不同pH值下腐殖酸反渗透膜污染中的界面相互作用解析

应用extended derjaguin-landau-verwey-overbeek (扩展DLVO) 理论评价不同pH值下范德华力、静电力、疏水性力3种界面相互作用对腐殖酸反渗透(reverse osmosis, RO)膜污染的贡献,探究pH值影响腐殖酸RO膜污染的主控机制.对3种常规RO膜的理论分析结果表明,静电力对腐殖酸RO膜污染的贡献很小,范德华力使膜污染加剧;疏水性力会减缓膜污染.与前期粘附阶段相比,后期粘聚阶段中范德华力的贡献有所增大,疏水性力在2个污染阶段中均起主导作用.膜污染随pH值的降低而加重,疏水性力作用能的改变是pH值影响系统界面自由能的主控机制.相应pH值下3种RO膜过滤实验数据及其相关性分析结果表明,扩展DLVO理论能定量评价3种界面相互作用的贡献,界面自由能和膜污染之间有很好的相关关系,RO膜纯水接触角的数值不宜作为评价膜污染的指标.     

XDLVO理论解析不同离子条件下海藻酸钠微滤膜污染

应用extended Derjaguin-Laudau-Verwey-Overbeek(XDLVO)理论定量解析海藻酸钠微滤膜污染中界面微距作用力,探讨不同离子条件对膜污染影响的主控机制.结果表明,对于亲水性膜表面,范德华力促进膜污染,极性作用力阻碍膜污染;而对于疏水性膜表面,范德华力减缓膜污染,极性作用力加速膜污染.海藻酸钠与微滤膜接触时双电层作用力对膜污染贡献相对微弱.离子强度及钙离子对海藻酸钠微滤膜污染的影响主要是通过改变极性作用力来实现的.较高的离子强度会降低极性作用力的排斥性或升高极性作用力的吸引性,从而加重海藻酸钠微滤膜污染.虽然钙离子使出水通量急速下降,但钙离子的存在使得物理清洗效率提高.不同离子条件下初始阶段及后期阶段污染趋势K分别与膜-海藻酸钠粘附自由能及海藻酸钠-海藻酸钠粘聚自由能具有良好的线性相关性,表明XDLVO理论适用于描述不同离子条件下海藻酸钠微滤膜污染行为.     

xDLVO理论解析微滤膜海藻酸钠污染中pH值影响机制

用extended Derjaguin-Laudau-Verwey-Overbeek(xDLVO)理论定量解析不同pH值下海藻酸钠微滤膜污染过程中的界面相互作用,评价范德华力(LW)、双电层作用力(EL)、极性力(AB)对海藻酸钠微滤膜污染的相对贡献.结果表明,在pH5~9范围内,AB相互作用能起着关键作用,决定了总界面相互作用能的性质与强度.不同pH值下海藻酸钠微滤膜污染趋势(K)为pH 5 > pH 7 > pH 8 > pH 9. 由于与海藻酸钠之间的界面作用为引力,疏水性膜在过滤初期膜污染更为严重;污染后期亲、疏水性膜污染行为差异不明显,因为此时海藻酸钠之间的排斥性界面作用为主导.初始、后期阶段K值分别与膜-海藻酸钠界面自由能、海藻酸钠-海藻酸钠界面自由能有较强的线性相关性,说明xDLVO理论可以有效预测不同pH值下海藻酸钠微滤膜污染行为.     

XDLVO理论解析有机物和钙离子对纳滤膜生物污染的影响

为了揭示有机物和Ca2+浓度对纳滤膜生物污染的影响机制,选用铜绿假单胞菌(PA)为模式菌株,海藻酸钠(SA)、牛血清白蛋白(BSA)和腐殖酸(HA)为典型废水有机物,采用extended derjaguin–landau–verwey–overbeek(XDLVO)理论定量解析了不同进水条件下膜预处理和生物污染过程的界面相互作用.结果表明,Ca2+浓度为5mmol/L时,SA预处理后膜面亲水性最强,粘聚自由能高达42.96mJ/m2,与PA、SA的界面自由能最高,分别为45.85和39.64mJ/m2,抑制膜的生物污染.而Ca2+浓度为2mmol/L时,BSA预处理后膜面疏水性最强,粘聚自由能低至–40.32mJ/m2,与PA、BSA的界面自由能最低,分别为3.49和–26.36mJ/m2,促进膜的生物污染.所有污染过程中,范德华作用能差异较小,而静电作用能绝对值极小,贡献微弱,有机物和Ca2+浓度对膜生物污染的影响主要体现在对疏水作用能的影响.     

典型有机物与超滤膜界面作用及膜污染机制研究

对二级出水中典型有机物的膜通量及膜污染变化情况进行分析比较,并应用扩展DLVO(x DLVO)理论分析了有机物超滤过程中的界面作用能对膜污染行为的影响机制.研究表明,海藻酸钠(SA)导致的膜通量下降最为显著,其次为腐殖酸(HA)和牛血清白蛋白(BSA);就3种有机物而言,膜污染均主要发生在粘附阶段,而在粘聚阶段中膜污染程度较小.对比而言,海藻酸钠(SA)主要形成可逆污染,腐殖酸(HA)和牛血清白蛋白(BSA)则以不可逆污染为主.在过滤过程中,极性界面作用能是控制膜污染的主要因素,HA和BSA的极性界面作用能为正值,能抑制膜污染,而SA的极性界面作用能为负值,会加剧膜污染.3种有机物在粘聚阶段的极性界面作用能均大于粘附阶段,说明粘附阶段的膜污染更严重.     

超滤膜材料对SiO2-有机物膜污染行为的影响

选用聚偏氟乙烯（PVDF）及乙烯乙烯醇共聚物（EVOH）2种超滤膜，针对SiO₂-牛血清蛋白（BSA）及SiO₂-腐殖酸（HA）2种无机-有机混合污染物，通过单种及混合污染物过滤实验，结合各污染物与膜之间作用力的测定，考察膜材料对SiO₂-有机混合污染物膜污染行为的影响机制.结果表明：与单种有机污染物HA或BSA相比，SiO₂-HA/BSA混合污染物对PVDF及EVOH超滤膜的污染会出现加剧和减缓2种相反的现象.结合作用力结果发现：当膜-SiO₂之间的作用力大于膜-有机污染物之间作用力时，与单种有机污染物相比，SiO₂的存在会加剧膜污染；相反，当膜-SiO₂之间作用力小于膜-有机污染物之间作用力时，SiO₂的存在会有效减缓膜污染.上述结果说明膜材料是控制无机-有机混合污染物膜污染行为的关键因素.     

微滤过程中腐殖酸与膜表面黏附特性的试验研究

为了进一步研究微滤过程中腐殖酸对微滤膜的污染机制,通过运用原子力显微镜(AFM),结合自制的PVDF胶体探针考察了不同的pH、离子强度以及钙离子浓度等水质条件下膜-腐殖酸与腐殖酸-腐殖酸之间微观黏附力的变化趋势以及与膜的通量衰减幅度之间的相关性.结果发现,微观黏附力是膜面污染产生的根本原因.由于pH的电性中和以及离子强度的电性屏蔽作用,膜-腐殖酸以及腐殖酸-腐殖酸之间黏附力随着pH的减小或离子强度的增大都呈增大趋势;而随着钙离子浓度的增大,由于少量钙离子的"架桥"作用以及过量时的电性中和作用,两种黏附力先增大后减小.各条件下,膜-腐殖酸与腐殖酸-腐殖酸之间黏附力都呈相同的变化趋势,且与对应污染膜的通量衰减幅度具有正相关性,为更加深入了解膜污染的形成机制提供了一定的理论支持.     

蛋白质对PVDF超滤膜污染行为的界面微观作用力解析

采用原子力显微镜,结合自制微颗粒探针,对膜-污染物及污染物-污染物间微观作用力进行了检测分析,考察了不同p H条件下牛血清蛋白(BSA)在不同界面特性PVDF超滤膜上的膜污染行为.结果表明,在膜过滤初期,通量剧烈衰减主要由BSA和膜之间黏附力作用导致,在膜过滤后期,BSA与BSA之间的黏聚作用则是影响后期膜污染行为的主要因素;PA膜-BSA和PP膜-BSA之间的黏附作用力均大于BSA-BSA之间的黏聚作用力,说明在整个膜过滤过程中,BSA与PVDF超滤膜之间的黏附作用对膜污染起主导作用;相同p H条件下,PA膜-BSA之间的微观作用小于PP膜-BSA之间的相互作用力,说明亲水性较强的PA膜具有较强的抗污染性;而PA膜和PP膜过滤后期BSA-BSA之间黏聚力相差不大,也进一步说明膜过滤过程中膜-污染物之间的微观作用力是影响膜污染行为的主要因素.     

荷电超滤膜对天然有机物去除及膜污染行为的影响

以Aldrich 腐殖酸溶液为水样,研究比较了溶液环境(pH值、离子强度和钙离子)对荷电改性再生纤维素超滤膜和传统中性未改性再生纤维素超滤膜过滤过程的影响.结果表明, ①pH值主要通过质子化作用影响荷电膜以及腐殖酸分子的荷电量,进而影响荷电超滤过程.溶液pH值从7.5下降到3.5时,荷电超滤膜对腐殖酸的截留率从92%减少到79%,超滤4 h时,膜通量下降从26%增加到36%.②离子强度的改变是通过影响腐殖酸分子的物化性质和静电屏蔽作用来影响超滤过程的.当溶液离子强度为0、 3和100 mmol/L时,初始截留率依次降低,分别为92%、 87%和48%,超滤4 h时,荷电超滤膜的通量下降依次增加,分别为26%、 35%和63%.③Ca2+浓度的影响,需要综合考虑静电屏蔽作用、Ca2+的架桥作用以及滤饼层的压实性等各方面的影响.④pH值、离子强度和钙离子对中性超滤膜过滤行为的影响趋势与荷电超滤膜相似,但其影响程度有着较大的差别.研究结果对荷电超滤膜技术在实际应用中选择合适环境条件提供了参考.     

溶液环境对荷电超滤膜和传统中性超滤膜去除天然有机物的影响

以Aldrich 腐殖酸溶液为水样,研究比较了溶液环境(pH值、离子强度和钙离子)对荷电改性再生纤维素超滤膜和传统中性未改性再生纤维素超滤膜过滤过程的影响.结果表明, ①pH值主要通过质子化作用影响荷电膜以及腐殖酸分子的荷电量,进而影响荷电超滤过程.溶液pH值从7.5下降到3.5时,荷电超滤膜对腐殖酸的截留率从92%减少到79%,超滤4 h时,膜通量下降从26%增加到36%.②离子强度的改变是通过影响腐殖酸分子的物化性质和静电屏蔽作用来影响超滤过程的.当溶液离子强度为0、 3和100 mmol/L时,初始截留率依次降低,分别为92%、 87%和48%,超滤4 h时,荷电超滤膜的通量下降依次增加,分别为26%、 35%和63%.③Ca2+浓度的影响,需要综合考虑静电屏蔽作用、Ca2+的架桥作用以及滤饼层的压实性等各方面的影响.④pH值、离子强度和钙离子对中性超滤膜过滤行为的影响趋势与荷电超滤膜相似,但其影响程度有着较大的差别.研究结果对荷电超滤膜技术在实际应用中选择合适环境条件提供了参考.     

Effects of protein properties on ultrafiltration membrane fouling performance in water treatment

Protein-like substances always induce severe ultrafiltration (UF) membrane fouling. To systematically understand the effect of proteins, regenerated cellulose UF membrane (commonly used for protein separation) performance was investigated in the presence of bovine serum albumin (BSA) under various water conditions. Results showed that although trypsin enhanced the membrane flux via proteolysis, catalysis took a long time. Membrane fouling was alleviated at high solution pH and low water temperature owing to the strong electrostatic repulsion force among BSA molecules. Both Na⁺ and Ca²⁺ could increase membrane flux. However, Ca²⁺ played a bridging role between adjacent BSA molecules, whereas membrane fouling was alleviated via a hydration repulsion force with Na⁺. The order of influence on membrane fouling was as follows: Ca²⁺ concentration > Na⁺ concentration > pH > temperature > trypsin concentration. Furthermore, a polyvinylidene fluoride UF membrane experiment showed that Ca²⁺ could reduce the fouling induced by BSA. Thus, the differences in UF membrane performance will have application potential for alleviating UF membrane fouling induced by proteins during water treatment.     

Towards a better hydraulic cleaning strategy for ultrafiltration membrane fouling by humic acid: Effect of backwash water composition

As a routine measurement to alleviate membrane fouling, hydraulic cleaning is of great significance for the steady operation of ultrafiltration (UF) systems in water treatment processes. In this work, a comparative study was performed to investigate the effects of the composition of backwash water on the hydraulic cleaning performance of UF membranes fouled by humic acid (HA). Various types of backwash water, including UF permeate, Milli-Q water, NaCl solution, CaCl₂ solution and HA solution, were compared in terms of hydraulically irreversible fouling index, total surface tension and residual HA. The results indicated that Milli-Q water backwash was superior to UF permeate backwash in cleaning HA-fouled membranes, and the backwash water containing Na⁺ or HA outperformed Milli-Q water in alleviating HA fouling. On the contrary, the presence of Ca^2 + in backwash water significantly decreased the backwash efficiency. Moreover, Ca^2 + played an important role in foulant removal, and the residual HA content closely related to the residual Ca^2 + content. Mechanism analysis suggested that the backwash process may involve fouling layer swelling, ion exchange, electric double layer release and competitive complexation. Ion exchange and competitive complexation played significant roles in the efficient hydraulic cleaning associated with Na⁺ and HA, respectively.     

Adsorptive behaviors of humic acid onto freshly prepared hydrous manganese dioxides

This study focused on the adsorptive behaviors of humic acid onto freshly prepared hydrous MnO₂(s) (δMnO₂), and investigated the feasibility of employing δMnO₂ for humic acid removal from drinking water. Effects of such parameters as molecular mass of humic acid, kinds of divalent cations on adsorptive behaviors and possible mechanisms involved were investigated. This study indicated that humic acid with higher molecular mass exhibited more tendency of adsorbing onto δMnO₂ than that with lower molecular mass. Ca²⁺ facilitated more humic acid adsorption than Mg²⁺; UV-Vis spectra analysis indicated higher capabilities of Ca²⁺ coordinating with acidic functional groups of humic acid than that of Mg²⁺. Additionally, ζ potential characterization indicated that Ca²⁺ showed higher potential of increasing gz potential of δMnO₂ than Mg²⁺. Ca²⁺ of 1.0 mmol/L increased ζ potential of δMnO₂ from −37 mV (pH 7.9) to +7 mV (pH 7.2), while 1.0 mmol/L Mg²⁺ increased to lower value as −9 mV (pH 6.5), correspondingly. Fourier transform infrared (FTIR) spectra demonstrated the adsorption of humic acid onto δMnO₂, showing the important roles of-COO⁻ functional groups and surface Mn-OH in the adsorption of humic acid onto δMnO₂. Translated from Acta Scientiae Circumstantiae, 2005, 25(3): 351–355 [译自: 环境科学学报]     

Effect of calcium on adsorption capacity of powdered activated carbon

We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca²⁺, were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca²⁺ was doped into HA. Also, HA and Ca²⁺ taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca²⁺ concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca²⁺, pH had a small rise, but the extent of pH of later solution was bigger.     

Effect of calcium on adsorption capacity of powdered activated carbon

We investigated the effect of calcium ion on the adsorption of humic acid (HA) (as a target pollutant) by powered activated carbon. The HA adsorption isotherms at different pH and kinetics of two different solutions including HA alone and HA doped Ca²⁺, were performed. It was showed that the adsorption capacity of powdered activated carbon (PAC) for HA was markedly enhanced when Ca²⁺ was doped into HA. Also, HA and Ca²⁺ taken as nitrate were tested on the uptake of each other respectively and it was showed that the adsorbed amounts of both of them were significantly promoted when HA and calcium co-existed. Furthermore, the adsorbed amount of HA slightly decreased with the increasing of Ca²⁺ concentration, whereas the amount of calcium increased with the increasing of HA concentration, but all above the amounts without addition. Finally, the change of pH before and after adsorption process is studied. In the two different solutions including HA alone and HA doped Ca²⁺, pH had a small rise, but the extent of pH of later solution was bigger.     

天然腐殖酸对黄土吸附敌草隆的影响

为研究添加天然腐殖酸条件下黄土对有机农药的吸附过程及影响机制,以敌草隆为目标污染物,采用批量平衡试验法,分析黄土与黄土+HA（在黄土中添加腐殖酸）处理对敌草隆的吸附动力学、吸附热力学、解吸动力学过程及其主要影响因素（如pH、离子强度等）.结果表明:①与黄土相比,黄土+HA对敌草隆的吸附时间较短,且二者均符合颗粒内部扩散模型.②Freundlich等温吸附模型能够较好地拟合黄土及黄土+HA对敌草隆的吸附热力学过程.黄土和黄土+HA对敌草隆的吸附自由能（ΔGθ）、熵变（ΔSθ）均小于0,表明反应是一个自发进行且混乱度逐渐减小的过程;添加HA使黄土对敌草隆的焓变（ΔHθ）由负值变为正值,即由放热过程转化为吸热过程,表明温度升高使HA表面的微孔数量增多,为敌草隆提供了更多的吸附位点.③随着pH的升高,黄土和黄土+HA对敌草隆的吸附量均缓慢减小,当pH>7时吸附趋于平衡.④不同离子（Ca2+、Na+、Mg2+）及离子强度下,黄土和黄土+HA对敌草隆的吸附量随着c（Ca2+）的减小而增大,与同浓度的Mg2+和Ca2+相比,Mg2+存在下黄土对敌草隆的吸附量较大;与同浓度的Ca2+和Na+相比,Na+存在下黄土对敌草隆的吸附量较大.⑤由解吸动力学过程可以看出,添加天然HA可延长敌草隆在黄土中的滞留时间.研究显示,HA的存在提高了敌草隆在黄土中的迁移能力,并使其吸附机制发生了改变.