硼酸、硼酸盐及其络合物在反渗透膜内扩散过程的分子模拟

利用分子模拟的方法建立了交联的反渗透膜模型,采用分子动力学模拟方法研究了水、氯化钠、硼酸、硼酸盐、山梨醇-硼酸盐络合物在反渗透膜和溶液中的扩散过程,以及其他几种硼酸盐与多羟基化合物（D-甘露醇、N-甲基D-葡糖胺和D-葡萄糖酸钠）的络合物在4种反渗透膜中的扩散过程。分析各粒子的均方位移曲线可得,各粒子在溶液中的扩散系数均大于在膜体系的扩散系数,水分子的扩散系数远大于各溶质分子和离子。与硼酸分子相比,硼酸盐离子与其体积相差不大,但受电荷效应的影响,其扩散系数小于硼酸分子一个数量级。与单络合物相比,双络合物由于分子体积增大,扩散系数更小。因此在反渗透络合强化脱硼过程中应保持过量的山梨醇添加量,以提高其双络合物浓度。在1,3,5-环己烷三甲酰氯/4-甲基间苯二胺（HT/MMPD）反渗透膜中,N-甲基D-葡糖胺-硼酸盐络合物的扩散系数是5种络合物中最低的,D-葡萄糖酸钠-硼酸盐络合物在含有间苯二胺（MPD）单体的膜类型中扩散系数较低,而D-甘露醇-硼酸盐络合物在含有MMPD单体的膜类型中扩散系数较低。由各粒子的轨迹图可知,各粒子在溶液中做较稀疏的无规则扩散运动,在膜内粒子由于受到聚酰胺膜结构的限制做较密集的扩散运动。     

聚乙烯电池隔膜为支撑层的反渗透膜的制备

以聚乙烯电池隔膜替代传统聚酯支撑层，利用相转换法在其上涂覆聚芳醚砜，然后利用界面聚合在表面制备聚酰胺分离层，最终成功得到以聚乙烯电池隔膜为支撑层的反渗透膜，并对膜的表面化学性能和物理结构进行了表征，利用错流过滤测试系统测试其分离性能，探究不同条件下所得反渗透膜的水通量和截留率。结果表明：聚芳醚砜、间苯二胺、1,3,5-苯三甲酰氯质量分数分别为12.00%,2.00%和0.10%时，所制反透渗膜具有均匀的脊谷结构，其对NaCl的截留率为96.87%，水通量为16.02 L/(m²·h)，且使用10 h仍保持良好的稳定性。     

膜集成技术处理氯化法钛白后处理废水的研究

氯化法钛白无机包膜处理工序会产生大量中性废水,其中包含少量钛白粉和水溶性盐,现阶段企业多以外排为主。采用膜集成（陶瓷膜+反渗透膜+纳滤膜）技术对氯化法钛白后处理废水的处理进行研究。将氯化法钛白后处理废水用陶瓷膜过滤,分离回收二氧化钛;将陶瓷膜清液用反渗透膜浓缩,清水回收利用;将反渗透浓液用纳滤膜分离硫酸钠和氯化钠。结果表明：利用陶瓷膜处理氯化法钛白后处理废水,平均通量为650 L/（m ²·h）,浓液中钛白粉质量浓度达到90 g/L以上,清液中钛白粉质量浓度低于0.001 g/L;使用反渗透膜截留清液中的硫酸钠和氯化钠,硫酸钠和氯化钠的截留率为99.5%,浓水中的盐质量分数达到4%以上;浓水中的硫酸钠和氯化钠通过纳滤膜分离,纳滤膜对硫酸钠的截留率为97%,硫酸钠质量分数达到14%以上。     

正渗透过程中水与溶质的传递现象

正渗透是一种利用渗透原理的新兴膜技术,近年来在国内外受到了广泛的关注。解析该过程中溶剂水的传递和驱动溶质的反向传递对其发展和应用至为关键。首先开展了两种膜的取向下,正渗透过程中的水通量和溶质反向摩尔通量的实验研究。当驱动溶液在膜分离层侧时,水通量更高,而溶质反向摩尔通量更低,表明水的传递对溶质的反向传递有限制作用。而后分别考察了不同的单一溶质和二元混合溶质作为驱动溶质时,水和溶质的传递现象。当单一中性溶质或电解质作为驱动溶质时,水通量和溶质反向摩尔通量均随驱动溶液浓度的升高而增大;在相同操作条件下,驱动溶质的扩散系数越小,溶质反向摩尔通量越小;中性溶质与电解质混合溶液为驱动溶液时,溶质分子之间存在耦合传递效应。     

正渗透过程中水与溶质的传递现象

正渗透是一种利用渗透原理的新兴膜技术,近年来在国内外受到了广泛的关注。解析该过程中溶剂水的传递和驱动溶质的反向传递对其发展和应用至为关键。首先开展了两种膜的取向下,正渗透过程中的水通量和溶质反向摩尔通量的实验研究。当驱动溶液在膜分离层侧时,水通量更高,而溶质反向摩尔通量更低,表明水的传递对溶质的反向传递有限制作用。而后分别考察了不同的单一溶质和二元混合溶质作为驱动溶质时,水和溶质的传递现象。当单一中性溶质或电解质作为驱动溶质时,水通量和溶质反向摩尔通量均随驱动溶液浓度的升高而增大;在相同操作条件下,驱动溶质的扩散系数越小,溶质反向摩尔通量越小;中性溶质与电解质混合溶液为驱动溶液时,溶质分子之间存在耦合传递效应。     

乳化液膜萃取乳酸稀溶液过程中的渗透溶胀及模拟

根据膜相中载体萃取的机理,指出载体在萃取溶质后形成的络合物具有一定的亲水性．采用气相色谱法,分别对含有表面活性剂和载体的膜相在与乳酸溶液接触后的溶水率进行了测定,结果发现其溶水率远高于与无溶质的外相水接触后的膜相溶水率．所以渗透溶胀进人内相的水除表面活性剂分子结合的迁移外还有载体-溶质络合物结合水．从而提出了实际萃取过程中乳化液膜渗透溶胀的反应-溶解-扩散机理,并提出了相应的数学模型,经与实验数据比较,结果吻合较好．     

石墨烯改性复合反渗透膜的结构和性能研究

在聚砜铸膜液中加入石墨烯分散液(GDN),以纯水为凝固浴,采用浸没沉淀相转化法制备支撑层,并以界面聚合法制备复合反渗透膜,利用场发射扫描电子显微镜、原子力显微镜、接触角测量仪等技术对支撑层和复合反渗透膜结构和性能进行表征测试。结果表明,GDN可以有效提高多孔支撑层表面皮层厚度,当PS铸膜液中GDN添加质量分数为0.1%时,复合反渗透膜水通量最高,接触角最低,在牛血清蛋白水溶液中测试通量衰减幅度最小。制备的复合反渗透膜具有表面粗糙度小、亲水性好和耐污染能力强等优点。     

改进的反渗透膜溶解-扩散模型及其验证

以反渗透膜溶解-扩散模型(SDM)为基础,考虑了溶质体积压力驱动项的影响,提出了改进的反渗透膜溶解-扩散模型(MSDM)。由方程的函数性质得到溶解-扩散模型中的参数B值随压力变化而变化,溶质脱除率随压力增大而增大,增大的幅度随压力增大而减小的结论。依据改进模型拟合的均方差在10?8～10?6之间,优于溶解-扩散模型(SDM)。由模型参数α值计算的Vs值与溶质摩尔体积真实值有些偏差,模型计算的溶质偏摩尔体积产生偏差的原因是参数α可能是一个与渗透通量、压力相关的函数。因而该模型可以作为一个半经验模型。     

反渗透污染膜水通量迁移方程的改进及应用研究

介绍了目前几种反渗透膜透过机理,通过文献调研认为目前聚酰胺膜反渗透膜的透过机理遵循优先吸附-毛细孔流理论,在此基础上从孔流理论出发对低压反渗透膜的分离机理进行初步研究,改进了孔流理论的水通量的基本迁移方程,并建立了用膜污染层厚度δ_f来预测膜污染时间的数学模型,通过反渗透实际工程的设计运行得到了试验验证,丰富了RO系统理论,特别是在预测膜污染清洗时间方面提供了新的依据.     

优化聚酰胺分离层制备高选择透过性反渗透膜

反渗透（RO）膜分离技术由于具有高效、低耗和产水水质高等优点，已成为现阶段解决水资源短缺的有效手段。进一步提高RO膜的选择透过性能有利于降低产水成本和提高产水质量，因此制备高选择透过性能的RO膜一直是膜领域研究的重点。从优化界面聚合工艺、优化基膜及开发新型制膜工艺三方面对近年来改善RO膜选择透过性能的研究进行了综述。通过优化界面聚合工艺和开发新型制膜工艺可以直接改变分离层的结构和性质，通过调节基膜的孔径、孔隙率及亲疏水性可以影响分离层的结构，从而改善RO膜的性能。最后对制备高选择透过性能的反渗透膜的研究方向与发展前景进行了总结与展望。     

反渗透、纳滤过程的物理化学研究(Ⅰ)多孔膜的溶质脱除率方程和膜渗透通量方程

引言 溶解扩散模型、摩擦模型、Sourirajan方程和表面力孔流模型均假设稳态条件下溶质通量和溶液体积通量恒定[13].     

Solute diffusion through swollen polymer membranes

Experiments were designed to study the role of the solvent in the transport of a solute through a solvent-swollen polymer membrane. A single solute (an organic dye), a single polymer (cross-linked natural rubber), and 24 different organic solvents were used for this purpose. The solute diffusion coefficient D was calculated from the measured permeability P and distribution coefficient K, and was compared to the diffusion coefficient of the solute in the pure solvent. The main parameters of the solvent were shown to be its viscosity and the degree it swells the polymer. At high swelling, the results are in agreement with a model that pictures the resistance to solute diffusion as hydrodynamic interaction with the solvent while the polymer acts as an obstruction that increases the tortuosity of the diffusion path. At very low swelling, the diffusion coefficient approaches an asymptotic limit which is independent of solvent viscosity. However, even with as low as 10% solvent, some effects of viscosity are still seen. These results are discussed in terms of a quantitative theory for the obstruction effect proposed by Meares and compared to other literature data.     

反渗透过程溶质脱除率方程

<正>溶解扩散理论、摩擦模型和表面力-孔流模型假设稳态时膜中溶质通量恒定“-”。本文分 析了该假设存在的理论依据,并基于膜的吸附-扩散模型’‘’建立了反渗透过程溶质脱除率方 程。     

Diffusion Characteristics in Microcapsules

An equation of diffusion for microcapsules(hollow sphere)was developed,employing the mathematicalmodel for the diffusion characteristics of solid sphere.In the proposed equation,a combination diffusion coeffi-cient was introduced as a substitute for the diffusion coefficient in the solid sphere mathematical model and ex-pressed as a function of the diffusion coefficient inside solution of hollow sphere,as well as in the polymer mem-brane.With this modified model,the diffusion coefficients of glucose in NaCS(sodium cellulose sulfate)-PDADMAC(Poly-diallyl-dimethyl-ammonium chloride)membrane and in Ca-alginate gel membrane were deter-mined.The diffusion coefficient in NaCS-PDADMAC membrane was found to be 2.12×10~(-11)m~2·s~(-1)and thatin Ca-alginate membrane 2.62×10~(-10)m~2·s~(-1).     

Tracer Concentration Gradients for Diffusion Coefficients Exponentially Dependent on Concentration

A diffusion equation having a tracer diffusion coefficient exponentially dependent on solute concentration, D*=D₀* exp (β C ), was solved numerically for thin-film and thick-film boundary conditions and varying values of annealing time, film thickness, and β. For values of β in the range 3 to 10 mol fraction⁻¹, the calculated distribution of solute remained remarkably Gaussian. The apparent diffusion coefficient evaluated from such solute gradients was greater than the true tracer diffusion coefficient D ₀* by ≤20% for large β and shallow tracer penetration. The results were used to estimate possible errors in data which have been reported for several oxide systems, and may be used as a guide for the selection of experimental parameters so that corrections will not be necessary.     

Phenol transport in cellulose acetate membranes

Past detailed studies of solute transport through reverse-osmosis membranes have been conducted only with simple salts. The present work with phenol was undertaken largely because of the practical observation that the transport of low molecular weight organics is much more rapid than that of the salts. Studies of phenol sorption from dilute aqueous solution indicate that the diffusion coefficient for phenol in water-saturated 39.8 wt.-% acetyl cellulose acetate is 9.6 × 10^-10 cm.²/sec., and the equilibrium distribution coefficient between the acetate phase and water is 42. Thus, the diffusion coefficient is quite close to that measured for sodium chloride, and the higher permeability of the membranes to phenol can be attributed entirely to their greater sorption of this solute. In direct osmosis experiments performed with significant water flow a measurable interaction or positive coupling between water and phenol flows has been observed. Further evidence of flow coupling is derived from reverse osmosis experiments in which significant negative solute rejection is observed; i.e., the permeate is enriched in phenol by as much as 20%. It is shown that a solution-diffusion transport model is not adequate to rationalize the results, and a more complex transport model is apparently required.     

Modeling of the variations of permeate flux,concentration polarization,and solute rejection in nanofiltration system

A numerical model is presented and experimentally validated for predicting the local concentration polarization and the related separation performance of nanofiltration (NF) system. The model combines computational fluid dynamics for describing the transport phenomena in NF channel, with Spiegler-Kedem-Katchalsky model for considering the permeation properties through NF membrane. Particular attention is given to the modeling of spatially varied solute rejection and solute transport through membrane, representing essential distinctions from the modeling of reverse osmosis (RO) membrane. Also, an experimental-numerical framework is proposed to determine model parameters related to solute transport, including reflection coefficient and solute permeability as functions of feed solute concentration. The usefulness of this model is highlighted by predicting concentration polarization under different conditions related to operations, membrane systems (NF vs. RO), and solute types (NaCl vs. MgSO₄). Also, the contributions by convection and diffusion to solute transport are clarified, benefiting by the modeling of solute transport. © 2018 American Institute of Chemical Engineers AIChE J, 65: 1076–1087, 2019     

硝基苯在Cu-SPE复合电极上的电还原反应特性研究

以国产NF - 1型离子膜为SPE膜材料 ,采用浸渍还原法制备了Cu SPE复合电极 ,研究了硝基苯在此电极上的电还原反应及其主要影响因素 ,并建立了相应的扩散模型。结果表明 :Cu SPE复合电极对硝基苯的电还原反应具有较高的电催化活性 ,硝基苯及其产物在SPE膜内的扩散是反应的控制步骤 ,反应主要发生在Cu SPE界面的内表面 ,其扩散系数D0 =8.1× 10 -7cm2 /s ;经HPLC分析表明电还原产物主要为苯胺。