聚砜膜制备及正渗透处理酸性矿井水试验研究

采用正渗透(FO)工艺处理酸性矿井水(AMD),以NaCl为原料液、MgCl2为汲取液,研究了汲取液浓度、膜取向、流速等操作条件对正渗透水通量及反向溶质扩散的影响。结果表明:FO对AMD中的Al3+、Fe2+、Cu2+、Zn2+等金属离子的截留率分别达到99.8%、100%、98.9%和99.5%,硫酸盐的截留率达到97.5%;采用纳滤工艺回收正渗透汲取液,对于Mg2+的截留率达到73.3%。     

正向渗透汲取剂研究进展

正向渗透(FO)是一种新兴的水处理技术,以选择性半透膜两侧的渗透压差为驱动力,使水穿过半透膜由低浓度侧到达高浓度侧。整个过程可自发进行,无需外加压力,具有低能耗、高能效、绿色环保等优点。汲取剂作为FO工艺的关键环节之一,其渗透压、分子量、溶解度等自身特性和回收途径的难易程度直接影响正渗透工艺过程的效率。该文从正向渗透的基本原理出发,总结近10 a来汲取剂的研究进展,比较多种汲取剂的优缺点,为实际应用中汲取剂的选择提供参考。     

正渗透技术在水和废水处理中的应用研究

正渗透(Forward osmosis,FO)技术是一种由渗透压驱动的膜技术,与传统的机械压力驱动的膜技术相比,具有出水水质高、能耗低、操作压力小、设备简单易操作、污染小等特点,近年来在水和废水处理的研究领域受到越来越多的关注.但FO技术目前仍然存在一些问题,如浓差极化、膜污染、汲取液溶质返混和汲取液的后处理等,使之目前仍未得到广泛的应用.本文对已有FO技术的相关文献进行较为全面系统的归纳,介绍了FO技术的原理,以及在海水脱盐、市政污水处理、特种废水处理等领域的应用,讨论了影响FO运行的主要因素(主要包括FO膜、汲取液、原水性质和运行条件等方面),并着重阐述了FO技术目前存在的问题(浓差极化、膜污染、汲取液溶质返混和汲取液的后处理).最后,对FO技术未来的研究和发展方向给出了建议.     

季铵化纳米SiO2-N+@PCMS荷电改性正渗透复合膜及其对四环素的分离性能

通过化学法合成叔胺化纳米SiO₂（SiO₂-N）和聚对氯甲基苯乙烯（PCMS）,利用SiO₂-N中的叔胺基与PCMS中的氯甲基反应,生成大分子季铵化纳米SiO₂（SiO₂-N⁺@PCMS）,通过进一步与聚偏氟乙烯（PVDF）共混,以相转化法制备纳米荷电改性的PCMS/PVDF支撑底膜,进而采用界面聚合法制备正渗透（FO）复合膜.采用红外光谱、扫描电镜、zeta电位计和接触角测定仪等对支撑底膜和FO膜表面的化学结构、形貌、荷电性和亲水性等进行了分析,并通过正渗透装置对膜的分离性能进行了测试.结果表明该改性正渗透膜具有较好的荷正电性能,且随着SiO₂-N的加入可以有效提高正渗透膜的亲水性和分离性能,添加2 %的SiO₂-N改性正渗透膜的纯水通量最高可达到22.76 L·m^-2·h^-1,对四环素的截留率可达到98.5 %,经3次水-四环素-水循环过滤后,纯水通量恢复率仍然可达到90.1%.     

初始pH值对正渗透浓缩城市污水和回收磷的影响

为实现从城市污水中回收磷和水资源并同时减少后续处理反应器容积的目的,采用正渗透膜对城市污水进行浓缩,并探究城市污水的初始pH值对浓缩效果和磷回收的影响.首先采用合成城市污水进行正渗透浓缩试验,当提高原料液（FS）的初始pH值至9.5时,FS体积浓缩接近初始体积的1/10后,膜上及垫网上吸附磷含量约为其初始总量的44%,有利于磷的回收.当采用实际城市污水作为FS时,在初始pH值为9.5条件下进行浓缩后,污染膜面存在松散团聚的圆球颗粒,使得该条件下膜面污染物更易被洗脱,膜清洗后水通量高于不调节pH值条件下的水通量.膜原位超声清洗后,浓缩污水变为悬浊液,经静置沉降后收集沉淀物,其主要成分为CaCO₃、鸟粪石和磷酸镁类物质.当初始pH值为9.5时浓缩所得沉淀物中的CaCO₃和鸟粪石含量更高.调节城市污水初始pH值至9.5左右,对其进行三轮42h的连续运行浓缩后,污水的体积浓缩倍数约为8倍,磷回收率可达到63.9%.浓缩结束后,对膜先后进行原位超声清洗和碱洗加酸洗的化学清洗,清洗后膜通量约为初始通量的78%.浓缩后污水的pH值在8.5~9.1之间,且COD/TN值明显提高（从3.6至11.5）,有利于后续的生物脱氮除磷.     

一体式膜生物反应器膜污染影响因素研究

试验采用聚丙烯中空纤维膜,通过正交试验考察了膜通量、抽停时间、曝气量对膜过滤压力的影响,得出适合的膜通量是减缓膜污染的决定性因素。并确定了适宜的运行条件：膜通量5L／（m2·h）,抽吸时间8min,停抽时间2min,曝气量0．6m3／h;同时考察了EPS中多糖和蛋白质对膜污染的影响,得出多糖是主要的污染物质。     

正渗透处理生活污水过程中的膜污染研究

采用海水为驱动液,研究了正渗透处理生活污水过程中的通量变化和膜污染行为.结果表明,采用分离层朝向原料液(AL-FS)的膜过滤方向可以降低膜污染程度,并获得稳定的通量.长时间(144h)的运行下膜两侧均出现不同程度的污染.膜污染分析显示支撑层的污染程度较低.但海水中的硅酸盐可能在其表面形成沉积物.相比之下,分离层形成了厚的污染层,主要是由污水中的物质如有机物、微生物、胶体类、盐类等沉积在膜表面造成,是通量降低的主要原因.正渗透膜对营养物质具有高的截留率,运行结束后海水的总有机碳、氨氮和总磷含量为2.49,2.40,0.05mg/L.说明正渗透采用海水为驱动液处理生活污水具有一定的应用前景.     

水力条件对PRO工艺效能影响及膜污染机理

研究以单宁酸和海藻酸钠为模型污染物,考察了有效渗透压差、汲取液侧操作压力、错流剪切力等水力条件对压力阻尼渗透工艺效能的影响,并利用XDLVO理论分析了膜污染机理.结果表明,相比海藻酸钠,单宁酸主要吸附在膜的多孔支撑层内部,造成的膜污染更为严重.当PRO过滤单宁酸时,较高的有效渗透压差和较大的错流剪切力提高了PRO工艺的水通量和功率密度水平,同时加重了膜污染,但是PRO膜对单宁酸的截留率均在85%以上.汲取液侧施加较高的操作压力,一方面减小了有效渗透压差,降低了水通量水平;另一方面提高了功率密度水平并缓解了膜污染,当操作压力从1bar增至4bar时,初始水通量降至10.5L/m2h,而产能提高了200%.XDLVO计算结果表明,单宁酸的界面自由能更高,更容易相互聚合并粘附在PRO膜上,结合水力条件的影响,其造成的通量损失比海藻酸钠更严重.     

聚砜-聚酰胺正渗透复合膜的制备及性能优化

采用相转化的方法制备聚砜支撑层,在其表面进行界面聚合得到聚砜-聚酰胺正渗透复合膜。系统研究了聚砜浓度、溶剂比例、支撑层厚度对膜性能的影响,并且优化了测试条件(如:膜面流速、错流方向、原料液温度以及驱动液浓度)。结果表明,在聚砜含量为w=12%、NMP与DMF质量比为3∶1、刮膜厚度为150μm、膜面流速为2.47 cm/s、反向错流方式下,聚砜-聚酰胺正渗透膜性能为:FO模式下,水通量为12.69 L/(m~2·h),反向盐通量为5.55 g/(m~2·h);PRO模式下,水通量为21.48 L/(m~2·h),反向盐通量为9.18 g/(m~2·h)。此外,原料液温度升高和驱动液浓度增加有利于提高膜的性能。正渗透复合膜的形貌和表面粗糙度通过SEM和AFM进行表征。     

电导率对厌氧产酸、正渗透与微生物燃料电池耦合工艺运行性能的影响

将厌氧产酸(AA)、正渗透技术(FO)与微生物燃料电池(MFC)进行耦合,构建了用于污水处理的AAFO-MFC耦合工艺,实现污水的同步产电和回用.由于电导率是AAFO-MFC运行的关键因素,考察了电导率对系统运行性能的影响.结果表明,较高的电导率可以降低MFC的内阻,提高产电,但是会加重FO膜污染,导致FO膜通量快速衰减,缩短运行时间.电导率对出水水质并没有显著影响,FO膜出水的总有机碳(TOC)和总磷(TP)浓度分别低于4 mg·L~(-1)和0.5 mg·L~(-1),但是FO膜对于氨氮(NH+4-N)的截留效果较差.控制反应器内电导率为7~8 m S·cm-1时,系统整体性能表现最佳,可以获得连续且相对稳定的输出电压,而且FO膜通量下降较为缓慢,运行周期达到29 d.     

Fouling distribution in forward osmosis membrane process

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis （FO） membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic （alginate） fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter- current flow operation of FO membrane process.     

正渗透去除地表水中DOM的效能研究

采用经砂滤处理后的滆湖水作为原料液,氯化钠溶液作为汲取液,在不同影响因素条件下进行正渗透试验,并对试验后的膜片进行清洗,探究膜污染的可逆性.结果表明:提高汲取液浓度、运行温度及膜面流速均可有效增加膜通量;正渗透对滆湖水体中的溶解性微生物代谢产物、类色氨酸、类富里酸和腐殖酸四种主要DOM成分均有较好的去除效果,DOC、UV₂₅₄截留率均在96%以上;短期运行通过水力清洗几乎可以完全恢复膜通量,而长期运行通过超声清洗可以基本恢复全部膜通量,通过分析膜清洗液可知造成膜污染的主要物质为类色氨酸类和类富里酸类物质.     

Fatty acid fouling of forward osmosis membrane: Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition

Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5 hr at unadjusted pH 3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5 mmol/L Ca^2 +, active layer facing draw solution (AL-DS) and 1.5 mol/L NaCl (DS); 2. No Ca^2 +, active layer-facing FS (AL-FS) and 4 mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH 3.56, and larger than the two values at pH 9.00. This manifested that, at pH 3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH 9.00, the mutual effects of OA and BSA eased the membrane fouling.     

采用膜污染指数评估天然有机物在低压超滤膜中的污染行为

针对超滤膜的过滤特性,采用膜污染指数（FI）来研究天然有机物（NOM）的膜污染行为.实验中,腐殖酸（HA）、牛血清蛋白（BSA）以及海藻酸钠（NaAlg）被用作模型有机物进行超滤膜污染研究.结果表明,NOM-膜滤先后经过快反应和慢反应污染阶段,其中快反应膜污染指数（TFIF）远大于慢反应膜污染指数（TFIS）.说明短时间内NOM容易在低压膜上积累,造成通量迅速下降,引起较为严重的污染.因此,反应最初阶段,低压膜与有机物的作用决定了整个膜污染的趋势.经过水力清洗,通量有一定恢复,膜阻力降低,能够去除部分污染物,但仍有少量有机物附着在膜丝,从而造成不可逆污染.3种有机物造成的不可逆污染比例依次为BSA〉HA〉NaAlg,而通过化学清洗后,其不可逆污染比例依次为：NaAlg〉BSA〉HA,腐殖酸和蛋白容易造成不可逆污染,但碱洗易于除去,多糖造成的不可逆污染相对较轻,但碱洗难以去除.污染物与膜之间的相互作用可能是造成污染的主要原因.总的说来,FI计算方法简单,能够综合描述膜污染情况,具有一定的应用价值.     

基于膜特征参数变化的蛋白质超滤过程膜污染研究

为进一步研究多种蛋白质体系超滤过程的膜污染机制,采用切割相对分子质量为50×103的聚醚砜(polyethersulfone,PES)超滤膜,对溶菌酶(lysozyme,LYS)、牛血清蛋白(bovine serum albumin,BSA)、LYS+BSA等3种不同蛋白质溶液的超滤过程进行了研究.运用接触角仪、场发射扫描电镜(field emission scanning electron microscope,FESEM)、原子力显微镜(atomic force microscope,AFM)测定了不同污染阶段膜特征参数的变化.结果表明,超滤膜通量变化明显呈现3个阶段:初期(约0~5min)衰减迅速、中期(约5~60 min)衰减缓慢、后期(约60~120 min)趋于稳定;整个超滤过程中,LYS污染膜的通量衰减幅度最大,LYS+BSA次之,BSA最小.膜特征参数变化表明:LYS对膜的初期污染主要以膜孔窄化为主,中期污染由膜孔堵塞和膜孔窄化共同控制;BSA初期膜污染以膜孔堵塞为主,中期污染以膜孔窄化为主;滤饼层过滤是BSA、LYS后期膜污染的主要机制.LYS+BSA二元混合溶液中的LYS对膜污染的产生起主导作用.     

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.     

胞外聚合物对MBR中改性无纺布过滤性能的影响

采用统计分析方法研究了胞外聚合物(extra-cellular polymeric sub6tances, EPS)对浸渍式膜生物反应器(submerged membrane bioreactor, SMBR)中聚乙烯醇改性聚丙烯无纺布过滤性能的影响.结果表明,无纺布膜组件表面污泥的溶解性EPS(soluble EPS, EPSs)、EPSs,组成(protein/carbohydrate, P/C)以及相对疏水性(relative hydrophobicity, RH)对膜的过滤性能有显著影响,与膜污染阻力的皮尔逊相关系数(rp)分别为:0.868、0.840、0.890;改性无纺布膜组件能有效抑制EPSs,的吸附、降低EPSs组分中P/C的比率、减少活性污泥的沉积.表明聚丙烯无纺布通过亲水改性后,过滤性能得到明显改善,表现出一定的耐污染性.