全硅沸石/聚二甲基硅氧烷渗透汽化膜制备及分离性能

考察了全硅沸石/聚二甲基硅氧烷(PDMS)渗透汽化均质膜制膜液中国液比(质量比)对渗透汽化膜性能的影响,利用均匀设计优化方法对交联时间、交联温度、全硅沸石填充鼍和PDMS中b胶量等对膜分离因子的影响进行了研究,制备了对丁醇分离性能较高的渗透汽化均质膜.50℃下,分离原料液质量分数为1.6%的丙酮-丁醇-乙醇-水溶液时,...     

硅橡胶渗透汽化复合膜在丁醇发酵中的应用

丁醇发酵受产物丁醇的抑制,产率和产物浓度低,过程经济性差,为减轻丁醇的抑制,制备了聚二甲基硅氧烷/聚偏氟乙烯(PIMS/PVDF)复合膜用于丙酮-丁醇-乙醇-水体系有机成分的分离.以分离因子和渗透通量为评价指标,考察了料液温度、质量分数和pH值对复合膜渗透汽化分离性能的影响.结果表明:料液温度升高能提高膜的分离性能;料...     

细菌纤维素膜渗透汽化分离二元有机物水溶液

采用动静结合的方式制备出了细菌纤维素膜。以乙醇水溶液、丙酮水溶液、乙酸水溶液为研究对象,研究了渗细菌纤维素膜的吸附性能,并讨论了透汽化过程中原料液浓度、温度对分离效果的影响及渗透汽化过程中可能的分离机理。结果表明,细菌纤维素膜能够优先透水,在渗透汽化分离乙醇和丙酮时,渗透通量随浓度的上升呈下降的趋势,温度对渗透通量的影响基本符合Arrhenius方程渗透汽化分离二者时,分离因子随浓度的增加先增加后减小。渗透汽化分离乙酸时,渗透通量随浓度的上升呈先上升后下降的趋势,分离因子变化不明显,温度对渗透通量的影响偏离Arrhenius方程较明显。     

细菌纤维素膜渗透汽化分离二元有机物水溶液

采用动静结合的方式制备出了细菌纤维素膜。以乙醇水溶液、丙酮水溶液、乙酸水溶液为研究对象,研究了渗细菌纤维素膜的吸附性能,并讨论了透汽化过程中原料液浓度、温度对分离效果的影响及渗透汽化过程中可能的分离机理。结果表明,细菌纤维素膜能够优先透水,在渗透汽化分离乙醇和丙酮时,渗透通量随浓度的上升呈下降的趋势,温度对渗透通量的影响基本符合Arrhenius方程渗透汽化分离二者时,分离因子随浓度的增加先增加后减小。渗透汽化分离乙酸时,渗透通量随浓度的上升呈先上升后下降的趋势,分离因子变化不明显,温度对渗透通量的影响偏离Arrhenius方程较明显。     

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。     

丙酮-丁醇发酵分离耦合技术的研究进展

介绍了近年来采用吸附、气提、液液萃取和渗透汽化从丙酮-丁醇发酵体系中分离丙酮,丁醇、乙醇的研究进展及最新的应用动态,评述了上述几种方法在分离丙酮.丁醇发酵产物(丙酮、丁醇、乙醇等)方面的优点和不足,并对各类方法做了比较,最后对丙酮.丁醇发酵分离耦合的发展方向进行了展望.     

玉米醇溶蛋白导向合成b轴取向Silicalite-1担载膜

采用旋涂工艺在多孔氧化铝(α-Al2O3)基片上制备玉米醇溶蛋白(zein)膜,以预涂zein膜的Al2O3基材为载体,通过原位水热法合成了silicalite-1担载膜。结果表明:以zein膜为模板可有效导向合成优先b轴取向silicalite-1晶体,所制备silicalite-1膜层表面平整且连续性好。而在未涂覆zein膜的Al2O3基材上所合成的silicalite-1晶体呈随机取向,表面缺陷较大,需多次重复水热合成制备。渗透蒸发实验中选择有机溶剂含量为3%(质量分数)的乙醇/水和丙酮/水二元体系,考察料液温度在25~40℃范围内优先b轴取向silicalite-1担载膜对有机组分的筛分浓缩能力。实验表明,对乙醇和丙酮两组分的分离因子大小顺序为乙醇、丙酮,渗透通量的大小则刚好相反。     

渗透汽化法从丙酮-丁醇-乙醇中分离浓缩丁醇

发酵法生产丁醇的产物质量浓度很低,为了实现丁醇的高效分离浓缩,文中采用渗透汽化膜分离技术对模型发酵液(丙酮、丁醇、乙醇混合溶液,ABE)进行浓缩实验。结果表明:随着温度、真空度、错流速度、料液质量浓度的增大,丁醇通量上升;渗透汽化膜对丁醇选择性在温度50℃时最佳,并随真空度的减小而减小,随料液质量浓度的增大而降低。实验证明,渗透汽化法能实现丁醇的高效分离浓缩,并且利用串联阻力溶解扩散模型可较好地预测ABE溶液体系中各组分的传质和分离效果。     

PDMS涂覆的Al2O3中空纤维膜在ABE/水体系分离中的应用

通过浸渍-提拉的方法制备了PDMS涂覆的Al2O3中空纤维膜,并系统地研究了其用于ABE/水体系的分离过程。首先对制备出的膜进行了形貌表征,SEM电镜照片表明,所用的Al2O3中空纤维支撑体具有非对称结构,海绵孔位于膜壁的中间而指状孔在其两侧。制备出的PDMS涂覆的Al2O3中空纤维复合膜表面致密完好没有缺陷,其厚度小于10μm,说明PDMS层被均匀地涂在支撑体外表面。然后在不同的模拟体系(丙酮-水、丁醇-水、乙醇-水)中,系统地考察了复合膜的性能。实验表明,复合膜具有优异的渗透汽化性能(通量和分离因子)。最后将该复合膜用于ABE-水体系的分离,考察了膜在操作过程中的渗透汽化性能和稳定性,同时将二元体系与四元体系过程对比,讨论渗透汽化对ABE体系的分离作用。     

羧甲基壳聚糖-聚乙烯醇渗透汽化膜分离乙醇-水的性能

本文制备了羧甲基壳聚糖-聚乙烯醇渗透汽化膜,研究了羧甲基壳聚糖和聚乙烯醇配比、戊二醛交联时间以及操作温度和乙醇浓度等因素对膜分离乙醇-水性能的影响。实验结果表明,当乙醇含量较低（10（wt）%）时,该膜优先透醇,羧甲基壳聚糖与聚乙烯醇的比例1∶1时,膜的分离因子达到最大16.45（wt）%的乙醇溶液）;随着戊二醛交联时间的增加,膜的渗透通量减小而分离因子增大;操作温度升高,膜的渗透通量增大,而分离因子降低。     

Separation by pervaporation of ethanol from aqueous solutions and effect of other components present in fermentation broths

BACKGROUND: In this work, the selective extraction of ethanol by pervaporation through a POMS (polyoctylmethyl siloxane) hydrophobic membrane supplied by GKKS (Germany) was investigated. First, binary ethanol aqueous solutions were studied considering the effect of ethanol feed concentration (0–11 wt%) and operating temperature (307.55–326.35 K). The effect of some by‐products of the ethanol fermentation, such as glycerol, succinic acid, butanol and acetone, on the pervaporation performance has been analyzed. RESULTS: For binary ethanol aqueous solutions, it was found that water permeation flux remained more or less constant while ethanol permeation flux increased continuously when increasing ethanol feed concentration. However, water and ethanol permeances did not change much in the concentration and temperature range studied. It was observed that the addition of glycerol and succinic acid sharply decreased the total permeation flux while ethanol concentration in the permeate was hardly affected. The addition of butanol and acetone resulted in a lower separation factor for ethanol through the POMS membrane. CONCLUSIONS: For ethanol aqueous solutions the POMS membrane was found to be selective towards ethanol, although it does not present higher separation factors than distillation in the concentration range covered in this work. The presence of other components of the fermentation broth has a great influence in the pervaporation behavior. Further work must be done on the study of multicomponent and real mixtures. Copyright © 2009 Society of Chemical Industry     

Selective separation of n‐butanol from aqueous solutions by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: To use butanol as a liquid fuel and feedstock, it is necessary to establish processes for refining low‐concentration butanol solutions. Pervaporation (PV) employing hydrophobic silicalite membranes for selective recovery of butanol is a promising approach. In this study, the adsorption behavior of components present in clostridia fermentation broths on membrane material (silicalite powder) was investigated. The potential of PV using silicone rubber‐coated silicalite membranes for the selective separation of butanol from model acetone–butanol–ethanol (ABE) solutions was investigated. RESULTS: The equilibrium adsorbed amounts of ABE per gram of silicalite from aqueous solutions of binary mixtures at 30 °C increased as follows: ethanol (95 mg) < acetone (100 mg) < n‐butanol (120 mg). The amount of butanol adsorbed is decreased by the adsorption of acetone and butyric acid. In the separation of ternary butanol/water/acetone mixtures, the enrichment factor for acetone decreased, compared with that in binary acetone/water mixtures. In the separation of a model acetone–butanol–ethanol (ABE) fermentation broth containing butyric acid by PV using a silicone rubber‐coated silicalite membrane, the permeate butanol concentration was comparable with that obtained in the separation of a model ABE broth without butyric acid. The total flux decreased with decreasing feed solution pH. CONCLUSION: A silicone rubber‐coated silicalite membrane exhibited highly selective PV performance in the separation of a model ABE solution. It is very important to demonstrate the effectiveness of PV in the separation of actual clostridia fermentation broths, and to identify the factors affecting PV performance. Copyright © 2011 Society of Chemical Industry     

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     

二苯基亚砜在有机溶剂中的溶解度测定和拟合

在温度288.30～334.32 K、常压条件下,采用合成法测定二苯基亚砜在乙醇、乙酸乙酯、甲苯、丙酮、氯仿以及一系列浓度的乙醇-水混合溶剂中的溶解度。实验结果表明,在相同温度下,5种纯溶剂中二苯基亚砜的溶解度大小顺序如下,氯仿 > 丙酮 > 甲苯 > 乙酸乙酯 > 乙醇;乙醇-水混合溶剂中溶解度随着乙醇浓度下降而迅速降低;该溶解过程为吸热熵增过程,且随着溶解Gibbs斯自由能增大,溶解度减小。数据采用改进的Apelblat方程和van’t Hoff方程进行拟合,在乙醇-水混合溶剂中的溶解度数据还采用Jouban-Acree方程拟合。拟合结果与实验数据基本吻合。测定的固液平衡数据可为二苯基亚砜的合成与提纯等过程的溶剂选择提供依据。     

Characterization of poly(dimethylsiloxane)‐poly(methyl hydrogen siloxane) composite membranes for organic water pervaporation separation

Hydrophobic composite membranes with a crosslinked poly(dimethylsiloxane)‐poly(methyl hydrogen siloxane) selective layer were prepared by using a new laboratory made catalyst agent. The pervaporation separation of five organic solvent–water mixtures was carried out with these composite membranes, together with swelling experiments in the same feed mixtures. The volatile organic compounds employed were ethanol, methanol, 1‐butanol, acetone, and ethyl acetate. The pervaporation and swelling experiments revealed that both the 1‐butanol and the ethyl acetate solutions showed the highest affinity for the composite membrane. When these components were employed as feed solutions, the membranes showed both high selectivity and high permeation. Mechanical–dynamical experiments of swollen and nonswollen composite membranes were also performed. The relaxation spectra were analyzed in terms of the interaction of the components of the different mixtures with the composite membrane, and the free volume corresponding to the each sample was obtained. Once the membranes had reached an equilibrium swelling, a decrease in the free volume was observed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 546–556, 2001     

生物乙醇提浓工艺中渗透蒸发膜材料的研究进展

渗透蒸发膜分离技术具有分离效率高、低能耗、易于和发酵装置耦合等优势,在生物乙醇的分离、提浓工艺中得到广泛应用。结合国内外生物乙醇的研究现状,综述了渗透蒸发膜分离技术的研究进展,并对渗透蒸发膜分离技术的核心材料--膜材料的制备与应用进行详细介绍,展望了生物乙醇的渗透蒸发膜分离技术的发展前景。     

Mixed matrix membranes of polydimethylsiloxane with activated carbon for ABE separation

The demand for the large-scale biofuels production is very high. The use of ethanol and butanol in flex-fuel vehicles have already been achieved, but still need improvement to decrease the gasoline-dependence. In addition to it, the preparation of ethanol and butanol by eco-friendly routes are still a challenge. The use of ABE route, in which acetone, butanol, and ethanol are prepared by fermentation of 5 or 6 carbon sugars, requires higher yields and better separation performance. The goal of this work was to evaluate the use of pervaporation through asymmetric activated carbon (AC) dispersed polymethylsiloxane membranes for the separation of ABE aqueous solution with 1 wt% total organics. The amount of the filler was varied from 0 to 3 wt%. Membranes were characterized by scanning electronic microscopy, Fourier transformed infrared spectroscopy, swelling in solvents, thermogravimetric analysis, and differential scanning calorimetry. Membrane with 1 wt% of AC membrane showed different behaviors both in thermal resistance, which was increased, and also in pervaporation separation index (PSI). In this condition, membrane total flux, separation factor, and PSI for ethanol were 13.2, 2.6, and 19.9 g m⁻² h⁻¹, so that sorption behavior and diffusion rates were changed. Thus, it was possible to modulate membrane properties.     

Stabilized production of highly concentrated bioethanol from fermentation broths by Zymomonas mobilis by pervaporation using silicone rubber‐coated silicalite membranes

Since pervaporation performance of ethanol‐permselective silicalite membrane, which is an aluminum‐free hydrophobic zeolite, in the separation of fermentation broths by yeast are negatively affected by succinic acid, the potential of pervaporation using silicone rubber‐coated silicalite membranes of ethanol fermentation broths, not containing succinic acid, by Zymomonas mobilis was investigated for the reliable production of concentrated bioethanol. In the separation of fermentation broths, the pervaporation performance was influenced by nutrients used for the preparation of fermentation broths. In the separation of a broth prepared with yeast extract, pervaporation performance was greatly compromised by accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm not only in total flux, but also in permeate ethanol concentration compared to the separation of binary ethanol/water mixtures. When supplying a prepared broth with corn steep liquor without the accumulation of a substance(s) having an ultraviolet absorption maximum at approximately 260 nm, the permeate ethanol concentration did not decrease. Treating the prepared broth with activated carbon was effective in restraining the decrease in total flux. Pervaporation performance is also deteriorated by the adsorption of lactic acid contained in corn steep liquor onto the silicalite crystals. In the separation of ternary mixtures of ethanol/water/lactic acid, accomplished by adjusting the ternary mixtures to pH > 5, more than 90% of the permeation flux in the separation of binary ethanol/water mixtures was obtained, and the permeate ethanol concentration was comparable to that obtained in the separation of binary mixtures. For stably performing pervaporation, it is important to prepare ethanol fermentation broths by Zymomonas mobilis in which lactic acid concentration is as low as possible. Copyright © 2007 Society of Chemical Industry