膜的H₂S/CH₄的分离因子分别为1.99和4.44,而ZSM-5分子筛膜的CH₄/H₂S的分离因子分别为6.71和12.85。     

离子液体在气体分离中的应用

离子液体是一类“可设计溶剂”,具有极低的蒸气压,几乎不挥发以及选择性溶解能力,近年来在气体分离领域得到了广泛的关注。本文综述了CO₂和SO₂等酸性气体、低碳链烷烃、烯烃和炔烃等有机气体,以及H₂、O₂、CO、N₂、Ar、Xe等其他气体在离子液体中的溶解性能,归纳了气体在离子液体中的溶解机理和溶解规律,分析了离子液体结构与溶解度、分离性质的定性关系,其中具有胺基、胍基等碱性基团的功能化离子液体对CO₂、SO₂等酸性气体具有良好的溶解性,含有不饱和基团的离子液体通过π-π相互作用可以改善烯烃在离子液体中的溶解度,炔烃则易溶于氢键碱性较强的离子液体;并介绍了离子液体/气体二元体系分子模拟、溶解度关联模型以及离子液体固定化用于气体分离等工作的研究进展,探讨了离子液体气体分离研究存在的问题和未来发展方向。     

薄片状MFI晶体无凝胶蒸汽辅助晶化制备b轴取向沸石膜

采用新型薄片状MFI沸石晶体作为晶种,通过无凝胶蒸汽辅助晶化法(gel-less steam-assisted crystallization,GLSAC)在烧结氧化硅多孔载体上制备了致密平整、b轴取向的MFI沸石膜。考察了GLSAC中模板剂浓度、釜底水量、生长温度及时间对MFI沸石膜的影响。扫描电子显微镜和X射线衍射结果显示,适量的模板剂和釡底水量能抑制晶种的面外生长。成功制备了厚度750 nm、致密平整的MFI沸石膜。制备的对丁烷异构体气体分离测试表明,25℃时,等物质的量的丁烷异构体的分离因子(SF_A/B)可达36,对正丁烷的渗透速率为1.5×10^-7mol·m^-2·s^-1·Pa^-1。     

中空纤维担载氧化硅膜的制备及结构研究

采用SXRD,HRTEM,FTIR,SEM和氮气吸附等测试手段对膜结构、形貌、孔径及其分布进行了表征.SXRD和HRTEM结果显示,所制备的膜具有短程有序结构.SEM分析发现膜表面完整.气体渗透实验表明,担载膜具有一定的气体选择性,在0.1MPa下对H₂/N₂和CH₄/N₂的分离因子分别为2.25和1.56,气体透过膜孔的扩散由努森机制所控制.等温氮气吸附实验显示,经500℃热处理后氧化硅膜的最可几孔径小于3.34nm,非担载膜的比表面积为919.8m²/g,孔容为0.43mL/g.     

复杂烟气条件下太西活性焦脱除Hg0的实验研究

为了解复杂烟气条件下活性焦吸附剂的脱汞特性,利用汞渗透管和主要气体成分模拟复杂烟气,在实验室规模的固态吸附剂汞吸附效能测定系统上,进行了太西活性焦吸附单质汞的实验研究,并采用FT-IR对活性焦表面进行了光谱表征。结果表明,在活性焦表面存在各种含氧官能团;在CO₂/N₂/O₂/SO₂/Hg⁰烟气体系中,当SO₂加入量为400、855、1 520 mL/m³时,出口汞浓度分别为36、43、48 μg/m³,SO₂对系统吸附Hg⁰的能力有抑制作用;在CO₂/N₂/O₂/NO/Hg⁰烟气体系中,较低浓度的NO对Hg⁰脱除有抑制作用,而高浓度值的NO抑制作用减弱;在CO₂/N₂/O₂/NO/SO₂/Hg⁰烟气体系下,提高NO浓度对Hg⁰脱除有一定的促进作用,而提高SO₂浓度初期促进汞的脱除,后期则表现为抑制作用。     

蒸汽相中c轴取向连续完美单层B-AI-ZSM-5沸石膜的原位制备

MFI型沸石分子筛，由于其具有较宽合成条件、合适均的一孔径、可修饰和改 性的骨架和孔道系统，高的热稳定性、水热稳定性、化学稳定性和机械强度，不仅 广泛应用于传统的催化和分离领域，而且也广泛地应用于膜的制备。由于MFI型沸 石晶体体型和晶内孔道系统 的各向异性，控制晶体在载体表面的定向生长对于膜 分离、膜催化、膜传感等都极其重要的。文献中报道的c轴取向MFI型沸石膜层的制 备方法有：（1）晶体在强电场作用下在载体表面上进行定向排 列，然后在排列好 的晶体间喷镀或电镀一层金属膜；（2）在有刻蚀槽的微结构硅片表面进行组装； （3）水热合成法；（4）晶种层的二次生长法等。     

Molecular dynamics simulations of gas separations using faujasite-type zeolite membranes

Gas separations with faujasite zeolite membranes have been examined using the method of molecular dynamics. Two binary mixtures are investigated, oxygen/nitrogen and nitrogen/carbon dioxide. These mixtures have been found experimentally to exhibit contrasting behavior. In O(2)/N(2) mixtures the ideal selectivity (pure systems) is higher than the mixture selectivity, while in N(2)/CO(2) the mixture selectivity is higher than the ideal selectivity. One of the key goals of this work was to seek a fundamental molecular level understanding of such divergent behavior. Our simulation results (using previously developed intermolecular models for both the gases and zeolites investigated) were found to replicate this experimental behavior. By examining the loading of the membranes and the diffusion rates inside the zeolites, we have been able to explain such contrasting behavior of O(2)/N(2) and N(2)/CO(2) mixtures. In the case of O(2)/N(2) mixtures, the adsorption and loading of both O(2) and N(2) in the membrane are quite competitive, and thus the drop in the selectivity in the mixture is primarily the result of oxygen slowing the diffusion of nitrogen and nitrogen somewhat increasing the diffusion of oxygen when they pass through the zeolite pores. In N(2)/CO(2) systems, CO(2) is rather selectively adsorbed and loaded in the zeolite, leaving very little room for N(2) adsorption. Thus although N(2) continues to have a higher diffusion rate than CO(2) even in the mixture, there are so few N(2) molecules in the zeolite in mixtures that the selectivity of the mixture increases significantly compared to the ideal (pure system) values. We have also compared simulation results with hydrodynamic theories that classify the permeance of membranes to be either due to surface diffusion, viscous flow, or Knudsen diffusion. Our results show surface diffusion to be the dominant mode, except in the case of N(2)/CO(2) binary mixtures where Knudsen diffusion also makes a contribution to N(2) transport.     

Novel preparation of NaA/carbon nanocomposite thin films with high permeance for CO2/CH4 separation

Novel NaA/carbon nanocomposite thin films were successfully prepared on a porous a-Al2O3 substrate by incorporatingnanosized NaA zeolite into novolak-type phenolic resin.The prepared films were characterized by XRD,SEM and single gaspermeation tests.The NaA zeolite/carbon nanocomposite thin films exhibited that the ideal separation factor of CO2/CH4 was 28.4and the carbon dioxide flux was 3.39*10-7mol/(Pa m2s)at room temperature and under a pressure difference of 100 kPa,whichwas two orders of magnitude higher than that of pure carbon membrane prepared at the same procedures and conditions as those ofcomposite films.From the SEM images,the films were continuous and highly intergrown.Compared with carbon membranes,thethickness of nanocomposite films was drastically decreased,which was helpful to reduce the diffusion resistance and increase theflux of gas permeance.     

H2 separation using defect-free, inorganic composite membranes

Defect-free, microporous Al(2)O(3)/SAPO-34 zeolite composite membranes were prepared by coating hydrothermally grown zeolite membranes with microporous alumina using molecular layer deposition. These inorganic composite membranes are highly efficient for H(2) separation: their highest H(2)/N(2) mixture selectivity was 1040, in contrast with selectivities of 8 for SAPO-34 membranes. The composite membranes were selective for H(2) for temperatures up to at least 473 K and feed pressures up to at least 1.5 MPa; at 473 K and 1.5 MPa, the H(2)/N(2) separation selectivity was 750. The H(2)/CO(2) separation selectivity was lower than the H(2)/N(2) selectivity and decreased slightly with increasing pressure; the selectivity was 20 at 473 K and 1.5 MPa. The high H(2) selectivity resulted either because most of the pores in the Al(2)O(3) layer were slightly smaller than 0.36 nm (the kinetic diameter of N(2)) or because the Al(2)O(3) layer slightly narrowed the SAPO-34 pore entrance. These composite membranes may represent a new class of inorganic membranes for gas separation.     

Characteristics of a zirconia composite membrane fabricated by a laser firing method

By a method of laser firing, a high zirconia containing (70%) composite membrane on porous ceramic tubing was successfully fabricated. The laser sintered composite membrane was characterized by gas separation/permeation experiments. In the separation experiment of a CO₂---CH₄ gaseous mixture, it was found that the separation factor of CH₄ over CO₂ was 1.15. In the pure gases permeation experiment, it was found that Knudsen diffusion is considered to be predominant in the permeation mechanism for pure gases H₂, He, CH₄, N₂, O₂, and CO₂, and the permeation mechanism of H₂O at lower temperature depends mainly on surface diffusion and on Knudsen diffusion at higher temperature.     

Combination of MOFs and zeolites for mixed-matrix membranes

Mixed-matrix membranes (MMMs) were prepared by combinations of two different kinds of porous fillers [metal-organic frameworks (MOFs) HKUST-1 and ZIF-8, and zeolite silicalite-1] and polysulfone. In the search for filler synergy, the MMMs were applied to the separation of CO(2)/N(2), CO(2)/CH(4), O(2)/N(2), and H(2)/CH(4) mixtures and we found important selectivity improvements with the HKUST-1-silicalite-1 system (CO(2)/CH(4) and CO(2)/N(2) separation factors of 22.4 and 38.0 with CO(2) permeabilities of 8.9 and 8.4 Barrer, respectively).     

Structures and Properties of Supported Polyimide/SnO2 Hybrid Membranes

A series of polyimide/SnO2 hybrid membranes supported on TiO2/kieselguhr-mullite were prepared from polyimide with a large amount of carboxyl and SnO2 sol via a sol-gel process. The SnO2 phase chemically linked with the polyimide through the pendant carboxyl along the polyimide. The hybrid membranes were highly homogeneous, and when the SnO2 contents reached 15wt% the SnO2 phase was observed as particles with a diameter of 5 nm dispersed in the hybrid membranes . The cross-linking between the SnO2 phase and polyimide effectively enhanced the glass temperature of the hybrid films. With the increasing of the SnO2 contents, the pore sizes of the membranes decreased, and their pore sizes were mainly focused on 3.8, 3.1, 2.8 and 2.4 nm. The hybrid membranes showed higher permeability for H2, CO2, CO and H2O when compared to the pure polyimide. The separation factors of the polyimide/SnO2 hybrid membranes with 15wt% SnO2 content for H2/N2, CO2/N2, CO/N2 and H2O/N2 were 54.1, 30.2, 35.9 and 40.1, respectively.     

Alumina-supported SAPO-34 membranes for CO2/CH4 separation

SAPO-34 membranes were prepared by in situ crystallization on alpha-Al2O3 porous supports. The crystal size of the seeds was effectively controlled in the 0.7 to 8.5 micron range by employing different structure-directing agents. Seeds smaller than 1 micron produced membranes with CO2/CH4 separation selectivities higher than 170 and unprecedented CO2 permeances as high as 2.0 x 10(-6) mol/m2.s.Pa at 295 K and a feed pressure of 224 kPa. The membranes effectively separated CO2/CH4 mixtures up to 1.7 MPa.     

NaA Zeolite Membrane with High Performance Synthesized by Vapor Phase Transformation Method

IntroductionZeolitemembranes ,asaremarkablebranchofinor ganicmembrane ,havepotentialadvantagesinmanyappli cationssuchascatalysisandseparation ,chemicalsensors ,ascousticwavedevices ,andmicroelectronicdevicesduetotheiruniformporesizeatthemolecularlevelandresis tancetohightemperature .1 5For 10years ,manyre searchershavepaidconsiderableattentiontosynthesisofzeolitemembraneswithhighperformance .Amongthere portedzeolitemembranes ,mostattentionwasfocusedonsynthesisofMFI typezeolitemembranebecausei…