基于NaOCl扩散行为的膜清洗条件影响及优化

为了探究基于NaOCl扩散行为进行膜清洗的影响因素,建立完善的添加剂强化NaOCl扩散的新型膜清洗方法,本文以牛血清蛋白（BSA）、海藻酸钠（SA）作为模型污染物,通过批次膜清洗实验对膜面剩余污染物浓度、洗脱污染物粒径和膜面污染物形貌进行了测定分析和动态监控,探究不同活性氯（Cl_T）浓度,不同pH值及不同添加剂（十二烷基硫酸钠,SDS）浓度对强化扩散NaOCl清洗的影响,并对操作参数进行了优化,同时也验证了不同条件下的膜清洗机制.结果表明,在Cl_T浓度为200mg/L,pH值为11,SDS浓度为0.4mmol/L的条件下对膜面的清洗效率 > 95%.     

高锰酸盐复合药剂预氧化缓解超滤膜藻类污染的中试研究

通过中试试验考察了高锰酸盐复合药剂(PPC)预氧化强化混凝/沉淀/超滤的组合工艺的除藻效能以及PPC预氧化对藻类引起的膜污染的缓解作用,并对其机理进行了探讨.试验结果表明,投加0.6mg·L-1PPC能使预处理阶段对藻类的平均去除率提高约28%.组合工艺处理高藻水时,PPC预氧化通过强化预处理,降低膜表面的污染负荷,对藻源污染物引起可逆和不可逆污染均具有一定的缓解作用.化学清洗试验结果表明,碱洗对超滤膜TMP恢复效果远远强于酸洗,因而有机物是超滤膜处理高藻水时的主要污染物质.     

超滤处理微污染地表水的膜污染化学清洗研究

针对超滤处理微污染地表水时产生的膜污染,利用电镜扫描和能谱技术分析其膜丝内表面污染物的组份,并考察了几种化学清洗剂对污染膜的清洗效果。试验结果表明,膜丝内表面的污染层是由有机物、微生物和无机物组成,其中有机物覆盖着无机物,以有机污染为主;膜清洗宜先碱洗后酸洗;单一清洗剂中NaOH、NaC1O和H2O2均有较好的清洗效果,但并不能使膜通量完全恢复,而复合清洗剂H2O2+柠檬酸具有显著的清洗效果,膜通量恢复率高达98%。     

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.     

纳滤膜过滤MBR出水的污染原因与清洗方法

为研究膜-生物反应器(MBR)出水对纳滤膜的污染原因及清洗方法,使用场发射扫描电镜、傅立叶变换红外光谱仪、原子力显微镜和接触角仪对经MBR出水污染的纳滤膜表面污染层进行了检测,结果表明,纳滤膜表面污染物包括有机物和无机物,所含元素包括磷、镁等,对经过不同清洗步骤的膜表面进行的检测表明,柠檬酸清洗可以去除镁和大部分磷,这些物质主要以无机形态存在于膜面污染物中;后续NaOH清洗可以进一步去除磷,这部分磷主要来自有机酸、有机磷或蛋白质等膜面污染物.污染使膜表面粗糙度由79.5 nm增大至111.2 nm,但接触角由55.6°变为62.1°,表明亲水性变化不大;酸洗后表面粗糙度显著减小至51.9 nm,接触角变为96.0°,表明有机污染物暴露出来,膜面呈现疏水性;再经碱洗后,膜面粗糙度与亲水性均接近于新膜.这些结果说明,先酸洗后碱洗的方法可以去除绝大部分的膜面污染物,进一步推知膜污染初期主要为有机污染,之后无机物的作用使污染进一步加重.     

MBR处理抗生素废水实验研究

以沈阳某制药厂为例,以制药厂废水处理工程UASB出水为原水,开展了MBR处理抗生素废水小试实验,对CODcr去除效果、氨氮去除效果以及膜的清洗与再生进行了研究。研究表明：当进水CODcr负荷小于7kg/m·3d时,出水CODcr在40mg/L以下,出水氨氮在40mg/L以下,处理效果良好;采用5%NaOH以及0.5%NaClO溶液作为化学清洗药剂时,清洗效果较好。     

太湖原水中膜污染物质的确定与表征

采用混凝沉淀和浸没式微滤膜联用技术处理太湖原水,考察组合工艺中的有机物亲疏水性和分子量分布变化,并分析化学清洗水的有机物组分,以期确定造成膜污染的主要物质成分.结果表明,混凝预处理可有效去除大分子的亲水性有机物,这类有机物仅能导致可逆污染,而中等和小分子的有机物会导致不可逆污染.此外,三维荧光光谱表明与膜污染关系最密切的2个区域为:λex=230nm/λem=330~350nm (区域Ⅰ)和λex=280nm/λem=300~350nm (区域Ⅳ),其对应的胞外蛋白质类有机物和溶解性微生物产物(SMP)是造成微滤膜不可逆污染的主要物质.     

Impacts of sodium hydroxide and sodium hypochlorite aging on polyvinylidene fluoride membranes fabricated with different methods

This study compared the effects of chemical aging on the polyvinylidene fluoride(PVDF)membranes fabricated with the methods of non-solvent induced phase separation(NIPS)(named NIPS-PVDF) and thermally induced phase separation(TIPS)(named TIPS-PVDF). The chemical solutions of sodium hypochlorite(NaClO) and sodium hydroxide(NaOH) were chosen at the concentration of 5000 mg/L. The equivalence of 5 and 10 years was respectively selected as the time of aging. The physicochemical evolutions of membrane aging are characterized on the base of morphology analysis, chemical components, permeation ability and mechanical properties. The aging of NIPS-PVDF membrane led to the elimination of surface hydrophilic additives, while NaO H focused on the dehydrofluorination process resulting in the formation of conjugated chains of polyene on the skeleton structure. The chemical components of the surface of TIPS-PVDF membrane were removed continuously during the aging processes of both NaClO and NaOH, which was caused by the saponification of surface additives and the chain scissions of skeleton structure, but without producing any obvious conjugated chains of polyene. All the aging processes led to the increase of contact angle and the decrease of mechanical properties, and the permeability was reduced first and increased later due to the enlargement of surface membrane pores and membrane block. With the influence of membrane aging, selectivity of membrane was decreased(except coliform bacteria). At the beginning of filtration, the turbidity and particle count were at relatively high levels and declined with the filtration process.     

天然有机物的相对分子质量分布及亲疏水性对微滤膜组合工艺中膜污染的影响

研究采用混凝沉淀+粉末活性炭吸附+高锰酸钾+浸没式微滤膜的组合工艺对太湖水进行中试试验,通过高效凝胶色谱(HPSEC-UV-TOC)和三维荧光(3DEEM)的测定方法,着重考察有机物的相对分子质量(Mr)分布和亲疏水性对膜不可逆污染的影响.凝胶色谱分析表明:预处理可几乎完全去除大分子有机物(Mr>10×103),但仅能去除部分的中等分子(10×103>Mr>1×103)和小分子(Mr<1×103)有机物.研究发现化学清洗水中的有机物相对分子质量多为中等分子和小分子,说明导致膜不可逆污染的主要是中等分子和小分子有机物.此外,洗膜水中强疏和中性亲水组分含量远高于弱疏和极性亲水,说明强疏和中性亲水组分是不可逆污染的主要物质.三维荧光分析表明,芳香族蛋白质和溶解性微生物产物是造成膜不可逆污染的主要污染物.     

Feasibility and simulation model of a pilot scale membrane bioreactor for wastewater treatment and reuse from Chinese traditional medicine

The lack and pollution of water resource make wastewater reuse necessary. The pilot scale long-term tests for submerged membrane bioreactor were conducted to treat the effluents of anaerobic or aerobic treatment process for the high-strength Chinese traditional medicine wastewater. This article was focused on the feasibility of the wastewater treatment and reuse at shorter hydraulic retention time （HRT） of 5.0, 3.2 and 2.13 h. MLSS growth, membrane flux, vacuum values and chemical cleaning periods were also investigated. The experimental results of treating two-phase anaerobic treatment effluent demonstrated that the CODfilt was less than 100 mg/L when the influent COD was between 500-10000 mg/L at HRT of 5.0 h, which could satisfy the normal discharged standard in China. The experimental results to treat cross flow aerobic reactor effluent demonstrated that the average value of CODfilt was 17.28 mg/L when the average value of influent COD was 192.84 mg/L at HRT of 2.13 h during 106 d, which could completely meet the normal standard for water reuse. The maximum MLSS and MLVSS reached 24000 and 14500 mg/L at HRT of 3.2 h respectively. Membrane flux had maximal resume degrees of 94.7% at vacuum value of 0.02 MPa after cleaning. Chemical cleaning periods of membrane module were 150 d. A simulation model of operational parameters was also established based on the theory of back propagation neural network and linear regression of traditional mathematical model. The simulation model showed that the optimum operational parameters were suggested as follows： HRT was 5.0 h, SRT was 100 d, the range of COD loading rate was between 10.664-20.451 kg/（m3.d）, the range of MLSS was between 7543-13694 mg/L.     

平板陶瓷膜深度处理石化废水试验研究

采用平板陶瓷膜中试装置处理石化废水,分析了处理效果与膜污染情况,获得了平板陶瓷膜稳定运行条件下的工艺参数。结果表明:在COD为50~100 mg/L、浊度为2~11 NTU的进水条件下,平板陶瓷膜出水COD与浊度分别为20~42 mg/L和0.05~0.2 NTU,与双层过滤器+中空纤维超滤工艺出水水质较为接近;在运行通量40 L/(m 2·h)、反洗周期45 min、反洗时间60 s的条件下,采用浓度为100~150 mg/L的次氯酸钠每7小时进行1次化学清洗,平板陶瓷膜系统运行较为稳定。     

Identifying the major fluorescent components responsible for ultrafiltration membrane fouling in different water sources

Three-dimensional fluorescence excitation–emission matrix(EEM) coupled with parallel factor analysis(PARAFAC) was performed for a total of 18 water samples taken from three water sources(two lakes and one wastewater treatment plant(WWTP) secondary effluent),with the purpose of identifying the major ultrafiltration(UF) membrane foulants in different water sources. Three fluorescent components(C1, C2 and C3) were identified,which represented terrestrially derived humic-like substances(C1), microbially derived humic-like substances(C2), and protein-like substances(C3). The correlations between the different fluorescent components and UF membrane fouling were analyzed. It was shown that for the WWTP secondary effluent, all three components(C1, C2 and C3) made a considerable contribution to the irreversible and total fouling of the UF membrane.However, for the two lakes, only the C3 exhibited a strong correlation with membrane fouling, indicating that the protein-like substances were the major membrane foulants in the lake waters. Significant attachment of C1, C2 and C3 to the UF membrane was also confirmed by mass balance analyses for the WWTP secondary effluent; while the attachment of C1 and C2 was shown to be negligible for the two lakes. The results may provide basic formation for developing suitable fouling control strategies for sustainable UF processes.     

染整废水深度处理纳滤工艺膜污染成因分析

为调查棉针织染整废水纳滤脱盐系统膜污染的类型和成因,使用电感耦合等离子发射光谱仪、扫描电子显微镜-EDX能谱仪、傅里叶变换红外光谱仪、热重分析仪、高倍光学显微镜和X射线荧光光谱仪,从膜进水水质、膜过程污染状况和膜清洗效果等三方面进行了联合互补检测和综合分析.结果表明,棉针织染整废水脱盐过程中纳滤膜的污染类型包括无机污染、有机污染和微生物污染;干燥(105℃)的污染物成分组成中结合水所占质量分数约8.2%,有机成分所占质量分数约41.0%,无机成分所占质量分数约50.8%;在无机污染物中铁盐污染较为突出,有机污染物所包含的主要官能团为—OH、—CH和—CC,微生物污染物中包含原生动物和后生动物;短期膜污染和长期膜污染分析结果表明有机污染和微生物污染的形成需要长时间的累积效应;纳滤膜清洗试验结果表明,有机污染和微生物污染是引起膜通量下降的主要原因,两者对膜通量影响的贡献率约53.3%.     

预处理对短流程超滤工艺不可逆膜污染影响的中试试验

以东江水为处理对象,进行直接超滤、微絮凝-超滤和絮凝/活性炭-超滤中试研究,探讨预处理对短流程超滤工艺不可逆膜污染的影响.利用扫描电镜形貌观察、三维荧光光谱(EEM)和高效排阻色谱法等手段对不可逆膜污染物进行表征分析,比较预处理对不可逆膜污染物含量和组分的影响,阐述预处理对不可逆膜污染影响的机制.结果表明,在10 L·(m~2·h)~(-1)低通量运行下,微絮凝预处理使不可逆膜污染增长速率从直接超滤的0.32 k Pa·d~(-1)下降到0.16 k Pa·d~(-1),絮凝/活性炭预处理后超滤工艺几乎零污染运行,且当絮凝/活性炭-超滤运行通量增加至17 L·(m~2·h)~(-1)时,仍没有观察到明显的不可逆膜污染增长.东江水中不可逆膜污染的主要组分是蛋白质类和富里酸等腐殖质类物质.微絮凝通过改变膜表面滤饼层的结构(厚度和密实性),提高物理清洗效率,减轻不可逆膜污染的积累;絮凝/活性炭预处理提高对不可逆膜污染物的去除效果,减轻膜污染负荷,控制不可逆膜污染.因此,采用絮凝和絮凝/活性炭预处理工艺,均可有效降低短流程超滤工艺不可逆膜污染积累.     

水质条件对膜-羧基官能团之间微观作用力的影响特征

为了探讨pH值、离子强度及膜材料对膜-污染物间相互作用力的影响特征,利用自制的典型膜污染物羧基官能团胶体探针,结合原子力显微镜定量考察了羧基官能团与PVDF及EVOH超滤膜间的相互作用力随pH值及离子强度的变化特征.结果表明:带有羧基基体的污染物与PVDF及EVOH超滤膜之间的相互作用力皆随着pH值的增大而减小;但是上述作用力随着离子强度的增加呈现特殊的变化趋势:在离子强度为0~10mmol/L时,膜-带有羧基基体的污染物之间相互作用力随着离子强度的增加而增大;在离子强度为10~500mmol/L时,膜-羧基之间相互作用力随着离子强度的增大而减小.在特定的水质条件下,EVOH-羧基间的作用力远小于PVDF-羧基之间的作用力.     

SRT对UCT-MBR反硝化除磷性能与膜污染行为的影响

采用脱氮除磷膜生物反应器(UCT-MBR)工艺处理冀南地区城市污水,考察了SRT对UCT-MBR工艺反硝化除磷性能与膜污染行为的影响.结果表明:较短(15d)与较长(40d)SRT均不利于反硝化聚磷菌(DPAOs)的富集;SRT控制在25d时系统的反硝化除磷性能得到最大程度强化,反硝化聚磷菌(DPAOs)占聚磷菌(PAOs)的数量比例及缺氧除磷率达到最大值,分别稳定在50.9%和88%,并且此时系统总磷(TP)、总氮(TN)去除率也达到最大值91.7%、73.6%,出水浓度分别稳定在0.48, 13.3mg/L左右;SRT对系统COD、氨氮(NH₄⁺-N)的去除效能影响不大,COD、NH₄⁺-N平均去除率分别为89.8%、99.7%,出水浓度分别稳定在30.8, 0.15mg/L;随着SRT的延长,膜池混合液固体(MLSS)浓度升高,分子量大于100kDa、小于1kDa的溶解性微生物代谢产物(SMP)浓度和胞外聚合物(EPS)比污泥浓度升高及污泥粒径(PSD)减小,是导致膜池污泥可滤性变差的主要原因,从而致使系统膜渗透性加速降低、持续运行周期缩短,而红外光谱(FT-IR)分析表明SRT对膜污染物质的组成无显著影响,光谱折射率与SMP、EPS含量呈现一致性.     

Performance and fouling mechanism of direct contact membrane distillation (DCMD) treating fermentation wastewater with high organic concentrations

In this study,direct contact membrane distillation(DCMD)was used for treating fermentation wastewater with high organic concentrations.DCMD performance characteristics including permeate flux,permeate water quality as well as membrane fouling were investigated systematically.Experimental results showed that,after 12 hr DCMD,the feed wastewater was concentrated by about a factor of 3.7 on a volumetric basis,with the permeate flux decreasing from the initial 8.7 L/m~2/hr to the final 4.3 L/m~2/hr due to membrane fouling;the protein concentration in the feed wastewater was increased by about 3.5 times and achieved a value of 6178 mg/L,which is suitable for reutilization.Although COD and TOC in permeate water increased continuously due to the transfer of volatile components from wastewater,organic rejection of over 95%was achieved in wastewater.GC–MS results suggested that the fermentation wastewater contained 128kinds of organics,in which 14 organics dominated.After 12 hr DCMD,not only volatile organics including trimethyl pyrazine,2-acetyl pyrrole,phenethyl alcohol and phenylacetic acid,but also non-volatile dibutyl phthalate was detected in permeate water due to membrane wetting.FT-IR and SEM–EDS results indicated that the deposits formed on the membrane inner surface mainly consisted of Ca,Mg,and amine,carboxylic acid and aromatic groups.The fouled membrane could be recovered,as most of the deposits could be removed using a HCl/Na OH chemical cleaning method.     

Comparison of membrane fouling during short-term filtration of aerobic granular sludge and activated sludge

Aerobic granular sludge was cultivated adopting internal-circulate sequencing batch airlift reactor.The contradistinctive experiment about short-term membrane fouling between aerobic granular sludge system and activated sludge system were investigated.The membrane foulants was also characterized by Fourier transform infrared(FTIR)spectroscopy technique.The results showed that the aerobic granular sludge had excellent denitrification ability;the removal efficiency of TN could reach 90%.The aerobic granular sludge could alleviate membrane fouling effectively.The steady membrane flux of aerobic granular sludge was twice as much as that of activated sludge system.In addition,it was found that the aerobic granular sludge could result in severe membrane pore-blocking, however,the activated sludge could cause severe cake fouling.The major components of the foulants were identified as comprising of proteins and polysaccharide materials.     

波纹微通道湍流促进器减缓SFMBR的膜污染效果分析

主要通过浸没式平板膜生物反应器的膜污染阻力分布和膜表面的污染特性来分析波纹微通道湍流促进器减缓浸没式平板膜生物反应器的膜污染效果.结果表明,波纹微通道湍流促进器有效地降低了总阻力Rt,降低率达到68.01%,其中的Rrf、Rc和Rp+Ra分别降低54.20%、87.98%和84.00%;滤饼层厚度、有机和无机污染成分都减少,且污染层更易去除.综合膜污染阻力分布和膜表面污染物表征结果从扰流作用强化机理、逆扩散机理、絮凝机理和微孔强化过滤机理四个方面分析了波纹微通道湍流促进器减缓浸没式平板膜生物反应器膜污染的效果.     

中空纤维超滤膜处理聚合物驱采油污水中膜污染特性分析

聚合物驱采油污水中大量聚合物的存在影响了污水的性质,它对超滤膜的污染机理与一般采油污水不同。研究了超滤过滤模拟含聚合物污水过程中,聚合物浓度对膜通量的影响,通过对过滤实际原水污染膜纤维进行化学清洗以及污染膜表面和断面扫描电镜分析,优选化学清洗方案。在此基础上,采用优选的化学清洗方案对工程应用中的膜组件进行清洗。结果表明:随着聚合物浓度升高,膜通量衰减逐渐加剧;NaOH和十二烷基苯磺酸钠组合对聚合物污染清洗效果最佳,可恢复初始通量的75%;分析清洗后膜表面的扫描电镜图表明,原水中物质会在膜面累积形成稳定凝胶层并对膜造成不可逆污染。