PDMS膜在ABE连续发酵中的渗透汽化性能研究

构建了膜生物反应器封闭循环ABE连续发酵系统,研究了系统中PDMS膜的渗透汽化性能.实验共进行2轮,第一轮进行274 h,采用发酵-渗透汽化间歇耦合的方式;第二轮进行312 h,前196 h采用发酵-渗透汽化连续耦合,之后实行间歇耦合.间歇耦合操作模式下,2轮的丁醇分离因子分别为11.00和12.94,总通量分别为711.07和579.98 g/(m2·h);连续耦合操作模式下,第二轮丁醇分离因子为5.54,总通量为555.80g/(m2·h).实验中膜性能稳定,分离性能良好,未出现膜堵塞和膜破损现象.     

Al2O3中空纤维的改性及原位合成ZIF-8膜

采用化学气相沉积的方法将石墨相氮化碳(GCN)沉积到Al₂O₃中空纤维表面进行改性,在改性后的载体上通过原位晶化制备连续ZIF-8膜。采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)和气体透过分离测试技术,考察了GCN负载温度、负载量和前体种类以及合成液中甲酸钠添加量的影响。研究发现,向Al₂O₃载体表面负载GCN的适宜温度为350℃,温度越高,载体表面GCN的碳与氮物质的量之比(C/N比)越高,N活性位点越少,越不利于ZIF-8膜的原位晶化。在相同的负载温度下,负载时间越长,GCN对Al₂O₃载体的覆盖程度(负载量)越高,负载量过少无法形成致密膜。与三聚氰胺相比,使用尿素作为化学气相沉积的前体,在相同负载条件下GCN负载量明显下降,最终无法形成致密膜。调控合成液中甲酸钠的含量,优化的合成液配方为Zn Cl₂、2-甲基咪唑(Hmim)、HCOONa与CH₃OH的物质的量之比为1:1....     

聚偏氟乙烯/聚二甲基硅氧烷渗透气化膜在丁醇分离中的应用

通过相转化法制备PVDF多孔支撑膜,在其上涂覆致密的PDMS分离层制备得到PVDF/PDMS复合膜,用于丁醇的分离纯化。以丁醇水溶液为原料液,流速为1.6 L·min-1,丁醇浓度为15 g·L-1,温度为37℃时,PVDF/PDMS复合膜的总通量为158.2 g·m-2·h-1,分离因子为17.3。向丁醇水溶液中按丁醇:丙酮:乙醇比例为6:3:1添加丙酮和乙醇模拟发酵液,PVDF/PDMS复合膜的总通量升高到189.5 g·m-2·h-1,分离因子降低到14.8。进一步考察了以丙酮-丁醇-乙醇(ABE)发酵液为原料液的渗透气化膜分离性能,发酵液中不存在菌体时,PVDF/PDMS复合膜的总通量和分离因子分别为120.2 g·m-2·h-1和19.7,而菌体存在时,复合膜的总通量和分离因子分别为122.1 g·m-2·h-1和16.7。与PDMS均质膜相比,PVDF/PDMS复合膜在丁醇分离过程中的分离性能有了显著的提升,具有潜在的应用价值。     

聚偏氟乙烯/聚二甲基硅氧烷渗透气化膜在丁醇分离中的应用

通过相转化法制备PVDF多孔支撑膜,在其上涂覆致密的PDMS分离层制备得到PVDF/PDMS复合膜,用于丁醇的分离纯化。以丁醇水溶液为原料液,流速为1.6 L·min^-1,丁醇浓度为15 g·L^-1,温度为37℃时, PVDF/PDMS复合膜的总通量为158.2 g·m^-2·h^-1,分离因子为17.3。向丁醇水溶液中按丁醇：丙酮：乙醇比例为6：3：1添加丙酮和乙醇模拟发酵液,PVDF/PDMS复合膜的总通量升高到189.5 g·m^-2·h^-1,分离因子降低到14.8。进一步考察了以丙酮-丁醇-乙醇（ABE）发酵液为原料液的渗透气化膜分离性能,发酵液中不存在菌体时,PVDF/PDMS复合膜的总通量和分离因子分别为120.2 g·m^-2·h^-1和19.7,而菌体存在时,复合膜的总通量和分离因子分别为122.1 g·m^-2·h^-1和16.7。与PDMS均质膜相比,PVDF/PDMS复合膜在丁醇分离过程中的分离性能有了显著的提升, 具有潜在的应用价值。     

纳米Al2O3粒子对PVDF中空纤维膜的改性研究

文章介绍了在聚偏氟乙烯铸膜液中添加了无机钠米Al2O3粒子,采用相转化法制备了Al2O3/PVDF复合中空纤维膜。使用电镜对膜的微观结构进行了分析,初步研究了无机粒子在膜孔形成的过程中所起的作用和机理。并且对膜的孔隙率、最大孔径、力学性能和截留率进行了分析。结果表明复合膜的性能与纯PVDF膜的相比有显著提高,最大孔径从0.75μm降至0.39μm,水通量和截留率分别从10.09 L/m2.h和19.12%提高到28.25 L/m2.h和71.00%,断裂应力从3.09 MPa提高到3.41 MPa。     

壳聚糖/聚砜复合中空纤维膜的制备及其CO2/N2分离性能研究

以壳聚糖(CS)为涂层材料,聚砜(PSf)为基膜材料,运用浸渍涂覆的方式制备了壳聚糖/聚砜复合中空纤维膜,考察了壳聚糖质量分数、涂覆时间以及操作温度和压力对CO2、N2的渗透分离性能的影响。结果显示,在聚砜基膜上涂覆壳聚糖材料后,可有效提高CO2/N2分离系数;CO2、N2的渗透速率符合Arrhenius关系式;CO2在复合中空纤维膜中的渗透由溶解-扩散和促进传递两方面主导,而N2的渗透符合溶解-扩散模型。     

乙醇/水及乙酸/水体系的渗透汽化分离

以乙醇/水及乙酸/水体系为研究对象,研究了渗透汽化过程中料液浓度、温度因素对分离效果的影响;结合乙醇、乙酸对聚二甲基硅氧烷(PDMS)膜的溶胀特性差别,分析并讨论了两者在渗透汽化过程中可能的分离机理. 研究表明,PDMS膜能够优先透醇,但乙酸分子的缔合物以及羧基与疏水PDMS膜高分子链的强相互作用降低了其在膜中的扩散速率,使低温时乙酸/水体系优先透水,只有当温度在60℃以上时才表现出优先透酸,且分离效果较差.     

响应面优化法在PDMS/PVDF膜制膜条件优化中的应用

用响应面优化法优化了乙烯基封端PDMS/PVDF渗透汽化透醇膜的制膜条件,研究了硅橡胶浓度、B/A质量比、交联温度和交联时间对膜性能的影响,拟合了分离因子、渗透通量与四因素之间的回归方程,并用方差分析法考察了四因素的主效应、二次效应以及相互作用效应对复合膜的分离因子与渗透通量的影响。研究发现,硅橡胶浓度对膜的分离因子与渗透通量的影响最为显著,交联时间对分离因子几乎没有影响。通过对回归方程的优化分析得知,在料液乙醇浓度为10%(wt),操作温度40℃条件下,当硅橡胶浓度为93%(wt),B/A质量比为0.08,交联温度为100℃,交联时间为13.83 h时,膜的综合分离性能达到最佳,此时分离因子与渗透通量预测值分别为9.47、77.57 g(m2 h)1,渗透侧乙醇浓度达到51.3%(wt)。回归方程的验证实验结果表明,回归方程的估计值与实验值较为吻合,可用于乙烯基封端的PDMS/PVDF复合膜的渗透汽化性能的预测与优化。     

PVDF-ZrO2复合中空纤维膜在乳化油废水中的应用

针对普通聚偏二氟乙烯(PVDF)中空纤维膜具有疏水性强、易污染的应用缺陷,在制备纳米粒子掺杂改性的PDVF-ZrO2复合中空纤维膜前期工作基础上,表征了其微观结构,并考察了其在油水体系中的分离效果。微观结构检测表明,随着ZrO2含量的增大,复合膜的断面微观结构完成由指状大孔向海绵状结构的转化。PDVF-ZrO2复合膜的接触角和牛血清蛋白(BSA)吸附实验结果显示其亲水性及抗污染性能均得到了提高。进一步考察了PDVF-ZrO2复合中空纤维渗透分离性能,ZrO2纳米粒子质量分数为0.3%时,显示了最佳的渗透性能。在乳化油废水处理过程中,在油质量浓度为1 g/L,操作压力为0.1MPa、搅拌强度为20 r/min条件下,通量为105 L/(m2.h),TOC去除率为95.4%,表明具有较好的废水处理效果。     

天然气脱CO2中空纤维膜接触器中试分离系统研制成功

近日,中科院大连化物所膜技术研究组与马来西亚石油公司(PETRONAS)共同研发的用于天然气脱CO2中空纤维膜接触器中试分离系统(MBC系统)研制成功。此系统设计压力6.6 MPa,运行压力5.7 MPa,可以把天然气中CO2含量降至1%以下。经PETRONAS代表现场测试鉴定,MBC系统制造流程符合PETRONAS标准,性能指标达到合同规定要求。日前已出厂发往马来西亚天然气处理厂工业试验现场。MBC合同签订以来,在袁权院士指导下,曹义鸣研究员带领团队克服研制时间短、国外膜达不到性能要求     

中空纤维渗透汽化膜分离研究现状与展望

本文综述了中空纤维渗透汽化膜分离的研究进展,包括中空纤维支撑膜的制备、复合膜的制备方法、中空纤维渗透汽化膜的工业应用和中空纤维渗透汽化膜传质特性等几个方面,对这个方面所存在的问题以及今后发展方向进行了展望.     

中空纤维渗透汽化复合膜及组件研究进展

中空纤维渗透汽化膜组件具有器件小型化及成本较低等方面的优势,其工业应用潜力巨大。本文介绍了中空纤维渗透汽化复合膜及组件的研究进展,阐述了膜材料、成膜方法以及组件结构参数等对组件渗透汽化性能的影响,并对中空纤维渗透汽化膜组件的中试研究进行了总结。通过组件放大及中试研究发现,中空纤维渗透汽化膜组件的装填密度、长度以及抽吸方式均会影响其下游侧的真空度,从而影响其渗透汽化性能。膜材料的分子设计、组件的结构参数优化以及耐溶剂耐高温封装将是中空纤维渗透汽化膜组件未来工业放大过程中的关键环节。     

Permeate pressure build-up in shellside-fed hollow fiber pervaporation membranes

Pervaporation of water, ethanol and isopropanol through polydimethylsiloxane hollow fiber membranes was studied, with emphasis on elucidating the significance of permeate pressure build-up inside the fibers when the shell-feed mode of operation was used. The differential form of the Hagen-Poiseuille equation was used to describe the permeate pressure profile, and the theoretical predictions of permeate productivity were confirmed by experimental data. A parametric analysis showed that the dimensions of the hollow fiber (inside and outside diameters, and length) significantly affected the overall pervaporation performance of a hollow fiber membrane module, and the fiber dimensions must be optimized in order to achieve high productivity.     

Pervaporative separation of butanol using a composite PDMS/PEI hollow fiber membrane

In the study, the separation and purification of butanol was carried out using the composite hollow fiber membrane having the active layer of polydimethylsiloxane (PDMS) on the macroporous support of polyetherimide (PEI). The pervaporation results with the initial butanol concentration showed a trade-off between flux and separation factor. However, both the flux and the separation factor increased as the operating temperature increased. The pervaporation results showed the butanol flux and the separation factor were higher than those of the reported results. In this study, butanol was concentrated by the pervaporation as a feasibility study for the biofuel applications.     

中空纤维式渗透汽化膜内流动的CFD模拟

采用计算流体动力学(CFD)数值模拟软件研究了入口速度和管径对中空纤维式渗透汽化膜内流动特征及分离性能的影响.结果表明,膜通道内压降和壁面剪切应力与入口速度呈正相关,与管径呈反相关;分离性能随着入口速度的增大,呈现先增大后减小的趋势;管径越小,分离性能越高.     

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 asymmetric chitosan hollow fiber membrane and its pervaporation performance for dimethyl carbonate/methanol mixtures

Chitosan hollow fiber membranes (CHFMs) were successfully fabricated by a phase inversion method. The CHFMs obtained by ethanol–hexane exchange drying displayed integrally skinned asymmetric morphologies by field‐emission scanning electron microscope observation. The CHFMs could be used for the pervaporation separation of dimethyl carbonate (DMC)/methanol mixtures. Swelling properties of the polymer material were investigated, and the effects of feed composition and operating temperature on the pervaporation separation performance of the CHFMs were evaluated. The relationship of permeation flux and temperature was in agreement with the Arrhenius equation. It was demonstrated that the integrally skinned asymmetric CHFMs exhibited an effective method for the separation of DMC/methanol azeotropic mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mass transfer simulation on pervaporation dehydration of ethanol through hollow fiber NaA zeolite membranes

A multi‐layer series‐resistance mass transfer model was developed to simulate mass transfer behaviors of water/ethanol mixture through hollow fiber NaA zeolite membranes. The mass transfer through zeolite layer was described by Maxwell‐Stefan mechanism based on adsorption and diffusion parameters obtained from molecular simulation. The mass transfer through asymmetric hollow fiber support was described by dusty gas model involving Knudsen diffusion and viscous flow. It was found that the sponge‐like layer of support besides of zeolite layer made an important contribution to overall membrane transfer resistance while the finger‐like layer had less effect. When permeate pressure shifted from 0.2 to 7.5 kPa, the mass transfer resistance contribution of sponge‐like layer varied from 27.1 to 17.8%. Effects of microstructure parameters of support on mass transfer through membrane were investigated extensively. Large pore size and thin thickness for sponge‐like layer of support were beneficial to improve water permeation flux. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2468–2478, 2016     

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。     

Second interfacial polymerization of thin-film composite hollow fibers with amine-cyclodextrins for pervaporation dehydration

High performance thin-film composite (TFC) hollow fiber membranes have been developed for pervaporation dehydration by second interfacial polymerization (SIP) modification with three kinds of amine-functionalized β-cyclodextrin (amine-CDs), which were synthesized by modifying β-CD with ammonia, ethylenediamine (EDA), and tris(2-aminoethyl)amine, respectively. The chemical properties of amine-CDs and SIP-modified TFC membranes were characterized by various techniques. The effects of amine-CD type and SIP parameters (pH or concentration of CD-EDA solution) were studied systematically to acquire the optimized selective layer of TFC membranes for ethanol dehydration. Among all SIP-modified TFC membranes, the one with SIP by 2 wt% CD-EDA aqueous solution (pH = 2) exhibited the most outstanding separation performance with a ultrahigh permeation flux (3,018.0 ± 12.0 g/m² hr) and permeate concentration (98.7 ± 0.2 wt% water) at 50°C (equivalent to separation factor of 415), contributed by the effectively incorporated CD with rich hydrophilic functional groups and intrinsic nanocavities facilitating the passage of water molecules.