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。     

壳聚糖／聚丙烯酸钠聚离子复合膜的醇－水渗透汽化分离性能

研究了壳聚糖－醋酸溶液与聚丙烯酸钠溶液形成的复合膜用于水－乙醇混合物的渗透汽化分离，在膜组成Ｃ＝０．８０时，分离系数出现最大值，对异丙醇－水体系的分离系数为∞。溶解－扩散过程对渗透汽化过程起着重大作用。由－ＮＨ＋３…ＯＯＣ－交联的聚离子复合膜对醇－水体系具有稳定的分离性能。     

利用膜分离技术回收正丁醇/水混合液的工艺研究

研究了聚乙烯醇（PVA）／聚丙烯腈（PAN）、海藻酸钠（SA）／PAN复合膜及海藻酸钠／醋酸纤维素（CA）共混膜等五种膜的渗透汽化特性,发现它们对正丁醇／水的混合液均表现为水优先透过,其渗透通量与选择分离系数都很高。并初步确定了正丁醇／水混合液渗透汽化分离的工业生产操作条件。     

壳聚糖／聚丙烯酸钠聚离子复合膜的醇—水渗透汽化分离性能

研究了壳聚糖－醋酸溶液与聚丙烯酸钠溶液形成的复合膜用于水－乙醇混合物的渗透汽化分离，在膜组成Ｃ＝０．８０时，分离系数出现最大值，对异丙醇－－水体系的分离系数为∞。溶解－扩散过程渗透汽化过程起着重大作用。由－ＮＨ３ＯＯＣ－交联的聚离子复合膜对醇０－水体系具有稳定的分离性能。     

甲醇/正己烷的渗透汽化分离的研究 Ⅰ.渗透汽化膜的研制

本文研制了从甲醇／正己烷体系中分离甲醇的渗透汽化复合膜ＣＡ／ＰＡＮ（ＰＥＳ）、ＰＶＡ／ＰＡＮ（ＰＥＳ）。实验证明膜对该体系有较高的选择分离性和良好的渗透性，当进料甲醇浓度为３％时，渗透通量Ｊ≈０．６００ｋｇ／ｈ·ｍ２，分离因子α→∝。本文还考察了不同操作条件对膜分离性能的影响及膜的稳定性和均匀性。     

甲醇／正己烷的渗透汽化分离的研究：I.渗透汽化膜的研制

本文研制了从甲醇／正己烷体系中分离甲醇的渗透汽化复合膜ＣＡ／ＰＡＮ（ＰＥＳ）、ＰＶＡ／ＰＡＮ（ＰＥＳ）。实验证明膜对该体系有较高的选择分离性和良好的渗透性，当进料甲醇浓度为３％时，渗透通量Ｊ≈０．６００ｋｇ／ｈ·ｍ＾２，分离因子α→∝。本文还考察了不同操作条件对膜分离性能的影响及膜的稳定性和均匀性。     

PDMS/陶瓷复合膜用于乙醇回收的中试研究

采用中试装置，测评商业化PDMS/陶瓷复合膜回收乙醇的分离性能，考察了进料流量、操作温度及进料液乙醇质量分数对乙醇分离性能的影响，其中，详细研究了进料液乙醇质量分数连续变化时，膜的分离因子和渗透侧乙醇质量分数及水通量等数据的变化趋势。结果表明：在测试范围内，进料流量对膜分离性能的影响不大；随着操作温度的增加或进料液乙醇质量分数的提高，渗透通量增加，渗透侧乙醇质量分数呈现出不同的变化趋势。进料液乙醇的质量分数从9.86%连续降至0.55%的过程中，乙醇/水分离因子逐步提高，乙醇通量逐步降低，水通量基本保持不变。     

PDMS/PEI膜渗透汽化分离正丁醇/乙醇/水的性能及渗透通量关联模型研究

采用聚二甲基硅氧烷/聚醚酰亚胺(PDMS/PEI)膜渗透汽化分离正丁醇/乙醇/水体系,考察进料温度、进料组成等条件对膜渗透汽化分离性能的影响;采用Arrhenius型半经验渗透通量关联模型描述PDMS-PEI膜分离正丁醇/乙醇/水体系膜通量变化。结果表明,当原料液中正丁醇质量分数分别为4.0%、4.5%和5.0%时,正丁醇/乙醇/水三元体系中正丁醇渗透通量分别至少提高14.2%、17.7%和23.4%。渗透通量关联模型能较好地描述PDMS-PEI膜分离正丁醇/乙醇/水体系膜渗透通量变化。     

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。     

壳聚糖渗透汽化膜分离醇／水的性能：Ⅱ.壳聚糖复合膜

用聚丙烯腈超滤膜为基膜制成的ＣＳ复合膜，对乙醇／水溶液的分离具有较稳定的透过性，复合膜先后运行于低浓度的乙醇溶液的９５ｗｔ％乙醇溶液，膜的稳定性能优于均质膜。实验还表明用多种交联剂代替硫酸处理超薄复合膜，可有效地提高膜的渗透选择性。     

Preparation of crosslinked alginate composite membrane for dehydration of ethanol–water mixtures

The purpose of this article was to develop new membranes with a high selectivity and permeation rate for separation of an alcohol/water system. Crosslinked alginate composite membranes were prepared by casting an aqueous solution of alginate and 1,6‐hexanediamine (HDM) onto a hydrolyzed microporous polyacrylonitrile (PAN) membrane. The influence of hydrolysis of the support membrane and crosslinking agent content in a dense layer on the selectivity and flux was studied and it was shown that both could improve the separation performance of the composite membrane greatly. The countercation of alginate coatings as a dense separating layer also influenced the separation properties of the membrane, which was better for K⁺ than for Na⁺. This novel composite membrane with K⁺ as a counterion has a high separation factor of 891 and a good permeation rate of 591 g m⁻² h⁻¹ for pervaporation of a 90 wt % ethanol aqueous solution at 70°C. At the same time, SEM micrographs showed that the pore structure of the PAN microporous membrane is changed by hydrolysis. The reason for the influence of the preparation conditions on the separation performance of the novel membrane is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3054–3061, 2000     

Pervaporation membranes based on imide‐containing poly(amic acid) and poly(phenylene oxide)

Three imide‐containing poly(amic acids) were synthesized and used for homogeneous and composite membrane preparation. The transport properties of composite membranes consisting of an imide‐containing poly(amic acid) top layer on an asymmetric porous poly(phenylene oxide) support were studied in the pervaporation of aqueous solutions of organic liquids (ethanol, isopropanol, acetone, and ethylacetate) and organic/organic mixtures (ethylacetate/ethanol, methanol/cyclohexane). For most of the aqueous/organic mixtures, the composite membranes exhibited dehydration properties. Dilute aqueous solutions of ethylacetate were an exception. In these solutions, the composite membranes exhibited organophilic properties, high permeability, and selectivity with respect to ethylacetate. In the pervaporation of methanol/cyclohexane mixtures, methanol was removed with very high selectivity. To account for specific features of pervaporation on the composite membranes, the sorption and transport properties of homogeneous membranes prepared from polymers comprising the composite membrane [imide‐containing poly(amic acids) and poly(phenylene oxide)] were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2361–2368, 2003     

Characteristics of permeation and separation of aqueous alcoholic solutions through a poly[bis(2,2,2-trifluoroethoxy)phosphazene] membrane by evapomeation and pervaporation

The characteristics of permeation and separation for aqueous solutions of methanol and ethanol through a poly[bis(2,2,2-trifluoroethoxy)phosphazene] (PBTFP) membrane were studied by pervaporation and evapomeation. In pervaporation technique, methanol was preferentially permeated in all of the feed solution compositions and ethanol was permeated in lower ethanol concentrations of the feed solution. Water was predominantly permeated from the feed solutions with higher ethanol concentration. In evapomeation technique, water was selectively permeated in both all of the feed vapor compositions for aqueous methanol and ethanol solutions. These different permselectivities depended on the feed composition and the membrane permeation technique and could be discussed by a difference in the mechanisms of permeation and separation. It was found that the permeation rate was influenced remarkably by the degree of swelling of the PBTFP membrane and the permselectivity for water of aqueous alcoholic solutions was enhanced by an increasing degree of swelling of the membrane. When the degree of swelling of the membrane with rising permeation temperature was small, both the permeation rate and permselectivity for alcohol in pervaporation and evapomeation increased with the permeation temperature. The above results are discussed considering the PBTFP membrane structure in evapomeation and pervaporation.     

Permeation and separation characteristics of alcohol–water mixtures through poly(dimethyl siloxane) membrane by pervaporation and evapomeation

Permeation and separation characteristics for aqueous alcoholic solutions such as methanol/water, ethanol/water and 1-propanol/water were studied using a poly(dimethyl siloxane) membrane by pervaporation and evapomeation. Poly(dimethyl siloxane) membrane preferentially permeated alcohol from aqueous alcoholic solutions in both methods. The concentration of alcohol in the permeate by evapomeation was higher than that by pervaporation. However, the permeation rate for the former method was smaller than that for the latter method. In evapomeation with a temperature difference between the feed solution and the membrane surroundings, when the temperature of the membrane surroundings was kept constant and the temperature of the feed solution was raised, both the permeation rate and the permselectivity for ethanol increased with increasing temperature of the feed solution. On the other hand, as the temperature of the feed solution was kept constant and the temperature of the membrane surroundings was changed, the permeation rate decreased, but the permselectivity for ethanol increased remarkably with dropping temperature in the membrane surrounding. Under permeation conditions of a feed solution of 40°C and a membrane surrounding temperature of ?30°C in evapomeation, an aqueous solution of 10 wt % ethanol in the feed was concentrated to about 90 wt % in the permeate. The permselectivity for alcohol was in the order of methanol <ethanol <1-propanol. The above permeation and separation characteristics are discussed from the viewpoint of the physicochemical properties of the poly(dimethyl siloxane) membrane and the permeating molecules.     

Characteristics of permeation and separation of aqueous alcoholic solutions with chitosan derivative membranes

Permeation and separation characteristics for the feed vapours from aqueous alcoholic solutions through chitosan derivative membranes such as chitosan acetate (GA-ChitoA), chitosan (GA-Chito), and carboxymethyl chitosan acetate (GA-CM-ChitoA) membrane crosslinked with glutaraldehyde were investigated by evapomeation. The GA-Chito and GA-CM-ChitoA membranes prepared from casting solutions containing an optimum amount of glutaraldehyde showed a high permeation rate and high water permselectivity for an azeotropic composition in an aqueous ethanol solution. The permselectivity for water through the GA-CM-ChitoA membrane in evapomeation was in the order of aqueous solutions of methanol < ethanol < 1-propanol. The effect of the chemical and physical structure of these hydrophilic membranes on the permeation and separation characteristics is discussed.     

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     

Pervaporation separation of binary and ternary mixtures with polydimethylsiloxane membranes

This study dealt with the separation of binary water–phenol and water–methanol mixtures and ternary water–phenol–methanol mixtures by pervaporation (PV) with polydimethylsiloxane (PDMS) membranes. The effects of the operating conditions (feed temperature, feed concentration, and feed flow rate) on the separation performance for binary mixtures were investigated. An increase in temperature or concentration increased the total permeation flux and decreased the organic separation factor. In other words, an increase in the temperature or feed organic concentration increased the water flux more significantly than the organic compound flux, which resulted in a separation factor reduction. Also, an increase in the feed flow rate increased the total flux and separation factor because the boundary layer effects diminished. The vapor–liquid equilibrium separation factor (α_VLE) and pervaporation separation factor (α_PV) values for the PDMS membrane were calculated, and this showed that α_PV for the water–phenol mixture was greater than α_VLE. This means that the membrane was highly efficient for the PV separation of phenol from dilute aqueous solutions relative to the separation of methanol. This was due to the fact that phenol has a higher solubility parameter than methanol in silicone membranes. To study the effect of a third component on membrane performance, PV experiments were also carried out with water–phenol–methanol mixtures. The results for total permeation flux and the phenol separation factor for PDMS membranes in contact with water–phenol–methanol ternary mixtures are similar to those in contact with water–phenol binary mixtures. The phenol separation factor of the membrane in contact with the ternary mixture was slightly lower than that in contact with the binary mixture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chemical modification of poly(substituted-acetylene). IV. Pervaporation of organic liquid/water mixture through poly(1-phenyl-1-propyne)/polydimethylsiloxane graft copolymer membrane

Poly(1-phenyl-1-propyne)/polydimethysiloxane (PPP/PDMS) graft copolymer membranes having various PDMS content were prepared by solvent casting method, and the permeation characteristics at pervaporation were examined upon the aqueous solutions containing organic liquids such as alcohols, acetone, dioxane, acetonitrile, pyridine, and DMF. At pervaporation of ethanol/water mixture, preferential permeation of ethanol was observed for all the copolymer membranes, although PPP membrane showed water permselectivity. The permselectivity of the copolymer membrane also depended on operation temperature, but was independent on the thickness of the membrane. Furthermore, an excellent permselectivity of organic liquids was observed at the pervaporation of several organic liquid/water mixtures except in the case of DMF/water mixture. Observed high selectivity is thought to be due to the depression of the membrane swelling and the high solubility of the liquids into the membrane.     

Vulcanized paper for separation of alcohol aqueous solutions by pervaporation

Paper membranes made from vulcanized cellulose were used for the pervaporation (PV) of aqueous solutions containing methanol, ethanol, and isopropanol. It was noted that the vulcanized cellulose paper membranes (VCPM) could effectively separate alcohol and water from the mixture solutions. To observe the effect of the separation of alcohol aqueous mixtures, the permeation behavior of water and alcohol was examined by means of the separation factor and the permeation flux. The values of the permeation flux in the ethanol/water mixtures were found to vary from 6.2 kg/m²h to 2.1 kg/m²h, as the concentration of ethanol increased from 8 to 87 wt %, and the separation factor (α) changed from α = 2.6 to 6.6, respectively. This showed that the VCPM enhanced the separation of water and alcohol. The highest value observed for the permeation flux was 11 kg/m²h at 87 wt % of methanol concentration and the separation factor at this condition was 4.1. It was shown also that an efficient separation was obtained in the isopropanol/water mixture with a separation factor of 16.6. The contact angles of alcohol/water droplets on the VCPM were measured as well as the wettability of the membrane. There was a tendency of decrease for the contact angle, as the alcohol concentration decreased. This suggested that the solvent wettability decreased in high alcohol concentrations. It was concluded that a high permeabilitty of water through the VCPM resulted in the separation of alcohols and water in the PV process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pervaporation properties of a three‐layer structure composite membrane

A novel composite membrane with a three‐layer structure has been prepared. The top layer is a thin dense film of chitosan crosslinked with glutaraldehyde, and the support layer is made of microporous polyacrylonitrile (PAN). Between the dense and the microporous layer, there is an intermolecular crosslinking layer. The performance data show that this is an excellent pervaporation membrane for alcohol dehydration and one‐stage separation is attainable for some alcohol/water mixtures such as ethanol/water and isopropanol/water systems, which has a good separation factor of 1410 and a good flux of 0.33 kg m⁻² h⁻¹ for the EtOH/H₂O mixture, and 5000 and 0.43 kg m⁻² h⁻¹ for the i‐PrOH/H₂O mixture using 90 wt % alcohol concentration at 70°C.Using 90 wt % methanol aqueous solution at 60°C, a flux of 0.17 kg m⁻² h⁻¹ and selectivity of 123 are also obtained. The structure and performance of the novel composite membrane varies with conditions of membrane preparation, such as hydrolysis degree of PAN membrane, content of crosslinking agent, and heat‐curing temperature. The results indicate that the separation factor and the permeation rate of this novel composite membrane increase with the increase of operating temperature. At the same time, the pervaporation properties can be adjusted by changing the structure of the top layer and the middle layer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 740–745, 2000