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.     

Controlling various contaminants in wastewater effluent through membranes and engineered wetland

For effective wastewater reclamation and water recovery, the treatment of natural and effluent organic matters (NOM and EfOM), toxic anions, and micropollutants was considered in this work. Two different NOM (humic acid of the Suwannee River, and NOM of US and Youngsan River, Korea), and one EfOM from the Damyang wastewater treatment plant, Korea, were selected for investigating the removal efficiencies of tight nanofiltration (NF) and ultrafiltration (UF) membranes with different properties. Nitrate, bromate, and perchlorate were selected as target toxic anions due to their well known high toxicities. Tri-(2-chloroethyl)-phosphate (TCEP), oxybenzone, and caffeine, due to their different K _ow and pK _a values, were selected as target micropollutants. As expected, the NF membranes provided high removal efficiencies in terms of all the tested contaminants, and the UF membrane provided fairly high removal efficiencies for anions (except for nitrate) and the relatively hydrophobic micropollutant, oxybenzon. Through the wetlands, nitrate was successfully removed. Therefore, a fair process of combining membranes with an engineered wetland could be proposed for sustainable wastewater reclamation and optimum control of contaminats.     

海藻酸钠强化超滤含铜废水

聚合有机物强化超滤技术因具有操作压力低、膜通量大且截留效果好的优点,而受到了广泛的关注.文章研究了天然有机物海藻酸钠强化超滤去除模拟含铜废水的特性及影响因素,试验结果表明,当海藻酸钠投加量为100 mg/L.pH=6.0,温度为25℃,Cu2+初始浓度为10mg/L时,MWCO(截留分子量)为4 kDa.6 kDa,1...     

Effect of additive on the formation of polyacrylonitrile membrane

The effect of additives CaCl2 and CaCl2/H2O on the properties of polyacrylonitrile(PAN) ultrafiltration(UF) membranes prepared by phase inversion process was studied. The dissolving capacity of the casting solution for CaCl2 was enhanced by the addition of H2O. The membranes are characterized in terms of the pure water flux and molecular weight cut-off(MWCO). The addition of CaCl2 or CaCl2/H2O to the casting solution increases the resulting membrane permeability.     

不同相对分子质量的有机物对膜通量的影响

采用截留分子量分别为10、30kDa的聚醚砜膜和100kDa的聚偏氟乙烯膜对原水进行分级处理,并采用截留分子量分别为150kDa的聚偏氟乙烯膜和0.1μm的醋酸纤维素膜对出水进行膜过滤试验,研究不同相对分子质量的有机物对膜通量的影响.结果表明,虽然相对分子质量>30kDa的大分子有机物仅为总有机物的15%,但它分别引起微滤膜的通量下降86%和超滤膜通量下降54%.混凝处理可以去除相对分子质量>100kDa的有机物,这部分有机物导致通量下降40%以上.因此,尽管混凝处理仅去除10%的有机物,但改善通量的效果显著.粉末活性炭可以去除相对分子量<30kDa的小分子有机物,这部分有机物对通量下降的贡献程度甚低.因此,尽管粉末活性炭去除76%的有机物,但改善通量的效果甚微.预处理改善通量的效果并不取决于去除有机物的多少,而是取决于所去除的有机物对通量的影响大小.     

荷电超滤膜去除水中天然有机物的研究进展

较传统的超滤过程,使用荷电膜的超滤技术能实现对水中天然有机物(NOM)更高的去除率,并同时减少膜污染。文章从膜材料性质、溶液环境和NOM性质这几方面来综述荷电超滤膜去除水中天然有机物的研究进展。最后对荷电超滤膜去除NOM方面的进一步研究工作提出了建议。     

超滤膜污染的光学在线监测和阻力分布研究

采用光散射颗粒分析仪(PDA)对截留液中颗粒物的浓度变化进行在线监测,并利用过滤体系中颗粒的质量守恒分析原理,建立了超滤膜污染的光学在线监测分析系统,并分别对截留分子量为1万,5万,10万三种聚醚砜超滤膜过滤高岭土悬浊液特性进行了分析研究。结果分析表明截留分子量越小的PES膜渗透单位体积液体时颗粒沉积量越多,也就是说具有相同沉积量的膜,截留分子量越小其具有的水力阻力越大。论文提出的光学在线监测方法为研究悬浮物质的膜污染提供了一种新的研究思路。     

Large pore size polyacrylonitrile membrane for ultrafiltration

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｒｅｃｅｎｔｙｅａｒｓ,ｔｈｅｔｅｃｈｎｉｑｕｅｆｏｒｕｌｔｒａｆｉｌｔｒａｔｉｏｎｈａｓｇａｉｎｅｄｒａｐｉｄｄｅｖｅｌｏｐｍｅｎｔ.Ｍｏｒｅａｎｄｍｏｒｅｋｉｎｄｓｏｆｍｅｍｂｒａｎｅｓａｒｅｓｔｕｄｉｅｄａｎｄｍａｎｕｆａｃｔｕｒｅｄ ,ａｎｄａｌａｒｇｅ ｓｃａｌｅｉｎｄｕｓｔｒｉａｌａｐｐｌｉｃａｔｉｏｎｈａｓｂｅｅｎｇｒｏｗｎ .ＰＡＮｐｏｌｙｍｅｒｉｓｅｘｔｅｎｓｉｖｅｌｙｕｓｅｄｔｏｐｒｅｐａｒｅＵＦｍｅｍｂｒａｎｅｓ(Ｓｔｏｉｋｏ,1 991 ) .Ｉｔｓｈｙｄｒｏｐ…     

碳纳米管径向尺寸对碳纳米管自支撑膜孔隙结构及通量的影响

为了探索碳纳米材料膜在水处理中应用的可能性,本实验选取4种径向尺寸的碳纳米管(Carbon Nanotubes, CNTs),采用压力辅助过滤技术制备CNTs自支撑膜.通过对CNTs自支撑膜的平均孔径、孔径分布及截留分子量(Molecular weight Cut-Off,MWCO)等进行分析,研究了CNTs径向尺寸变化对CNTs自支撑膜孔隙结构的影响.结果表明,CNTs的径向尺寸越小,制备得到的CNTs自支撑膜越趋向于形成小孔径的膜孔,且孔径分布更加均匀,孔隙面积比越高,膜的MWCO越小.单壁碳纳米管(Single-walled carbon nanotube, SWNT)与多壁碳纳米管(Multi-walled carbon nanotube, MWNT)相比,前者更容易形成膜平均孔径更小且孔径分布更均匀的CNTs自支撑膜.膜通量测定结果表明,研究制备的CNTs自支撑膜的通量属于低压膜范围,通量在230～347 L·m~(-2)·h~(-1)·bar~(-1)之间.其中,虽然由径向尺寸较小的CNTs所制备的CNTs自支撑膜的平均孔径更小,但由于其具有更高的孔隙面积比和更小的膜厚度,其纯水通量相对高于由大径向尺寸CNTs制备的CNTs自支撑膜.     

Membrane flux dynamics in the submerged ultrafiltration hybrid treatment process during particle and natural organic matter removal

Exponential relationship was developed to quantify the normalized membrane flux dynamics during the filtration period and fitted the results well.     

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.     

有机膜的无机改性及其性能研究

以无机纳米氧化铝粒子作为无机添加剂与聚偏氟乙烯（PVDF）共混,采用相转换法合成了有机-无机共混超滤膜.通过测定膜与纯水的接触角,表征膜的亲水性;用激光共聚焦显微镜(CLSM)、扫描电镜（SEM）和透射电镜（TEM）观察了膜的表面结构、表面孔分布和断面孔的结构及纳米颗粒在膜中的分散情况;利用杯式超滤装置对改性膜的透过性能、截留性能以及抗污染性能进行了测试;用强度测定仪测定了膜强度.结果表明,纳米Al₂O₃ 的加入改善了PVDF膜的表面亲水性、通量、强度和抗污染性.     

多壁碳纳米管序列修饰聚氯乙烯超滤膜的制备及性能研究

采用硫酸、硝酸混酸改性多壁碳纳米管(MWCNTs),通过化学水热法在改性的MWCNTs表面负载纳米Fe_3O_4,将负载Fe_3O_4的MWCNTs(MWCNTs/Fe_3O_4)与PVC在无磁场、有磁场作用下共混制膜,获得MWCNTs无序排列、有序排列修饰的PVC超滤膜,同时,制备了纯PVC膜以作比较.对共混膜有序修饰机制及断面形态进行了分析,对相关性能参数如接触角、膜的溶胀、膜孔隙率、膜平均孔径、纯水通量、截留性能及吸附性能等进行了研究.研究结果表明:MWCNTs/Fe_3O_4的加入使膜的亲水性、纯水通量、截留性能等有了显著提高,MWCNTs有序排列修饰使膜在表皮层形成了更加致密,更为狭长的微孔结构,具有了更优异的导流网络通道,在长时间运行条件下仍能保持良好的过滤负荷,提高了膜的性能.     

有机物对UF膜过滤通量的影响

采用截留分子量为30000的聚醚砜超滤膜进行膜过滤试验,研究有机物的特性,如亲疏水性以及相对分子质量对超滤膜通量的影响.试验结果表明,过滤亲水性组分时膜通量明显高于过滤疏水性组分.对2种不同水源的试验表明,尽管有机物含量相同,但由于亲疏水性的比例不同,造成的膜通量下降不同.疏水性越大的原水,其膜通量下降也越大.因此,疏水性组分是造成通量下降的主要因素.试验还表明,相对分子质量较大的有机物并非通量下降的主要因素,有机物的分散性可能是影响通量的主要因素.     

添加剂PEG对共混超滤膜结构和性能的影响

以不同分子量聚乙二醇 (PEG)作为PSf/A共混超滤膜的添加剂 ,测定所制备膜的水通量、截留率 .结果表明 ,膜的水通量随PEG分子量的变化呈现非线性关系 .当PEG分子量为4000时 ,水通量达到最大值115.2mL·(cm²·h)^-1,是不加PEG时的6倍 .通过超滤实验结果以及膜结构的电镜照片的观察 ,研究了PSf/A共混超滤膜体系中PEG作用的规律 .PEG分子量的增加改变了PSf/A铸膜液体系的相平衡关系 ,使铸膜液成为热力学不稳定体系 ,加速了相分离的发生 ;另外 ,PEG分子量的增加提高了铸膜液的粘度 ,引起相分离的延迟,这2种作用影响了膜的最终结构和性能.     

在超滤草浆黑液过程中膜阻力的分布

采用截留分子量30000,20000,10000和6000的超滤膜,对草浆黑液进行了超滤过程中膜阻力分布的研究.通过测定不同条件下膜样品的通量,对聚乙二醇标准物的截留率,指出在超滤黑液过程中各部分阻力的比例和超滤膜的分离特性的变化.各种膜样品的热重分析结果表明,膜污染是由微量有机物引起的污染.     

超滤去除水中内分泌干扰物（BPA）的效果和影响因素

采用终端超滤工艺去除饮用水中内分泌干扰物双酚A（BPA）,主要考察了BPA初始浓度、膜截留相对分子质量、pH、离子强度和有机物对BPA去除效果的影响.结果表明,超滤对饮用水中BPA具有良好的去除效果.当BPA的初始浓度在100～600μg/L范围内,截留相对分子质量2?000～10?000的超滤膜对BPA的去除率均在92.0%以上.溶液的pH值接近BPA的pK_a（9.6～11.3）时,BPA去除率明显降低.离子强度对去除率的影响较小.溶液中的腐殖酸对超滤去除BPA的影响较小.试验证实,吸附是超滤去除疏水性BPA分子的主要机理.     

The role of extracellular organic matter on the cyanobacteria ultrafiltration process

The membrane fouling caused by extracellular organic matter (EOM) and algal cells and organic matter removal of two typical cyanobacteria (M. aeruginosa and Pseudoanabaena sp.) during ultrafiltration (UF) process were studied in this work. The results showed that EOM had a broad molecular weight (Mw) distribution and the irreversible membrane fouling was basically caused by EOM. Moreover, humic acid and microbial metabolites were major components of EOM of two typical cyanobacteria. Since EOM could fill the voids of cake layers formed by the algal cells, EOM and algal cells played synergistic roles in membrane fouling. Fourier transform infrared spectroscopy analysis indicated that the CH₂ and CH₃ chemical bonds may play an important role in membrane fouling caused by EOM. Interestingly, the cake layer formed by the algal cells could trap the organic matter produced by algae and alleviate some irreversible membrane fouling. The results also showed that although the cake layer formed by the algal cells cause severe permeate flux decline, it could play a double interception role with UF membrane and increase organic matter removal efficiency. Therefore, when using UF to treat algae-laden water, the balance of membrane fouling and organic matter removal should be considered to meet the needs of practical applications.     

海藻酸及腐殖酸共存对PVDF超滤膜的污染行为

为了揭示有机物对PVDF超滤膜的污染行为,选用典型亲/疏水性有机污染物海藻酸(SA)及腐殖酸(HA),采用原子力显微镜结合自制的PVDF膜材料探针和污染物探针定量测定了PVDF-污染物及污染物-污染物间的作用力,并进行PVDF膜污染试验和污染物去除效果分析.结果表明:亲水性SA-PVDF及SA-SA之间的作用力皆大于疏水性HA-PVDF及HA-HA间的作用力,且SA污染膜的通量衰减速率与衰减幅度明显大于HA污染膜,说明了亲水性有机物是引起PVDF超滤膜污染的优势污染物.HA/SA混合污染物试验表明,膜污染行为与混合污染物中优势污染物的含量密切相关;与单种污染物的膜污染行为相比,混合污染物间不存在明显的协同作用促进膜污染.此外,污染物的去除率与相应微观作用力大小及膜污染速率成正相关关系.     

预涂动态膜强化超滤去除海水中有机物及其对膜污染的影响

以粉末活性炭和硅藻土为涂膜材料,在聚醚砜超滤膜表面形成预涂动态膜,考察了预涂动态膜对海水中有机物的去除效果和作用机制,通过比较分析直接超滤和预涂动态膜过滤海水前后膜表面亲疏水性、形貌结构、粗糙度及膜阻力分布的变化,探讨了活性炭和硅藻土预涂覆对超滤膜污染的影响.结果表明,预涂动态膜可提高超滤膜对海水中溶解有机碳(DOC)和UV_(254)的去除率,活性炭预涂动态膜对海水中DOC和UV_(254)的去除率较直接超滤分别提高11.2%和11.3%.硅藻土预涂膜主要利用超滤膜表面形成的硅藻土滤饼层强化海水中蛋白质类有机物的截留,活性炭对海水中小分子有机物的额外吸附导致海水过滤过程中活性炭预涂膜对有机物的去除效果优于硅藻土预涂膜.与直接超滤相比,预涂动态膜过滤海水后膜表面亲水性更好,膜表面粗糙度更低,膜过滤阻力也更小,活性炭预涂动态膜净化海水时膜过滤总阻力较直接超滤降低50.3%.利用涂膜材料在超滤膜表面形成的滤饼层将超滤膜与有机物进行了"隔离",避免了超滤膜与有机污染物直接接触,降低了小分子有机物在膜孔内的吸附堵塞,能够有效减缓超滤膜的不可逆污染.