海藻酸钠渗透汽化分离膜的研究进展及展望

在简述海藻酸钠(sodium aleinate,NaAI或SA)结构和渗透汽化原理的基础上,综述了海藻酸钠为基材的渗透汽化膜在醇类脱水、有机溶剂脱水、乙酸脱水方面的应用,并分析了操作参数对渗透汽化过程的影响.对其今后的发展方向进行了评述.     

渗透汽化有机-无机杂化膜研究进展

近年来,有机-无机杂化膜的研究受到了广泛关注,随着有机-无机杂化膜制备方法的多样化和分离性能的提高,其研究前景也越来越广阔.该文首先分析了有机-无机杂化膜相比于普通无机膜和有机膜在结构和性能上存在的优势,其次综述了有机-无机杂化膜的制备方法以及其在醇类、有机酸等有机溶剂或有机混合物中的分离提纯应用,重点讨论了其在渗透汽...     

用于渗透汽化的有机—无机杂化膜研究进展

近年来,有机-无机杂化膜的研究受到学术界广泛关注,随着有机-无机杂化膜制备方法的多样化和分离性能的提高,其研究前景也越来越广阔。该文首先分析了有机-无机杂化膜相比于普通无机膜和有机膜在结构和性能上存在的优势,其次综述了有机-无机杂化膜的制备方法以及其在醇类、有机酸等有机溶剂或有机混合物中的分离提纯应用,重点讨论了其在渗透汽化中的应用。最后,对有机-无机杂化膜的研究前景进行展望。未来有机-无机杂化膜的研究应借助于新的计算工具,侧重于材料的选择或制备方法的改进,如探索具有多功能化学基团和具有明确层次结构的多孔填料的聚合物材料等,使有机-无机杂化膜具有更加广阔的应用前景。     

有机硅烷改性PDMS/Silicalite渗透汽化杂化膜制备及其分离性能

采用硅烷偶联剂对全硅沸石Silicalite-1进行表面改性,以聚二甲基硅氧烷(PDMS)为基体,制备了渗透汽化PDMS/Silicalite杂化膜. 用FT-IR, TGA等对改性的效果和杂化膜的热稳定性能进行了表征,并以低浓度乙醇/水体系为研究对象,以渗透通量和分离因子为评价指标,考察了料液组成、进料温度、循环流速、膜下游侧真空度等因素对改性杂化膜分离性能的影响. 结果表明,硅烷改性沸石所制杂化膜对低浓度乙醇/水体系的分离因子比空白膜和未改性杂化膜分别提高136%和45%. 随料液中乙醇浓度从5%增加到69%,膜分离因子从22降低到7,而其他因素对膜的选择性影响较小.     

有机/无机杂化渗透汽化优先透醇膜研究进展

渗透汽化优先透醇膜分离技术可有效解决燃料乙醇和丁醇生产中发酵产率较低的瓶颈问题,受到广泛关注。膜材料的选择与改性以及膜结构的构建是提高透醇性能的关键。有机/无机杂化膜可以实现有机和无机材料的优势互补,被认为是未来分离膜领域最重要的发展方向之一。本文扼要回顾了用于优先透醇渗透汽化分离的有机无机杂化材料,结合本文作者课题组的研究工作,重点阐述了杂化粒子的结构、粒径、界面相容性、纳微分散、负载量等因素对渗透汽化传递过程的作用机制,进一步对近年来发展的成膜新方法进行了总结。在此基础上,提出今后有机/无机杂化渗透汽化优先透醇膜研究的主要方向是发展新型纳米级、超疏水并与有机聚合物具有高度界面相容性的无机粒子,以及构建高负载量的纳微结构与超亲醇表面。     

无机杂化海藻酸钠渗透汽化膜的制备与分离性能对比

为提高海藻酸钠(SA)膜的渗透汽化分离性能,分别采用纳米氧化铝、纳米氧化锆和纳米氧化钛对SA膜进行改性,对比分析了3种不同杂化膜渗透汽化分离性能的差异,并将分离性能较好的杂化膜应用到乙酸与乙醇酯化反应脱水的体系中。系统考察了无机纳米粒子含量对SA膜渗透汽化分离性能的影响,对杂化膜进行了接触角、傅里叶红外(FTIR)、扫描电子显微镜(SEM)、热重/差示扫描量热(TG/DSC)、X射线衍射(XRD)和拉伸强度等表征与分析。结果表明,无机纳米粒子能提高SA膜的热稳定性、机械强度和渗透通量,当无机纳米粒子与SA质量比为0.3时,掺杂TiO_2、ZrO_2和Al_2O_3的杂化膜二碘甲烷的接触角依次升高,同时渗透通量也依次升高。SA-0.3Al_2O_3杂化膜亲水性较好,然而SA-0.3ZrO_2杂化膜分离性能最优,50℃下分离水含量10%的乙醇-水溶液,膜渗透通量达到336 g·m~(-2)·h~(-1),渗透侧水含量99.97%,分离因子29990。酯化反应脱水实验表明,在80℃时,酯化反应脱水实验乙酸转化率均高于无脱水实验乙酸转化率,平衡转化率不断被打破,反应12 h后,转化率由平衡时的79.3%提高到93.9%。     

功能化PVI/MOR杂化膜的制备及乙酸脱水分离性能

通过自由基接枝聚合的方法将1-乙烯基咪唑单体接枝到MOR沸石膜的表面,制备出一种新型的亲水性的聚(1-乙烯基咪唑)/丝光沸石(PVI/MOR)杂化膜.并通过扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶红外漫反射光谱(DRIFTS)和热重分析等来表征膜的形貌和特性.将膜应用于乙酸脱水分离,考察了不同Ⅵ单体浓度和进料浓度对膜的渗透汽化性能的影响.分析得知以15%的Ⅵ单体浓度制备的PVI/MOR杂化膜具有最好的分离性能,在80℃下和71%～94%的进料浓度范围内均达到理想选择性分离,也就是说在透过侧产品水的含量达到100%.这些实验结果表明将PVI基团接枝到MOR沸石膜层能实现真正意义上的功能化修补膜的缺陷和大大提高膜的分离性能的目的.     

高亲水性海藻酸钠膜渗透汽化分离甲醇水溶液

在海藻酸钠基质中引入磷钨酸颗粒,制备了一种高亲水性渗透汽化杂化膜。由热失重等分析手段对膜进行了表征,并在不同温度下（30～60 ℃）通过分离80%～95%的甲醇水溶液,测试了杂化膜的渗透汽化性能,实验结果表明：添加了磷钨酸的杂化膜,其分离性能显著高于纯海藻酸钠膜,当磷钨酸含量为6%时,30 ℃下分离水含量5%的溶液,膜通量达到318.2 g/(m2?h),分离因子达到656.9,分别是纯海藻酸钠膜的3.7倍和26.3倍。利用阿累尼乌斯关系式考察了膜通量与温度之间的关系,发现溶液通过膜的活化能随着磷钨酸含量的增加而降低。表明,磷钨酸的加入使得渗透物在杂化膜内更容易透过。     

木质素磺酸钙/海藻酸钠渗透汽化膜的制备及性能调控

当前石化资源遇到储量有限、利用过程对环境不友好等挑战,生物质燃料乙醇作为一种替代性能源崭露头角。渗透汽化是一种分离乙醇的方式,节能、环保,开发天然高选择性渗透汽化膜成为研究热点之一。本文提出利用木质素磺酸钙（CaLS）的亲水性和成膜性,将其与天然多糖海藻酸钠（SA）进行共混,制备了不同CaLS含量的CaLS/SA交联膜。采用傅里叶红外、X射线衍射、接触角和扫描电子显微镜等方法对交联膜进行了表征和分析。结果表明,CaLS能与SA充分均匀混合,并且CaLS的加入能提高SA膜的亲水性。进一步考察了CaLS添加量和操作温度对10%水含量的乙醇溶液分离性能的影响,当CaLS/SA质量比为5%时,CaLS/SA交联膜分离因子达到2872,渗透通量达到796g/(m² · h),较纯SA膜分别提高了160%和70%,证实了CaLS在膜分离领域的应用潜力。     

Silicalite-1/PAAS杂化膜的二甲苯异构体渗透汽化分离研究

Silicalite-1经3-氨丙基-三乙氧基硅烷(APTES)改性后,通过共混制备silicalite-l/聚丙烯酸钠(PAAS)杂化膜,用于二甲苯异构体的渗透汽化分离.膜的SEM分析表明,改性后silicalite-1与PAAS之间的相容性有较大改善.溶胀和渗透汽化实验发现:(1)对、邻二甲苯在杂化膜中的平衡溶胀量...     

Activated charcoal‐loaded composite membranes of sodium alginate in pervaporation separation of water‐organic azeotropes

Composite membranes of sodium alginate prepared by incorporating nanosized‐activated charcoal particles were prepared and characterized for the extent of cross‐linking, thermal stability, and mechanical strength properties using Fourier transform infrared, differential scanning calorimetry, and universal testing machine, respectively. The membranes were tested for pervaporation (PV) dehydration of isopropanol (IPA), ethanol (EtOH), 1,4‐dioxane (1,4‐D), and tetrahydrofuran (THF) at their azeotropic compositions. Improved PV performances of the composite membranes were observed compared with plain sodium alginate membrane for all the azeotropes. Sorption was studied to evaluate the extent of interactions between liquids and membranes as well as degree of swelling of the membranes in the chosen aqueous‐organic mixtures. Adding different amounts of activated charcoal into NaAlg offered high water selectivity values of 99.7, 99.1, 99.4, and 99.41%, respectively, for IPA, THF, 1,4‐D, and EtOH. Arrhenius activation parameters were computed from the temperature versus flux plots, which showed systematic trends for different liquids that depended upon their interactions with membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of sodium alginate membrane crosslinked with glutaraldehyde in pervaporation separation

Dense sodium alginate (SA) membranes crosslinked with glutaraldehyde (GA) have been prepared by the solution method, wherein a nonsolvent of SA (acetone) was used in a reaction solution instead of an aqueous salt solution. Through infrared radation, X-ray diffractometry, and the swelling measurement, the crosslinking reaction between the hydroxyl groups of SA and the aldehyde groups of GA was characterized. To investigate the selective sorption behavior of the crosslinked SA membranes, swelling measurements of the membranes in ethanol-water mixtures of 70–90 wt % ethanol contents were conducted by equipment that was able to measure precisely the concentration and amount of the liquid absorbed in the membranes. It was observed that the crosslinking could reduce both the solubility of water in the resulting membrane and the permselectivity of the membrane toward water at the expense of membrane stability against water. The pervaporation separation of a ethanol-water mixture was conducted with the membranes prepared at different GA contents in the reaction solution. When the membrane was prepared at a higher GA content, both flux and separation factor to water were found to be reduced, thus resulting from the more crosslinking structure in it. The pervaporation separations of ethanol-water mixtures were also performed at different feed compositions and temperatures ranging from 40 to 80°C. A decline in the pervaporative performance was observed due to the relaxation of polymeric chains taking place during pervaporation, depending on operating temperature and feed composition. The relaxational phenomena were also elucidated through an analysis on experimental data of the membrane performance measured by repeating the operation in the given temperature range. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 209–219, 1998     

Characterization of sodium alginate and poly(vinyl alcohol) blend membranes in pervaporation separation

By blending a rigid polymer, sodium alginate (SA), and a flexible polymer, poly(vinyl alcohol) (PVA), SA/PVA blend membranes were prepared for the pervaporation separation of ethanol–water mixtures. The rigid SA membrane showed a serious decline in flux and a increase in separation factor due to the relaxation of polymeric chains, whereas the flexible PVA membrane kept consistent membrane performance during pervaporation. Compared with the nascent SA membrane, all of the blend membranes prepared could have an enhanced membrane mobility by which the relaxation during pervaporation operation could be reduced. From the pervaporation separation of the ethanol–water mixtures along with the temperature range of 50–80°C, the effects of operating temperature and PVA content in membrane were investigated on membrane performance, as well as the extent of the relaxation. The morphology of the blend membrane was observed with PVA content by a scanning electron microscopy. The relaxational phenomena during pervaporation were also elucidated through an analysis on experimental data of membrane performance measured by repeating the operation in the given temperature range. SA/PVA blend membrane with 10 wt % of PVA content was crosslinked with glutaraldehyde to enhance membrane stability in water, and the result of pervaporation separation of an ethanol–water mixture through the membrane was discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:949–959, 1998     

Novel sodium alginate/polyethyleneimine polyion complex membranes for pervaporation dehydration at the azeotropic composition of various alcohols

Dense polyion complex membranes of anionic sodium alginate (NaAlg) and cationic polyethyleneimine (PEI) were prepareand crosslinked with glutaraldehyde for dehydration of alcohol–water mixtures by pervaporation (PV). The membranes were characterized by ion‐exchange capacity measurement, Fourier transform infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy to investigate the extent of cross‐linking, intermolecular interactions, thermal stability, and surface and cross‐sectional morphologies, respectively. Wide‐angle X‐ray diffraction was used to investigate the crystallinity of the membranes. PV dehydration characteristics of the membranes were determined as a function of PEI content, crosslinking time as well as feed water composition. Transport parameters such as sorption, diffusion and permeability of water and alcohols through the membranes were determined. Among the four different membrane compositions, the polyion complex containing 40% PEI was found to yield optimum separation data in terms of membrane stability, selectivity and permeability. On the other hand, 10% PEI‐containing membrane gave the highest selectivity with the lowest flux at ambient temperature, but the membranes were not sufficiently stable. Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of polyacrylamide‐grafted sodium alginate copolymeric membranes and their use in pervaporation separation of water and tetrahydrofuran mixtures

Polyacrylamide‐grafted sodium alginate (PAAm‐g‐Na‐Alg) copolymeric membranes have been prepared, characterized, and used in the pervaporation separation of 10–80 mass % water‐containing tetrahydrofuran mixtures. Totally three membranes were prepared: (1) neat Na‐Alg with 10 mass % of polyethylene glycol (PEG) and 5 mass % of polyvinyl alcohol (PVA), (2) 46 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA, and (3) 93 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA. Using the transport data, important parameters like permeation flux, selectivity, pervaporation separation index, swelling index, and diffusion coefficient have been calculated at 30°C. Diffusion coefficients were also calculated from sorption gravimetric data of water–tetrahydrofuran mixtures using Fick's equation. Arrhenius activation parameters for the transport processes were calculated for 10 mass % of water in the feed mixture using flux and diffusion data obtained at 30, 35, and 40°C. The separation selectivity of the membranes ranged between 216 and 591. The highest permeation flux of 0.677 kg/m² h was observed for 93% grafted membrane at 80 mass % of water in the feed mixture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 272–281, 2002     

Ultrasonic treatment of polyacrylic acid sodium/NaA zeolite hybrid membranes for the pervaporation dehydration of ethanol

Ultrasonics was used to improve the dispersion of NaA zeolite in polyacrylic acid sodium (PAAS) membranes. The effect of ultrasonication time on the dispersion of NaA zeolite in the membranes, the membrane structure, and performance were investigated. The casting solution and resulting membranes were characterized by viscosity measurement, polarizing optical microscopy (POM), scanning electron microscopy, and X‐ray diffraction (XRD). With increasing ultrasonication time, the viscosity of the casting solution decreased as the chain entanglements decreased. The POM and XRD results showed that crystallization occurred in the PAAS membrane after ultrasonic processing. A more homogeneous morphology was obtained due to improvement in the dispersion of zeolite under ultrasonic treatment for 0.5–1.0 h. As a result, the separation performance was enhanced. The water/ethanol separation factor increased from 176.2 to 577.8. However, the relative separation factor decreased when the ultrasonic time exceeded 2.5 h, due to the appearance of a lamellar structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3979–3984, 2013     

Synthesis and characterization of polyacrylamidegrafted sodium alginate membranes for pervaporation separation of water + isopropanol mixtures

Polyacrylamide‐grafted‐sodium alginate copolymers were prepared by persulfate‐induced radical polymerization by using polymer‐to‐monomer ratios of 2 : 1 and 1 : 1. Polymers were characterized by Fourier transform infrared spectroscopy, differential thermal analysis, and viscosity. Membranes were prepared from the polymers, crosslinked with glutaraldehyde, and used in the pervaporation separation of water + isopropanol mixtures at 30°C. Equilibrium swelling experiments were performed for mixtures containing 10 to 80 mass % of water in the feed. Both the grafted copolymer membranes were ruptured while separating 10 mass % of water in the feed mixture. However, beyond 20 mass % of water in the feed mixture, flux increased with increasing grafting ratio, while selectivity decreased. Pervaporation separation experiments were carried out at 30, 40, and 50°C for 20 mass % of water in the feed mixture. By increasing the temperature, flux increased, whereas selectivity decreased. Arrhenius activation parameters for pervaporation and diffusion decreased with increasing grafting ratio of the membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2030–2037, 2004