沸石填充硅橡胶渗透汽化膜的制备及其优先透醇性能研究

由ZSM-5沸石和聚二甲基硅氧烷(PDMS)制备超薄沸石填充PDMS复合膜,考察沸石填充量、沸石结构中硅铝比和操作温度对沸石填充硅橡胶膜渗透汽化性能的影响。结果表明,超薄复合膜的制备可以改善渗透通量小的缺陷。沸石填充量30%时分离因子最大;具有相同填充量的PDMS膜,硅铝比较大的填充膜,其分离因子和渗透通量均较高;随着操作温度的升高,复合膜分离因子先升高后降低,在50℃达到最大值,其渗透通量呈升高趋势。     

渗透汽化膜的制备及其应用进展

渗透汽化（pervaportion, PV）作为一种新颖的分离技术在工业范围内得以应用,至关重要的是它在恒沸混合物、近沸混合物分离方面的显著优势。相比分馏、精馏、萃取等传统分离方法,渗透汽化技术具有经济、高效、便于管理的优点,但目前缺少优质的渗透汽化膜材料和先进的膜制备方法。本文综述了近年来渗透汽化技术以及渗透汽化膜的研究现状,首先介绍了PV技术的分离机理、PV膜的制备方法、PV技术在工业上的应用领域等,并重点讨论了料液温度、料液浓度、料液流速、膜上下游蒸汽压差、膜材料等关键因素对渗透汽化分离性能的影响。文中提出未来渗透汽化技术应在膜材料方面积极探索,选用聚合物为材料,并结合先进的膜制备方法来进一步降低膜的厚度,从而明显地提高膜渗透通量。     

PDMS/PTFE沸石填充复合膜及渗透汽化性能研究

以MFI疏水沸石作为填充剂,制备了PDMS（聚二甲基硅氧烷）/PTFE沸石填充复合膜,并利用SEM、XRD等手段对其进行了表征。以环己酮/水溶液为分离实验体系,考察了沸石填充量对PDMS/PTFE沸石填充复合膜渗透汽化性能的影响。     

SiO2填充的聚二甲基硅氧烷膜在渗透汽化透醇领域的应用

制备一系列底膜为聚偏氟乙烯(PVDF)、m(SiO_2)∶m(PPMS)比不同的SiO_2/聚二甲基硅氧烷(PDMS)杂化膜。考察了m(SiO_2)∶m(PPMS)比、操作温度等因素对杂化膜透醇性能的影响,并对其微观形貌(SEM)、溶胀性质以及正电子湮没寿命谱(PALS)进行了表征。结果表明,在室温下,以PDMS为主体的m(SiO2)∶m(PPMS)比杂化膜的自由体积孔穴平均半径(0.39nm)介于水、乙醇的分子动力学半径之间,是造成此类膜材料渗透通量普遍偏小的原因。杂化膜的自由体积孔穴数量随着SiO_2填充的增加而下降。     

A型沸石分子筛膜微波合成及渗透汽化性能

引　言沸石分子筛具有均匀的分子尺寸微孔结构和良好的热稳定性、机械强度、催化作用 ,是当前无机膜材料研究的热点之一 .沸石分子筛膜合成方法主要有原位水热合成法和汽相合成法 ,应用这些方法已成功合成出Ａ型[1] 、Ｙ型[2 ] 、Ｐ型[3 ] 、ＭＦＩ等[4 ] 等沸石分子筛膜 .Ａ型沸石分子筛由于具有0 .3～ 0 .5ｎｍ的有效孔径和三维孔道结构 ,亲水性强 ,有可能在小分子气体如低碳烃类分离及有机物脱水等方面得到应用 .Ｊａｎｓｅｎ等[5] 认为晶体粒径愈大 ,产生堆积孔径愈大 ,所合成的沸石分子筛膜存在缺陷可能性愈大 .但从文献报道看 ,沸石分…     

芳烃优先透过的渗透汽化复合膜的制备及分离性能研究

采用紫外光接枝填充聚合技术,以非对称聚丙烯腈(PAN)超滤膜为底膜,聚乙二醇甲醚甲基丙烯酸酯(MePEO300MA)为大分子单体,制备了芳烃优先透过的渗透汽化复合膜。考察了单体浓度和紫外光照射反应时间对复合膜甲苯/正庚烷渗透汽化分离性能的影响,并对复合膜降低石脑油芳烃含量,优化乙烯裂解原料进行了初步探索。研究结果表明,复合膜对甲苯质量分数为20%的甲苯/正庚烷混合物(80℃)的分离系数达到5.6,渗透通量为2.47 kg/(m2.h);当切割比为20%时,石脑油的芳烃质量分数由7.52%降至4.11%,降低了45%,初步说明渗透汽化复合膜在降低石脑油的芳烃含量,优化乙烯裂解原料方面的应用前景。     

细菌纤维素膜渗透汽化分离二元有机物水溶液

采用动静结合的方式制备出了细菌纤维素膜。以乙醇水溶液、丙酮水溶液、乙酸水溶液为研究对象,研究了渗细菌纤维素膜的吸附性能,并讨论了透汽化过程中原料液浓度、温度对分离效果的影响及渗透汽化过程中可能的分离机理。结果表明,细菌纤维素膜能够优先透水,在渗透汽化分离乙醇和丙酮时,渗透通量随浓度的上升呈下降的趋势,温度对渗透通量的影响基本符合Arrhenius方程渗透汽化分离二者时,分离因子随浓度的增加先增加后减小。渗透汽化分离乙酸时,渗透通量随浓度的上升呈先上升后下降的趋势,分离因子变化不明显,温度对渗透通量的影响偏离Arrhenius方程较明显。     

细菌纤维素膜渗透汽化分离二元有机物水溶液

采用动静结合的方式制备出了细菌纤维素膜。以乙醇水溶液、丙酮水溶液、乙酸水溶液为研究对象,研究了渗细菌纤维素膜的吸附性能,并讨论了透汽化过程中原料液浓度、温度对分离效果的影响及渗透汽化过程中可能的分离机理。结果表明,细菌纤维素膜能够优先透水,在渗透汽化分离乙醇和丙酮时,渗透通量随浓度的上升呈下降的趋势,温度对渗透通量的影响基本符合Arrhenius方程渗透汽化分离二者时,分离因子随浓度的增加先增加后减小。渗透汽化分离乙酸时,渗透通量随浓度的上升呈先上升后下降的趋势,分离因子变化不明显,温度对渗透通量的影响偏离Arrhenius方程较明显。     

地质聚合物原位合成八面沸石膜及其渗透汽化性能

以煅烧高岭土和水玻璃为原料制备地质聚合物,采用水热合成法原位合成了自支撑八面沸石(简称FAU型)膜。利用X射线衍射、扫描电子显微镜、万能压力试验机表征了沸石膜材料的抗压强度和微观结构,通过渗透汽化实验及数学模型考察了乙醇/水混合物体系进料组成和温度对沸石膜的渗透通量以及分离因数的影响。结果表明:该沸石膜表面的晶粒细小,膜覆盖完全且连续致密;提高养护时间有利于提高地质聚合物的压缩强度,提高水热时间有利于改善FAU型沸石膜表面形貌和相组成。在进料温度为50℃、原料中乙醇的含量为70%的优化条件下,FAU型沸石膜具有较高的渗透通量和分离因数,其渗透通量和分离因数分别达到1.41kg/(h m2)和16.8。     

碳纳米管填充聚氨酯膜的制备及渗透汽化性能研究

渗透汽化膜分离技术在苯酚/水领域引起广泛关注。文章对端羟基聚丁二烯(HTPB)基的聚氨酯膜进行填充改性并研究其对苯酚/水体系的渗透汽化性能。利用物理和化学方法将β-环糊精(β-CD)接枝到羟基碳纳米管(MWNTs-OH)上,制备两种碳纳米管,并对改性后的碳纳米管进行元素分析。将改性后的两种碳纳米管填充到聚氨酯中。研究发现,物理改性羟基化碳纳米管的渗透通量最大,80℃达175.56 kg·μm·m-2·h-1,但是分离因子为2.8;化学改性的羟基化碳纳米管的分离性能较优,80℃下膜的分离因子为3.6,渗透通量为101.73 kg·μm·m-2·h-1。     

碳纳米管填充PDMS膜的渗透汽化性能

将碳纳米管（CNTs）填充到PDMS中制备出CNTs/PDMS杂化膜,并将其用于乙醇/水体系的分离,发现由多壁碳纳米管制备的膜分离性能优于单壁碳纳米管填充膜,在40℃下,进料乙醇浓度为5%（质量分数）时,膜的分离因子可由8.3提高到10.0,渗透通量为206.2 g·（m²·h）^-1;采用十二烷基三氯硅烷对多壁碳纳米管进行修饰,并对修饰前后碳纳米管的性能进行表征,研究表明修饰后碳纳米管表面形成疏水层,碳纳米管的疏水性增强;将修饰后的碳纳米管填充到PDMS中,可进一步提高杂化膜对乙醇的选择性,膜的分离因子可提高到11.3,渗透通量为130.9 g·（m²·h）^-1。     

Influence of binding interface between active and support layers in composite PDMS membranes on permeation performance

Effect of the binding interfaces of composite polydimethylsiloxane (PDMS) membranes on their pervaporation performance was studied. The membranes were made up of PDMS as active skin layer and polysulfone (PSF) or polyamide (PA) as supporting layer. PDMS‐PSF membrane was numbered 1, and PDMS‐PA membrane numbered 2. The pervaporation experiments were carried out by using the composite membranes and dilute ethanol–water mixture. The experimental measurements for the permeation performance under various operating conditions (e.g., feed concentration and temperature) showed that the specific permeation rate of membrane 2 was over membrane 1 by seven times at least. A resistance‐in‐series model was applied to formularize the transport of the permeants. Influence of the binding interfaces between the active skin layer and support layers in these membranes on pervaporation performance was analyzed. The cross section morphology of the membranes and chemical element distribution along membrane thickness were examined by using SEM and EDS. It was found that, although the PDMS intrusion layer into PSF near the interface was only about 2 μm, it gave significant effect on the permeation performance. It implied that the resistance produced by the intrusion layer into PSF was apparently larger than that of PDMS intruding PA and over intrinsic PDMS resistance. These should be probably attributed to structures and formation of the binding interfaces. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2468–2477, 2007     

Pervaporation separation of ethanol/water mixture using modified zeolite filled PDMS membranes

In this article, the composite polydimethylsiloxane (PDMS) membranes supported by cellulose acetate (CA) microfiltration membrane were successfully prepared by adding modified zeolite particles with a silane coupling agent, NH₃–C₃H₆–Si(OC₂H₅)₃. The sorption and diffusion behaviors of ethanol and water in the films were studied. The results showed that with the increase in the modified zeolite content, the solubility selectivity increased, but the diffusion selectivity first increased, then decreased. The effects of modified zeolite content and feed temperature on the pervaporation performance of the composite membranes in 10 wt % ethanol/water mixture were also investigated. When modified zeolite loading was 20 wt %, for 10 wt % ethanol/water mixture at 40°C, the permeate flux was 348.7 g·m^?2·h^?1, the separation factor was 14.1, and the permeate separate index was 4568, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41897.     

白炭黑填充PDMS/PVDF复合膜的纳滤分离性能及传质特性

将纳米级白炭黑填充于PDMS制备了白炭黑填充PDMS/PVDF复合膜,采用红外(FT-IR)、热失重(TGA)和接触角(CA)等方法对填充复合膜进行了分析和表征,并采用纳滤的方法系统研究了复合膜对大豆油/己烷混合油的分离性能。结果表明,白炭黑填充能有效促进PDMS的交联,提高PDMS的疏水性、热失重温度以及对溶剂的稳定性;白炭黑填充量增加使复合膜渗透通量降低,但截留率从96%提高到98%;随溶液浓度增加,渗透通量和截留率同时降低;随温度的升高,渗透通量上升,截留率降低。大豆油和己烷在膜中的传质特性可用不完全的溶解-扩散模型描述,溶液渗透压实验值与计算值符合较好。     

Mechanical and film formation behavior from PDMS/NaY zeolite composite membranes

In this study, polydimethylsiloxane (PDMS) and NaY zeolite doped composite membranes were prepared for the films varying from 0 to 15 NaY zeolite wt %. All the membranes were characterized by attenuated total reflectance–Fourier transform infrared (FTIR), X-ray diffraction, scanning electron microscopy, thermogravimetry/differential thermal analysis methods. The FTIR spectral results showed that there is physical interaction existing between the PDMS matrix and NaY zeolite. Additionally, film formation from the pure PDMS and PDMS/NaY composites were investigated by photon transmission technique. Activation energies corresponding to the void closure and the interdiffusion stages were calculated. The NaY zeolite added films led to the significant improvement in the mechanical properties that both the tensile strength and Young's modulus increased three times. Thermal properties of the films were also investigated and the addition of NaY zeolite into the PDMS matrix could significantly improve the thermal stability of the composite membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48549.     

4A沸石填充聚氨酯杂化膜的制备及气体分离性能

两步法制备了4A沸石填充的端羟基聚丁二烯基聚氨酯膜HTPB-PU/4A,并研究了CO2、H2、O2、N2的气体透过性能.结果表明:沸石与膜的相容性较好,添加4A沸石后,膜的热稳定性明显提高,O2渗透性及O2/N2选择性显著改善;随沸石添加时间的增加,膜对各种气体体系的选择性先增加后减小,而渗透性则先增加后趋于稳定;随硬...     

Modification of carbon membranes and preparation of carbon-zeolite composite membranes with zeolite growth

A novel method for the modification of carbon membranes was developed by zeolite growth on the surface of porous carbon tubes using a hydrothermal synthesis method and carbon-zeolite composite membranes were successfully obtained. Zeolite seeds for the zeolite growth were introduced to the inner surface of the tubes by using a slip-casting technique in 1 wt.% seed ethanol solution and continuous and highly intergrown zeolite layers on the seeded tubes were formed by subsequent hydrothermal synthesis. Different types of zeolite layers can be grown on porous carbon tubes by using different types of zeolite seeds. Without zeolite seeds, a zeolite layer could not be formed on the carbon surface. SEM, XRD and pure gas permeation characterization indicates that the carbon-zeolite membranes are continuous and defect-free.     

支撑层对硅橡胶复合膜渗透汽化分离性能的影响

引言 为了扩大渗透汽化技术的应用领域,科研工作者需要进一步增强渗透汽化膜的分离性能.从工业化的观点而言,用于实际应用的渗透汽化膜大多是复合膜,它由选择层(或分离层)和支撑层组成.一般认为,选择层决定着复合膜的选择性和通量,支撑层起支撑和机械稳定作用.Nijhuis[1]在从甲苯-水体系中分离甲苯的过程中对均质膜和以聚砜为支撑层的复合膜的分离性能进行了比较;Sturken[2]分别用聚醚酰亚胺和聚偏氟乙烯为支撑层的硅橡胶膜从二氯乙烷-水体系中提取二氯乙烷,他们得到了相同的结论:支撑层的影响可以忽略.然而Scholz[3],Heinzelmann[4],Rautenbach[5],Borges[6],Vankelecom[7],Farooq[8],Lipnizki[9]等均在各自研究中发现,由于基膜和分离层的物理化学性质以及制膜方法等众多因素的存在使得支撑层在一定程度上影响复合膜的分离性能;Feng[10]对均质硅橡胶膜和有微孔支撑层的硅橡胶复合膜的分离性能进行了比较,发现均质硅橡胶膜优先透过异丙醇,而有微孔亲水性支撑层的硅橡胶复合膜则优先透过水,这表明在一定的情况下,支撑层甚至起主导作用并能够决定复合膜的分离性能.因此,通过系统研究以不同多孔材料为支撑层的复合膜对有机物-水溶液的分离性能的影响,能够找到最优的复合膜支撑层,从而能够提高复合膜的分离性能.然而,至今关于支撑层对渗透汽化膜分离性能影响的系统研究仍相当少.     

无机盐对聚二甲基硅氧烷/陶瓷复合膜渗透汽化性能的影响

将渗透汽化应用于醇/水体系的分离,具有诸多显著的优势。然而,目前的研究大都基于二元体系,而实际的应用体系是多元的,还包含少量无机盐和糖类等,它们的存在对膜的性能具有一定的影响。本文研究了NaCl、KCl和MgCl2 3种无机盐的加入对聚二甲基硅氧烷 （PDMS）/陶瓷复合膜渗透汽化性能的影响。结果表明,在313 K,无机盐的加入使复合膜的分离因子和通量均有所提高。其中二价盐MgCl2对渗透汽化性能的影响最为显著,分离因子最大提高到醇/水体系的2.8倍。而一价盐NaCl和KCl的加入,使分离因子分别提高为醇/水体系的2.5倍和2.4倍。同时借助于Setschenow扩展方程计算了乙醇活度,对实验结果进行了初步的解释。     

Preparation of zeolite filled glassy polymer membranes

The incorporation of zeolite particles in the micrometer range into polymeric matrices was investigated as a way to improve the gas separation properties of the polymer materials used in the form of membranes. The adhesion between the polymer phase and the external surface of the particles appeared to be a major problem in the preparation of such membranes when the polymer is in the glassy state at room temperature. Various methods were investigated to improve the internal membrane structure, that is, surface modification of the zeolite external surface, preparation above the glass-transition temperature, and heat treatment. Improved structures were obtained as observed by scanning electron microscopy, but the influence on the gas separation properties was not in agreement with the observed structural improvements. © 1994 John Wiley & Sons, Inc.