壳聚糖／羧甲基纤维素聚电解质络合物膜的乙醇／水渗透汽化性能研究

采用壳聚糖和羧甲基纤维素进行聚离子反应．制备聚电解质络合物膜。该膜用于乙醇／水的渗透汽化分离，显示具有优先透水性，在乙醇浓度90％，温度60℃下，渗透通量和分离系数分别达197g／m2·h，1588。随料液乙醇浓度的增加，膜渗透通量下降，而分离系数增加，分离系数在乙醇浓度90％左右有一极大值。随温度升高，膜渗透通量和分离系数同步上升，渗透通量随温度的关系符合Arrhe－nius方程，渗透汽化表现活化能为34kJ／mol。     

乳胶渗透蒸发膜分离醇水混合物

以苯乙烯、丙烯酸丁酯为单体进行乳液聚合,将聚合获得的乳胶直接浇铸制备出乳胶膜．将该膜用于水－乙醇混合物的渗透蒸发分离,优先透水,渗透通量为50一450g／（m2·h）,分离因子为80～260．考察了乳胶膜的选择性及料液浓度对乳胶膜分离性能的影响．研究了塑化效应和耦合效应对组分渗透的影响,发现在乳胶膜中,乙醇的存在有利于水的渗透,而水的存在会阻止乙醇的渗透．     

渗透汽化膜行为为研究（I）

讨论了渗透汽化膜的渗透行为，以乙醇－－水混合溶液为进料，在全浓度范围内，分别 ４张不同硫酸交联程度的悫聚糖膜的渗透汽化性能及平衡溶解吸附性能，结果表明，硫酸交联增强了水的渗透，抑制了醇的渗透，从而使膜分离性能明显改善，膜对水及乙醇的透量与膜对水及乙醇的溶胀度之间存在明显的对应关系，在引入溶解吸附分离系数α３和扩散蒸发分离系数ａＤＶ后计算表明，膜的分离性能主要取决于水和乙醇在膜界上的溶解分配平衡。     

管状Silicalite—1分子筛膜的乙醇／水渗透汽化分离性能

采用原位水热合成的方法在管状α－ Ａｌ２ Ｏ３ 基膜上合成了 Ｓｉｌｉｃａｌｉｔｅ － １ 分子筛膜． Ｘ Ｒ Ｄ、 Ｓ Ｅ Ｍ、 Ｅ Ｄ Ｘ 和气体渗透等表征方法表明该膜没有裂缺．研究了原料液中乙醇浓度和渗透温度对乙醇／ 水渗透汽化分离的影响．研究发现,当温度为３０ ℃、原料液乙醇的摩尔分数为１ ．２ ％ 时,乙醇／水的分离系数为６０ ,透量为３ ．１ ｍｏｌ／（ ｍ ２·ｈ） ;温度升高,分离系数稍有下降,透量大大提高;当温度为６０ ℃、原料液乙醇浓度不变,乙醇／ 水的分离系数为４６ ,透量为１３ ．３ ｍｏｌ／（ ｍ ２·ｈ） ．原料液中乙醇浓度增加,乙醇／ 水的分离系数有一最大值;透量则随原料液中乙醇浓度的增加而降低．吸附－ 扩散机理很好地解释了实验结果．     

模拟发酵液中渗透汽化膜分离乙醇性能劣化研究

渗透汽化技术(PV)与乙醇发酵过程耦合可将发酵液中的乙醇原位移除,从而缓解产物抑制作用,提高乙醇产率.但是发酵液中所含的物质复杂,且其对膜渗透汽化性能的影响尚无定论.通过在乙醇水溶液中添加葡萄糖、甘油、琥珀酸以及无机盐等发酵液中的代表性物质,考察其对乙醇透过性能的影响.结果表明,无机盐、葡萄糖和甘油对PDMS膜的渗透汽化性能没有明显影响.琥珀酸容易在膜表面吸附沉积并进入膜内阻塞乙醇与水的通道,使渗透通量下降7%,是导致发酵-渗透汽化耦合过程中膜劣化的主要物质.琥珀酸、葡萄糖和甘油的协同作用使PDMS膜的渗透通量下降11.2%.     

金属钯修饰PAn／PTFE复合膜的制备及其氢气响应性的研究

以聚四氟乙烯多孔膜为基膜，采用膜相渗透原位化学氧化聚合法制备了PAn／PTFE复合膜；在该复合膜表面通过电化学沉积金属钯微粒，得到了Pd／PAn／PTFE复合膜，通过测定复合膜在空气中和一定浓度氢气气氛中的V-I特性，表征复合膜对氢气响应性能。实验考察了电沉积过程中沉积时间、氯化钯浓度和盐酸浓度对复合膜性能的影响，当氯化钯浓度为2mol／L、盐酸浓度为0．5mol／L、沉积时间为6min时，复合膜在吸氢前后表现出最大的电流变化值，通过扫描电镜和X射线衍射仪对复合膜进行了表征。初步讨论了该复合膜对氢气表现出电流响应性的机理。     

制膜条件对硅橡胶膜微结构及分离性能的影响

以PVDF超滤膜为支撑层,以107、108、RT-615为3种硅橡胶的复合层,制备了交联硅橡胶/PVDF复合膜用于渗透汽化乙醇/水的分离。采用SEM表征了硅橡胶/PVDF复合膜的表面及断面形貌,测定了交联硅橡胶均质膜的溶胀度、密度和交联链长度,考察了硅橡胶交联结构、交联剂用量、交联温度对硅橡胶膜微观结构与分离性能的影响,得到了硅橡胶最佳制膜条件。研究发现与加成型交联硅橡胶(RT-615)相比,脱醇型交联硅橡胶(108、107)交联链长度较大,膜自由体积较大,更适于低浓度乙醇/水混合物的分离。     

藻朊酸盐膜对水／有机物混合液的PV分离

研究了藻朊酸、藻朊酸钠及二价金属离子交联的藻朊酸钠对水／乙醇体系的渗透汽化性能，同时，还研究了藻朊酸盐膜对水／甲醇、水／异丙醇、水／丙三醇、水／丙酮体系的分离性能，表明，藻朊酸盐膜上述几种体系均具有良好的分离性能。     

透明涂层光干涉彩色不锈钢的制作方法

一种透明涂层光干涉彩色不锈钢的制作方法是，先将不锈钢放在CrO3和H2SO4的溶液中，在其表面生成光干涉色氧化膜；再放在CrO3 250g／L和H2SO4 2．5g／L的电解坚膜溶液中进行处理；然后放在Na2SiO3、浓度为10％的水溶液中进行封闭处理。为了增强上述彩色不锈钢装饰表面的抗污性和耐磨性能，     

液膜接触法处理含铜废水的实验研究

探讨以P204为流动载体的液体表面活性剂膜从酸性水溶液中分离二价铜离子的过程，并对影响二价铜离子透过液膜的重要变量进行分析，这些变量主要是外部水相中的起始铜浓度、外相溶液中的起始pH值、液膜流动载体浓度、乳水比、内相峻浓度等．实验结果表明：较佳膜相组成的液膜能把废水溶液中铜离子浓度从100mg/L降到0．9mg/L;铜萃取率大于99％．     

低温氧等离子体改性聚乙烯醇渗透汽化膜

用低温等离子体处理聚乙烯醇膜，通过红外光谱，表 ，扫描电镜等分析测定证明了用氧等离子体处理后膜表面带上羰基，增加了羟基，同时使原来未水解的部分乙酸乙烯酯全部裂解掉。当分别用未处理的原始ＰＶＣＡ膜处理面以着原料液膜以及处理面对着低压侧膜对乙醇－水溶液进行渗透汽化分离时，发现上，下表面均对渗透汽化过程有重大影响，其上表面主要作用膜的溶解过程，而下表面则对膜的扩散控制有较大贡献。     

海洋鱼类弧菌病疫苗的制备--新型简易鳗弧菌(Vibrio anguillarum)培养基优化①

以一株从我国山东海域爆发弧菌病鲈鱼体内分离得到的病原菌鳗弧菌（Vibrio anguillarum MV425 O1型）为研究对象,对其实现高密度生产海洋鱼类弧菌病疫苗的培养基进行了优化研究。研究表明,碳源的NaCl造成的渗透压以及由发酵碳源和氮源导致的pH值变化是影响细胞正常生长的重要因素。海水中微量元素（除铁元素）对菌体生长的作用可被酵母浸出物补偿,高铁浓度有助于菌体生长。在确定显著影响因子的基础上,采用可旋转中心复合设计方案和响应面法进行了统计模型优化,优化设计有效地提高了细胞培养密度,实现在摇瓶条件下细胞干重5．8g/L和30L规模反应器中26．2g/L的较好的初步放大结果,并可替代海水培养基。     

高通量ZSM-5填充硅橡胶复合膜渗透汽化性能研究

以硅铝比为360的ZSM-5型沸石对聚二甲基硅氧烷(PDMS)进行填充,以聚偏氟乙烯(PVSF)为支撑层,制备了ZSM-5填充PDMS/PVDF复合膜,用于渗透汽化乙醇/水混合物的分离.研究了沸石填充量、操作温度、进料液浓度对乙醇/水的渗透汽化分离性能的影响,发现该复合膜较文献报道中的沸石填充膜,其渗透通量有了明显的提高,在50℃沸石填充量为40%时,对乙醇的分离因子为11.7,其渗透通量达到749.8 g/(m2·h).随着操作温度的升高或料液中乙醇浓度升高,渗透通量增大,分离因子下降.     

渗透汽化膜表面结构对分离过程的影响

用低温氧等离子体处理聚乙烯膜,被处理的膜通过红外、表面接触角、电子扫描显微镜、元素分析等手段证明在其表面形成了多量的羟基、羰基和羧基等含氧基团。当将这种处理膜的处理面对着原料液（ＵＰＥ）、处理面对着低压侧（ＤＰＥ）及原始膜（ＰＥ）分别用来渗透汽化分离乙醇水混合物,发现ＰＥ膜为优先透醇膜。ＵＰＥ渗透汽化产物的醇浓度下降,透量增加,并且透过速率对原料液浓度曲线呈反Ｓ形。ＤＰＥ膜则完全变成了优先透水膜,并且透过速率明显下降,说明渗透汽化膜表面的结构及组成对渗透汽化过程予以重大的影响,膜的上表面主要发生溶解,下表面则对被分离物予以强有力的扩散控制。     

On-line determination of the intracellular poly(beta-hydroxybutyric acid) content in transformed Escherichia coli and glucose during PHB production using stopped-flow attenuated total reflection FT-IR spectrometry

An automated approach for rapid on-line monitoring of the solid and liquid phases present in bioprocesses based on mid-IR Fourier transform spectrometry is introduced. The principles of this new approach are presented using the example of the quantitative and qualitative analysis of poly(beta-hydroxybutyric acid) (PHB) accumulated in living bacterial cells as well as dissolved glucose during two 27-h fermentation processes. FT-IR spectra were recorded on-line using a diamond-attenuated total reflection (ATR) cell connected to the fermentation broth by means of a computer-controlled flow system. For calibration of the FT-IR method, standard reference analysis procedures for PHB (gas chromatography) and glucose (HPLC) were used. While pumping the fermentation broth through the flow cell, the recorded spectra corresponded to the fermentation solution, which allowed the determination of glucose in a range from 3.8 to -10.3 g/L. Upon stopping the flow, the cells settled on the ATR surface, and the thus recorded spectra enabled the determination of the intracellular PHB content of Escherichia coli in a range from 0.005 to 0.766 g/L. Errors of cross-validation of 0.264 g/L for glucose and 0.037 g/L for PHB were obtained. Application of one PLS calibration model to another fermentation was possible with prediction errors of 0.493 g/L for glucose and 0.105 g/L for PHB. Furthermore, from the position and shape of the PHB carbonyl band, it could be concluded that the PHB granules inside the E. coli are predominantly amorphous.     

壳聚糖-三聚磷酸钠聚离子复合膜的研究

以红外光谱表征壳聚糖-三聚磷酸钠聚离子复合膜的结构。研究了膜组成、料液浓度、温度等对乙醇-水溶液的渗透汽化分离性能的影响。实验结果表明,该复合膜对乙醇-水溶液具有很高的渗透汽化脱水的选择分离性能和渗透通量。同时对渗透汽化机理及影响因素进行了初步探讨。     

聚醚酰亚胺耐溶剂超滤膜的制备及性能研究EI北大核心CSCD

采用浸没沉淀相转化法制备聚醚酰亚胺(PEI)平板超滤膜,考察了铸膜液中聚合物PEI浓度、添加剂聚乙烯吡咯烷酮(PVP)浓度对膜结构和性能的影响。为提高超滤膜的耐溶剂性能,采用己二胺(HDA)进行化学交联,并研究了不同交联时间下膜性能的差异。结果表明:在不降低膜分离性能的情况下,交联后的膜渗透通量得到了有效提高,在0.1 MPa运行压力下纯水通量由667.1 L/(m^(2)·h)提高到1126.1 L/(m^(2)·h),而对1.0 g/L牛血清白蛋白(BSA)溶液的截留率保持在97%以上。膜溶剂吸附实验发现,在6种不同溶剂中浸泡48 h后,未交联膜在N,N-二甲基甲酰胺(DMF)中已完全溶解,而交联膜仍保持着良好的膜形态,吸附量为0.86 g/g,在乙醇、异丙醇、正己烷、1 mol/L HCl溶液中的吸附量均小于未交联膜,在1 mol/L NaOH溶液中反而增加,说明制备得到的交联膜具有良好的耐溶剂性能和耐强酸性能,耐强碱性能反而变差。     

Plasma-treated polyethersulfone coated with crosslinked poly(vinyl alcohol): composite membranes for pervaporation dehydration of ethanol

Composite membranes with crosslinked poly(vinyl alcohol) matrix as selective layer coated on a polyethersulfone supporting porous layer were prepared aiming at separating ethanol/water mixtures by pervaporation. A polyethersulfone asymmetric microporous membrane was synthesized by the wet phase inversion process. The support membrane was then exposed to air plasma to activate the surface. The selective dense layer was obtained by coating of PVA and a crosslinking agent over the polyethersulfone substrate, followed by thermal treatment. The morphology was examined by scanning electron microscopy (SEM) for both, support membrane and the coated polymeric layers. Surface physicochemical properties were evaluated through measuring the contact angle (θ) and the estimation of surface free energy (γ_S) and adhesion work. The surface chemical composition of support membrane and coated hydrophilic layers were characterized by infrared spectra with horizontal attenuated total reflectance (FT-IR/HATR). The swelling degree of PVA dense membranes, and the pervaporation performance of the crosslinked PVA/PES composite membranes, manufactured with several coating steps, were evaluated with water/ethanol (20/80 wt%) mixtures at temperatures in the range of 30–60 C. Results of the effective pervaporation dehydration of ethanol are discussed in terms of membrane morphology and the solution-diffusion transport mechanism.     

One-step dynamic assembly of polyelectrolyte complex membranes

During the past decades, layer-by-layer (LbL) assembly technique based on electrostatic adsorption of oppositely charged polyelectrolytes (PEs) has been one of the most frequently utilized processes for assembling ultra-thin film. However, LbL process is also recognized as a time-consuming process, especially for assembly of dense membranes. In this paper, a one-step dynamic assembly based on electrostatic adsorption was developed to prepare the PE complex membranes. The chitosan (CS), used as a model polycation, was dynamically deposited on a hydrolyzed polyacrylonitrile (PAN) support membrane with negative charges under a selected pressure to form a PE complex membrane for pervaporation separation of water–ethanol mixture. Compared with traditional dip-coating method, this new assembly process could offer some advantages such as the formation of selective layer with dilute solution, easily used for different membrane module types and suitable for large scale applications. The assembly conditions such as dynamic pressure, CS molecular weight, and CS concentration were investigated. The appropriate conditions for assembly were: dynamic pressure, 0.2 MPa; CS molecular weight, 82,000; and CS concentration, 0.5 wt.%. In the case of pervaporation of 95 wt.% ethanol/water mixtures, the separation factor and the permeate flux of the CS polyelectrolyte complex membranes were 422 and 230 g/(m² h) (60 °C), respectively. The cross-linking treatment with glutaraldehyde and sulfuric acid were subsequently performed. It was found that the separation performance was improved by the cross-linking treatment. Finally, inner skin hollow fiber PE complex membranes were also successfully explored using one-step dynamic assembly for pervaporation dehydration. The proposed process will offer a new approach to obtain a relatively integrated PE complex membrane.     

改性聚乙烯醇复合膜对微水重石脑油的渗透汽化脱水研究

用甲醛对聚乙烯醇进行改性,并用于质量分数约为100 μg/g微水重石脑油体系的渗透汽化(PV)深度脱水.考察了操作温度T、料液浓度C_w、操作流量q_v,等因素对分离性能的影响.渗透通量J与分离系数α随T、C_w的升高分别增大和减小,且J随g_v的增大而增大.实验证明在操作温度80℃,膜后压力1.5 kPa,流量500 L/h下,实现了J=60.6 g/(m~2·h),α=221.9的最佳分离效果,该技术有效脱除了油品中的微量水分,具有很好的工业应用前景.