偶联剂对纳米二氧化硅/PDMS复合膜渗透汽化性能影响的研究

用3种硅烷偶联剂3-氨丙基三乙氧基硅烷(AMES)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(MEMS)、十六烷基三甲氧基硅烷(HEMS)分别对纳米二氧化硅粒子进行改性,利用制备的改性粒子与PDMS制备了一系列平板复合渗透汽化分离膜,用于乙醇/水溶液分离.实验结果表明:复合膜的渗透汽化性能得到显著的提高.3种改性粒子在提高渗透通量方面:HEMS＞MEMS＞ AMES;在提高分离因子方面,MEMS与AMES对复合膜的影响十分接近,而HEMS远小于前两者.当MEMS改性二氧化硅的质量分数为4％时,在40℃质量分数为10％的乙醇/水溶液中,复合膜的分离因子达到最高值11.17,渗透通量为216.1g/(m2 ·h).     

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.     

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。     

三层结构PDMS/POS/PAN渗透汽化复合膜的制备及其分离性能

分别将四甲基二乙烯基二硅氧烷(DVTMS)和2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷(TMTV)与交联剂聚二甲基硅氧烷(PDMS)的B组分(B)聚合形成两种聚硅氧烷DB和TB,涂覆于聚丙烯腈(PAN)表面形成过渡层DB(TB)/PAN,涂覆PDMS分离层得3层结构的PDMS/DB(TB)/PAN渗透汽化复合膜,用于1%正丁醇水溶液的分离,表征了过渡层的结构,研究了硅氧烷/交联剂比和膜液中固形物含量对复合膜渗透汽化性能的影响.结果表明,在分离层和过渡层总厚度相同的情况下,涂覆DB和TB有效提高了膜的渗透汽化性能,最佳膜配方DVTMS:B=3:1(ω)及DB含量5%(ω)时,PDMS/DB/PAN膜的分离因子为40.96,渗透通量为628.40 g/(m2?h);TMTV:B=1:1(ω)及TB含量为3%(ω)时,PDMS/TB/PAN膜的分离因子为41.58,渗透通量为540.00 g/(m2?h).PDMS/DB/PAN膜和PDMS/TB/PAN膜的分离因子分别比相同分离层厚度的PDMS/PAN膜的分离因子提高8.5%和10.2%,渗透通量提高29.5%和11.3%.     

填充法改性PDMS膜及其对乙酸/水的渗透汽化分离性能

用CTAB-蒙脱石填充改性PDMS膜,运用XRD, SEM等手段表征了不同填充量的复合膜结构,证明有机柱撑蒙脱石与聚合物形成插层型复合物后,膜的热稳定性明显改善. 研究了填充膜对乙酸/水体系的渗透汽化分离性能,结果表明,随着温度的升高,渗透通量增大而分离因子降低,通量随填充量增加单调上升,分离因子随填充量增加先增大后降低,填充量为7.4(%, w)时达到最大值. 从膜的结构及其与组分的相互作用对填充膜中蒙脱石可能存在的渗透通道作用进行了探讨.     

PTFE-PDMS/PVDF复合膜制备及其渗透汽化性能

制备了以聚偏氟乙烯PVDF超滤膜为底膜的聚四氟乙烯PTFE超细粉体填充聚二甲基硅氧烷PDMS复合膜,并用于氯仿水溶液体系的渗透汽化。采用SEM和接触角分析研究了膜结构及表面性能。研究了PTFE:PDMS质量比、料液流速、料液浓度对渗透汽化性能的影响;采用串联阻力模型分析了渗透汽化氯仿水溶液的传质过程。研究表明,填充PTFE提高了PDMS膜渗透汽化性能;流量大于200 mL min 1时渗透汽化传质阻力主要由膜阻力控制;在流速低于200 mL min 1时,浓差极化产生的氯仿传质边界层阻力最大可达膜阻力的29倍。     

PTFE对PDMS复合膜在低浓度有机物水溶液中渗透汽化性能的影响

制备了聚四氟乙烯（PTFE）超细粉体填充聚二甲基硅氧烷（PDMS）复合膜,通过扫描电子显微镜、傅里叶变换红外光谱仪、热失重分析仪等测试仪器对复合膜进行了表征,利用低浓度有机物（乙醇、丙酮、正丙醇）水溶液体系进行渗透汽化,并由单组分溶解实验计算了有机物（乙醇、丙酮、正丙醇）在复合膜中的溶解度。结果表明,PTFE含量由0增加至10 %（质量分数,下同）时, 复合膜的表面积及热稳定性得到了提高,有机物乙醇、丙酮、正丙醇在复合膜中的溶解度分别由0.0923、0.1589和0.2691 g/g提高至0.0991、0.1678和0.2773 g/g;加入PTFE后提高了复合膜的渗透汽化性能。     

模拟的发酵液组分对聚二甲基硅氧烷/陶瓷复合膜渗透汽化性能的影响

对所制备的聚二甲基硅氧烷（PDMS）/陶瓷复合膜进行了渗透汽化性能表征。通过在乙醇-水混合体系中添加不同的模拟发酵液组分;如葡萄糖（多羟基醛）、甘油（多元醇）、丁二酸（有机酸）、KCl（无机盐）;考察了各组分对复合膜渗透汽化性能的影响。研究发现：在333 K下;在乙醇浓度为65 g·L-1的混合物中添加不同浓度的第三组分;有机添加物对膜的渗透汽化性能没有明显影响;而无机盐的加入使膜的分离因子稍有提高。所制备的PDMS/陶瓷复合膜;在上述渗透汽化过程中表现出良好的稳定性和对乙醇的优先选择性;渗透通量和分离因子（醇/水）分别在4.5～4.7 kg·m^-2·h^-1、8.3～10.3之间。     

渗透汽化汽油脱硫技术研究进展

随着环保法规的日益严格,世界各国对清洁汽油中硫含量做出了严格的规定,汽油的低硫化甚至无硫化已成为一种必然趋势,汽油的深度脱硫技术已成为各石油公司和相关研究者的研究热点。渗透汽化是一种新型高效的膜分离技术,其在汽油深度脱硫技术方面具有独特优势。介绍了渗透汽化汽油脱硫技术的基本原理、工艺特点及国内外有关研究进展情况。     

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。     

Hollow monocrystalline silicalite-1 hybrid membranes for efficient pervaporative desulfurization

Hollow monocrystalline silicalite-1 (HMS) nanoparticles were successfully synthesized and firstly incorporated into poly(ether-block-amide) (Pebax) to prepare hybrid membranes. The uniformly dispersed HMS in Pebax matrix interrupt the crystalline region and optimize the free volume property. The micropores on the HMS shell enhance the selectivity because of sieving effect, whereas the inner cavity benefits the rapid diffusion of penetrant and elevates the flux. When the content of HMS (200 nm) is 20 wt %, the hybrid membrane possesses a permeation flux of 20.63 kg/(m² h) and an enrichment factor of 6.11 (82% and 23% higher than that of Pebax membrane, respectively), which surpass the upper bound of the state-of-the-art reported polymeric membranes. Moreover, the hybrid membranes display the remarkable antiswelling and long-term operation stability. This is a step forward in fabricating the hybrid membranes with superior separation performance by incorporating porous fillers with hollow structure. © 2018 American Institute of Chemical Engineers AIChE J, 65: 196–206, 2019     

Calix[4]arene‐filled poly dimethylsiloxane (PDMS) membranes for the pervaporative removal of benzene from dilute aqueous solution

In this article, tert‐butylcalix [4]arene (CA)‐filled poly dimethylsiloxane (PDMS) membranes (CA‐f‐PDMS) were prepared for pervaporative removal of benzene from aqueous solution. In comparison with unfilled PDMS membrane, CA‐f‐PDMS membranes showed higher permselectivity towards benzene due to the inclusion interaction between benzene and CA. The separation factor increased from 3275 to 5604 when the CA content varies from 0 to 3 wt % in the PDMS membrane. On the other hand, the normalized permeation rate of benzene (NPR_b) decreased with the increase of the degree of crystallization of the membranes due to the crystallinity of CA. The membrane with 1 wt % CA content had the highest degree of crystallization and thus the lowest NPR_b, whereas the membrane with 3 wt % CA content was the opposite. Furthermore, the addition of CA increased the elastic modulus of membranes slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 90–100, 2006     

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.     

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     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

硅溶胶/PDMS渗透汽化膜的制备及分离水中正丁醇

基于乳液成膜技术,以硅溶胶为填充剂,制备了硅溶胶聚二甲基硅氧烷/PDMS杂化膜,用于分离水中正丁醇。对膜进行了FI-IR分析及形貌、热稳定性、接触角和力学性能表征;研究了硅溶胶的加入对膜渗透汽化性能的影响。结果表明,硅溶胶与PDMS基质结合良好,没有明显相界面,膜的渗透汽化性能明显提高。在料液质量分数为1%、操作温度为40℃时,随着膜中硅溶胶含量的增加,膜的分离选择性和对丁醇的渗透性均呈现先升高后下降的趋势;在硅溶胶含量为3.75%时,分离选择性高达9.03;在硅溶胶含量为7.5%时,膜对丁醇的渗透性高达2.9×10⁶Barrer。     

PDMS复合膜回收酯化反应废水中的异丁醇

乙酸与异丁醇酯化反应生产乙酸异丁酯,产生大量含异丁醇的废水,常规生化处理负荷重,浪费资源。采用PDMS复合膜分离回收酯化废水中的异丁醇,考察了异丁醇浓度对PDMS复合膜溶胀度及分离性能的影响,优化渗透汽化过程操作参数,研究了乙酸异丁酯对PDMS复合膜回收异丁醇效果的影响。结果表明,随着异丁醇浓度从1%增大到3%(质量),PDMS复合膜溶胀度先增大后趋于平稳,异丁醇的渗透通量呈增大趋势,分离因子保持在15左右;操作温度从30℃升至60℃时,渗透通量增大,异丁醇的分离因子下降,总表观活化能为33.87kJ/mol;流速增加,Reynolds数增大,异丁醇渗透通量变化不大,但分离因子略有增大;微量乙酸异丁酯的存在可促进渗透汽化膜回收异丁醇。采用PDMS复合膜分离酯化废水中的异丁醇,回收率大于94.0%,渗余液中异丁醇浓度可降至0.1%(质量)左右。研究结果可为PDMS复合膜处理低浓度有机溶剂废水提供依据。     

Recovery of isobutanol from esterified wastewater by PDMS composite membrane

The esterification reaction of acetic acid and isobutanol produces isobutyl acetate, which generates a large amount of wastewater containing isobutanol. The conventional biochemical treatment is heavy and wastes resources. The effects of isobutanol concentration on the swelling degree and separation performance of polydimethylsiloxane (PDMS) membrane, the operating parameters of the pervaporation process and the effect of isobutyl acetate on the recovery of isobutanol by PDMS membrane were studied. The results show that with the isobutanol concentration increases from 1%(mass) to 3%(mass), the swelling degree of the PDMS membrane increases first and then stabilizes, the flux of isobutanol increases, and the separation factor is about 15. When the operating temperature increases from 30℃ to 60℃, the flux increases, the separation factor of isobutanol decreases, and the total apparent activation energy is 33.87 kJ/mol. With increase of the flow rate, the isobutanol flux is stability while the separation factor increases slightly. The trace amounts of isobutyl acetate can promote the recovery of isobutanol by the membrane. The recovery rate of isobutanol by PDMS membrane is greater than 94.0%, and the concentration of isobutanol in the retentate can be reduced to 0.1%(mass). The research results can provide a basis for PDMS composite membrane to treat low-concentration organic solvent wastewater.