交联聚乙烯醇渗透蒸发膜用于酯化反应过程

研究了交联聚乙烯渗透蒸发膜在酯化反应过程中的应用，以乙酸与正丁醇酯化反应为实验对象，通过渗透蒸发膜选择性地移走产物水，使最终反尖转化率超越平衡转化率，实验考察了温度，进料初始摩尔比，催化剂浓度对过程的影响。     

二元醇/水溶液在渗透蒸发均质膜中的扩散模型

用交联聚乙烯酸膜对不同浓度的乙二醇/水溶液在不同温度下分别进行了渗透蒸发实验研究．针对小分子在致密膜中的扩散行为提出了一个新见解,并借用改进的Vigne方程得到了一个新的热力学扩散系数方程,用此方程结合Lee-Thods方程、Wilke-Chang方程、Vrentas和Duda改进的自由体积理论、扩散方程和溶胀平衡方程预测了水和乙二醇分子在不同温度下通过交联聚乙烯醇膜的渗透蒸发行为,其预测结果与实验值基本一致．     

聚乙烯醇膜的研制及乙醇水溶液的渗透蒸发（PV）分离

选择以聚乙烯醇(PVA)作膜材料,制成具有一定通量及分离效果的聚乙烯醇均质膜及聚乙烯醇/聚砜复合膜。讨论了膜的抗水性及抗化学腐蚀性。用透射电镜及扫描电镜进行了结构测定,并研究了这两种膜在分离95%(重量浓度)乙醇水溶液时的性能以及温度、交联度对膜性能的影响。实验发现聚乙烯醇均质膜具有较高的分离系数;聚乙烯醇/聚砜复合膜在基本维持均质膜分离性能的前提下,通量有较大提高。还发现经Cr~(3 )的饱和溶液处理后再进一步交联的膜,交联度及稳定性都有提高,分离系数略有下降。     

石墨填充聚乙烯醇膜渗透蒸发分离苯和环己烷

采用液相共混法制备了石墨填充聚乙烯醇膜,采用FTIR,SEM,XRD等对石墨填充聚乙烯醇膜的物理和化学结构进行了分析表征,结果表明石墨与聚乙烯醇存在较强的氢键作用,石墨在聚乙烯醇中分散均匀,且具有一定的取向性.考察了石墨填充聚乙烯醇膜在苯和环己烷溶液中的溶胀和吸附行为.采用正电子湮没寿命谱仪表征了石墨聚乙烯醇膜的自由体积特性,计算得到石墨聚乙烯醇膜的表观自由体积分数,并且与渗透通量进行关联性对比.最后,研究了石墨含量和粒径对渗透蒸发分离性能的影响,结果表明,石墨的引入有利于苯的优先透过,石墨填充聚乙烯醇膜对苯和环己烷混合物具有良好的分离效果,苯的渗透通量和分离因子分别可达90.7 g•m^-2•h^-1和100.1.     

甲醛－水渗透蒸发膜分离

制备了乙烯共聚醋酸乙烯酯复合膜和聚酰亚胺均相致密膜，研究了这两种膜与全氟磺酸型离子交换膜的渗透蒸发分离性能。实验测得最大分离系数α＝２７４，并发现料液的甲醛浓度增加，膜的分离系数提高。     

聚乙烯醇/超支化聚酯交联渗透汽化膜的制备及其溶解扩散性能分析

将超支化聚酯（HBPE）与聚乙烯醇（PVA）共混交联制备了PVA/HBPE交联渗透汽化膜,研究了PVA/HBPE交联膜内的溶解扩散及渗透汽化性能。结果表明,随着温度的增加,水在交联膜内的渗透系数（Pwater）增加,且变化趋势与纯水通量一致,在55 ℃时达到最大值71.952 g/m2·h;随着HBPE含量的增加,渗透系数Pwater及纯水通量呈现增加的趋势,当HBPE含量为40 %时,纯水通量达到最大值185.726 g/m2·h。     

共混高分子膜渗透蒸发分离乙醇水溶液

应用湿法离子交联技术，研制了聚砜酰胺共混聚丙烯酸复合膜，针对乙醇水溶液，测定了膜的分离系数和渗透通量。实验发现，这种共混膜对乙醇－水具有较高的分离选择性。     

二元水溶液在渗透蒸发膜中的传质模型

对二元水溶液在渗透蒸发膜中的传质过程进行了研究,基于Flory Huggins高分子热力学理论和Fujita自由体积理论建立了改进的溶解 扩散模型。在该模型中考虑了组分间相互作用,组分体积分数、温度、膜材料和渗透物特性对传质过程的影响,考察了组分体积分数对相互作用参数的影响,膜材料对水的溶解选择性的影响,原料液组分体积分数、操作温度以及膜厚对渗透通量和分离因子的影响。     

有机混合物的渗透蒸发分离

有机混合物渗透蒸发分离技术在技术发展很快,膜的种类繁多,和化学性质差别很大,本文首先总结了分离有机混合物渗透蒸发膜的详细分类 及膜对应的分离物系,不同膜的物理性能和分离效果比较,在后对膜的多种改性方法作了较合面的论述。     

Pervaporation and Vapor Permeation Tutorial: Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

Pervaporation and vapor permeation are membrane-based processes proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol, or butanol recovery from fermentation broths, solvent/biofuel dehydration to meet dryness specifications, and organic-organic separations such as the removal of sulfur compounds from gasoline. Unlike membrane filtration processes, which rely on an applied liquid pressure gradient and size sieving to accomplish a separation, pervaporation and vapor permeation separate compounds based on a chemical activity driving force and the sorption and diffusion of the compounds through the membrane. These properties enable the separation of even miscible liquid mixtures.     

Effects of CNTs Content on Physicochemical and Pervaporation Separation Properties of PVA Membranes

In this study, the morphological and separation characteristics of PVA membranes incorporated with functionalized CNTs are reported. CNTs was extensively characterized using TGA, FESEM, and TEM. The physicochemical properties of PVA-CNTs membranes were characterized using FESEM, tensile test, DSC, and XRD. DSC measurements showed an increase in melting and glass transition temperature, implying enhancement of polymer chains compacting. XRD analysis confirmed the results of DSC and showed that CNTs can promote crystallinity of the PVA membranes. In addition, tensile measurements revealed that incorporating CNTs into the PVA membranes improves their mechanical properties. The synthesized nanocomposite membranes were then evaluated in pervaporation (PV) dehydration of isopropanol (IPA). The separation results showed that incorporating CNTs into the PVA membranes significantly increases water selectivity of the PVA membranes. This can be attributed to the fact that incorporating CNTs compacts and rigidifies PVA matrix and decreases its free volume. Furthermore, permeation of water molecules through the nanocomposite membranes decrease as a result of the polymer chains rigidification. Effects of feed composition and temperature on PVA-CNTs nanocomposite membranes were investigated. Besides, effects of CNTs content on permeation properties and activation energies of PVA membranes were evaluated.     

Maxwell-Stefan理论模拟NaA沸石膜分离一氯甲烷中微量水的渗透特性

通过热浸渍晶种法制备了高质量的NaA沸石膜,并将其应用于蒸汽渗透脱除一氯甲烷中的微量水. 实验结果表明,NaA膜对该体系显示了优异的分离性能,水对一氯甲烷的分离系数高达74831,产品中的水含量从0.2582%(w)降低到0.005%(w). 将基于Maxwell-Stenfan理论和Langmuir理想吸附理论推导的吸附-扩散模型用于模拟水渗透流速与渗透侧真空度和进料温度的关系,预测趋势与实验值吻合很好,且拟合得到的参数与文献报道较接近,表明水蒸汽在NaA沸石膜中的传递为表面扩散机制,水蒸汽的吸附对渗透速率的贡献很大. 水蒸汽的吸附热为-34.15 kJ/mol.     

渗透汽化分离DMF/水混合物的PVA-g-AAm膜的制备和表征

使用聚乙烯醇及丙烯酰胺这两种材料,合成了不同枝度的共聚物(PVA-g-AAm),并对两种渗透汽化复合膜(PVA-g-AAm)进行制备。黏均分子量是运用用黏度法测定的,而表征则分别由接触角,红外光谱(FT-IR)和热重(TGA)等方法进行测定。而DMF/水混合体系的渗透汽化分离主要是复合膜的运用,并对膜分离的影响因素进行分析。实验结果显示,分离性能最好的是接枝度为90%的PVA。而PVA的渗透量随着DMF质量分数的增加而减少,PVA的通量最小时是在0.25~0.65 kg/(m~2·h)之间,在0.2~而膜的分离因子达到最大时DMF质量分数为33%。而温度的增加可是渗透量增大,分离因子减小。     

分光光度法测定超滤膜分离聚乙二醇条件的研究

采用分光光度计法测定超滤膜对不同分子量聚乙二醇的截留效果。研究了不同分子量聚乙二醇的最大吸收波长,考察了显色剂用量、显色时间等因素对聚乙二醇溶液吸光度的影响,得到的优化测试条件为：碘用量为1.0 mL,BaCl2用量为1.2 mL,显色时间控制为10 min。该方法操作简单、稳定性好、准确度高,便于推广应用。     

Sorption and Permeation of Aqueous Alkyl Piperazines through Hydrophilic and Organophilic Membranes: A Transport Analysis

ABSTRACT

A detailed analysis of separation of N-methyl piperazine (NMP), N-ethyl pipera-zine (NEP), and water was undertaken by the pervaporation technique. A systematic study of sorption and permeation of the aqueous alkyl piperazines through poly(dimethylsiloxane) (PDMS), styrene-butadiene rubber (SBR), PDMS filled with zeolites NaX and silicalite (SA-5), polyimide (PI), and poly(acrylonitrile-co-acrylic acid) (PAN-co-AA) was carried out at different concentrations and temperatures. Organophilic membranes showed higher selectivity toward alkyl piperazines during sorption, but permeation was in favor of water. Hydrophilic membranes, however, showed higher affinity toward water during both sorption and permeation. PI membrane showed higher selectivity for water than PAN-co-AA. A model was used to estimate the diffusion coefficients of the various permeants. It was found that the transport selectivity for water in organophilic membranes was due to high diffusion selectivity (for water) although sorption selectivity favored the piperazines.     

中空纤维PVA/PAN复合膜填料的乙醇水溶液精馏性能

以乙醇/水溶液为分离对象,中空纤维PVA/PAN复合膜作为精馏填料,考察了不同膜组件的传质分离效率。实验结果表明:各种组件的分离效率均随塔釜加热功率的增加而减小;和大多数中空纤维膜接触器一样,其总传质系数Ky随中空纤维膜组件填充密度φ的增加而减少;相比于传统精馏填料而言,用中空纤维膜做精馏填料分离乙醇水溶液的分离效果更好,可以在常规填料不能操作的液泛线以上进行操作。当塔釜加热功率为120 W,45根中空纤维膜封装在内径为1.6 cm玻璃管中的传质单元高度(HTU)为5.64 cm。     

Pervaporative Dehydration of Binary Ethanol/Water and Ternary Ethanol/Water/Methanol Mixtures Using a Methylated Silica Membrane: A Mechanistic Approach

The pervaporation properties of a methylated-silica membrane were studied on binary ethanol/water and ternary ethanol/water/methanol mixtures. The aim was to acquire a better understanding of the pervaporation mechanisms by studying the effects of feed temperature, permeate pressure, and feed composition on molecular transport. Emphasis was placed on the role of competitive adsorption and dragging and blocking effects between the components in the context of the adsorption-diffusion model. The results show the potential of the membrane for the coupled removal of water and methanol from bioethanol. This attractive application for process intensification was suggested for the first time in this paper.     

Effect of Reaction and Permeation Rates on the Performance of a Catalytic Membrane Reactor for Methylcyclohexane Dehydrogenation

Abstract

The effect of the relative rates of reaction and H₂ permeation through palladium-silver (Pd-Ag) membranes upon the performance of a catalytic membrane reactor (CMR) for methylcyclohexane dehydrogenation has been investigated. Mathematical models have been used to identify the conditions at which a membrane reactor gives yields of toluene (TOL) and H₂ significantly in excess of equilibrium values at throughputs of industrial interest. The simulation shows that a catalyst with no product TOL inhibition performs exceptionally well in a CMR, giving conversions considerably above the equilibrium values at favorable operating conditions. Using a membrane unit between two conventional packed-bed reactors to separate the H₂ ex-situ gives significant improvement in performance over the shell-and-tube type CMR, resulting in conversions substantially higher than equilibrium at 633 K, 1.5 MPa, and liquid hourly space velocities of 3–10 volume feed/h/catalyst volumes.