离子筛与醋酸纤维素混合超滤膜的制备及降氟性能

在超滤膜制备过程中，向铸膜液中引入亲氟物质———水合氧化镧，经熟化后制备的混合超滤膜具有分离大分子和降低水体中氟离子浓度两种功能．以含氟饮用水为研究对象，对其混合膜的降氟机理进行了探讨．     

聚偏氟乙烯大孔超滤膜的研究

以国产聚偏氟乙烯（ＰＶＤＦ）为原料,选择不同种类的单一溶剂、混合溶剂和添加剂为铸膜液组成,研究了若干制膜因素对膜性能的影响,采用混合溶剂ＤＭＡＣ／ＡＣ之比控制ＡＣ含量在４０％─６０％,添加剂含量在１０％─２０％,制膜的气氛温度为２５—３０Ｃ,铸膜液温度为５０℃左右,可制得截留分子量为１５万和２４万,透水速度达３０—７０ｍｌ／（ｃｍ２·ｈ）,截留率为９０％以上的大孔超滤膜。     

超滤膜的制备、贮存、安装和更换

超滤膜的制备超滤膜是超滤器的“心脏”,因此,在制备超滤膜时应特别注意控制那些能影响膜质量的关键因素。用二醋酸纤维素为基料,用丙酮作溶剂,以甲酰胺为成孔剂,配成三元溶液,在常温条件下即可成膜,其程序是:     

纤维素膜超滤大豆蛋白溶液过程传质特性的研究

以N-甲基吗啉-N-氧化物(NMMO)作为纤维素溶剂,用L-S相转化法制备纤维素超滤膜。通过研究大豆蛋白溶液在纤维素膜材料超滤过程中膜通量的变化规律,根据凝胶层理论和浓差极化理论,得到大豆蛋白溶液超滤过程中,操作压力、超滤溶液浓度与膜通量的变化关系的传质方程,同时建立了超滤法纯化大豆蛋白溶液的动力学模型,为利用纤维素超滤膜材料进行大豆蛋白分离的工业化生产提供技术上的理论指导。     

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.     

低浓度NaClO和NaOH对聚偏氟乙烯超滤膜老化的影响

利用质量分数分别为0.2%的NaClO和0.1%的NaOH溶液老化聚偏氟乙烯(PVDF)超滤膜,研究低浓度化学清洗剂对PVDF超滤膜老化的影响.通过纯水通量、膜孔径分布、扫描电镜、拉伸性能、接触角、红外光谱和有机物截留效果,对老化后超滤膜的特征和性能进行评估.结果表明,经过NaClO和NaOH处理后,超滤膜孔径增大,对总有机碳(TOC)的截留率甶36.0%分别降低至16.2%~32.4%和13.9%~24.4%.老化使PVDF膜表面发生了脱氟化氢反应,生成了C=C和C=O等新基团,改变了膜的化学组成和结构,增强了膜的疏水性.老化后膜的机械性能变差,拉断力和断裂伸长率均随老化时间的延长而降低.NaOH对PVDF膜机械性能的影响高于NaClO.     

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.     

等离子体改性PVDF中空纤维超滤膜的动电性质研究

为减轻膜污染以丙烯酸和丙烯酰胺为接枝单体,对聚偏氟乙烯中空纤维超滤膜用低温等离子体方法进行改性。用流动电位法,测定电解质溶液中膜的流动电位并研究电解质溶液的种类、浓度及pH值的影响,对比改性前后的膜流动电位变化情况。结果表明,流动电位绝对值随着电解质浓度的增大而减小,随着电解质溶液中阳离子价态的升高而减小;改性后膜的zeta电位略高于原膜。     

聚醚砜超滤膜的制备及其工艺条件研究

以聚醚砜（PES）为膜材料,聚乙烯吡咯烷酮（PVP）为添加剂,N,N-二甲基乙酰胺（DMAc）为溶剂,用相转化法制备了超滤膜。利用正交试验法,研究了制膜参数PES浓度、PVP浓度、凝固浴温度、凝固时间对膜性能的影响显著程度,其中PES浓度、PVP浓度、凝固浴温度对膜通量和截流率都有显著影响;并进一步探讨了这三个显著因素对膜性能的影响规律,得出制备截留分子量为67000的超滤膜的最佳条件为：PES浓度16％-22％,PVP浓度10％～12％,凝固浴温度308K-313K,凝固时间1200s～1800s。     

腐殖酸溶液对超滤膜污染的原因研究

针对腐殖酸溶液对超滤膜污染的原因,对超滤膜在过滤腐殖酸溶液时受到污染的变化进行了探讨,通过测试的数据比较了待测腐殖酸溶液与膜通量的关系,同时对腐殖酸溶液和添加钙离子后,对超滤膜污染的影响状况,同时还对超滤膜在过滤过程中的UV254变化规律进行了探讨。结果表明,不同质量浓度的腐殖酸溶液,它们对膜通量的影响比较显著,在相同的过滤时间内,膜通量分别下降了不同的百分组成。在腐植酸溶液中添加钙离子后,膜通量下降更大。     

原位植入TiO2纳米颗粒改性聚砜超滤膜及其抗生物污染性能研究

选用TiO_2纳米颗粒通过原位植入法对聚砜超滤膜表面进行改性,通过调节p H及沉淀浴中TiO_2浓度制备出不同TiO_2覆盖率的改性聚砜超滤膜,并分别用扫描电子显微镜、接触角测定仪、激光共聚焦显微镜等对改性膜性能进行评价.结果表明,p H为4时TiO_2分散良好并植入到聚砜膜表面,改变沉淀浴的浓度可以有效控制TiO_2在聚砜膜表面的覆盖率.聚砜膜的亲水性随TiO_2覆盖率的提高而不断增强.在纯水通量下降不明显的情况下,TiO_2改性超滤膜的抗生物污染性能均优于未改性膜,随着覆盖率的提高,抗生物污染性能呈现先增强后减弱的趋势,在覆盖率介于22.4%~27.7%之间时改性膜具有最优的抗生物污染性能,可使微生物粘附减少93%,黑暗培养24 h的生物膜厚度减少70%以上.     

Comparison of the effects of aluminum and iron(III) salts on ultrafiltration membrane biofouling in drinking water treatment

Coagulation plays an important role in alleviating membrane fouling, and a noticeable problem is the development of microorganisms after long-time operation, which gradually secrete extracellular polymeric substances (EPS). To date, few studies have paid attention to the behavior of microorganisms in drinking water treatment with ultrafiltration (UF) membranes. Herein, the membrane biofouling was investigated with different aluminum and iron salts. We found that Al₂(SO₄)₃·18H₂O performed better in reducing membrane fouling due to the slower growth rate of microorganisms. In comparison to Al₂(SO₄)₃·18H₂O, more EPS were induced with Fe₂(SO₄)₃·xH₂O, both in the membrane tank and the sludge on the cake layer. We also found that bacteria were the major microorganisms, of which the concentration was much higher than those of fungi and archaea. Further analyses showed that Proteobacteria was dominant in bacterial communities, which caused severe membrane fouling by forming a biofilm, especially for Fe₂(SO₄)₃·xH₂O. Additionally, the abundances of Bacteroidetes and Verrucomicrobia were relatively higher in the presence of Al₂(SO₄)₃·18H₂O, resulting in less severe biofouling by effectively degrading the protein and polysaccharide in EPS. As a result, in terms of microorganism behaviors, Al-based salts should be given preference as coagulants during actual operations.     

碳纳米管改性PVDF中空纤维超滤膜处理二级出水抗污染性能研究

采用碳纳米管改性PVDF中空纤维超滤膜以缓解膜污染.考察了CNTs的乙醇分散液浓度、CNTs尺寸和负载量对改性中空纤维膜的抗污染性能和改性膜内表面CNTs层稳定性的影响,分析了该改性膜对二级出水DOC、UV254的去除效果,并对改性膜出水的荧光特性进行了表征.结果表明,选用体积分数为50%的乙醇分散液、外径为30~50 nm碳纳米管、负载量为3 g·m-2时,制备的改性中空纤维膜CNTs层稳定,抗污染能力显著提高.与未改性膜相比,改性膜对二级出水DOC和UV254的去除率分别提高了37%和56%;且对二级出水中的腐殖类和蛋白质类物质去除能力明显增强.     

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.     

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.     

Purification, characterization and application of dual coagulants containing chitosan and different Al species in coagulation and ultrafiltration process

The objective of this study was to investigate the effect of different Al species and chitosan (CS) dosages on coagulation performance, floc characteristics (floc sizes, strength and regrowth ability and fractal dimension) and membrane resistance in a coagulation–ultrafiltration hybrid process. Results showed that different Al species combined with humic acid in diverse ways. Al_a had better removal efficiency, as determined by UV₂₅₄ and dissolved organic carbon, which could be further improved by the addition of CS. In addition, the optimal dosage of different Al species was determined to be 4.0 mg/L with the CS concentration of 1.0 mg/L, by orthogonal coagulation experiments. Combining Al_a/Al_b/Al_c with CS resulted in larger flocs, higher recovery, and higher fractal dimension values corresponding to denser flocs; in particular, the floc size at the steady state stage was four times larger than that obtained with Al species coagulants alone. The results of ultrafiltration experiments indicated that the external fouling percentage was significantly higher than that of internal fouling, at around 85% and 15%, respectively. In addition, the total membrane resistance was significantly decreased due to CS addition.     

含氟氯类危险废物焚烧灰渣的熔融特性研究

为了解决低熔点含氟氯类危险废物（简称＂危废＂）在回转窑焚烧炉内燃烧时,灰渣熔化导致窑内结圈的问题,实验采用氧化物分析纯（SiO2、Al2O3、CaO、Fe2O3、Al2O3）和NaCl、KCl、NaF分析纯来模拟危废炉渣组分,研究了危废焚烧炉灰渣的熔融特性,并采用神经网络预测危废灰渣的熔融温度.结果表明,SiO2、Al...     

海水淡化超滤-反渗透工艺沿程溴代消毒副产物变化规律

研究了海水淡化超滤-反渗透(UF-RO)工艺沿程有机物和溴代消毒副产物(Br-DBPs)变化特征.该海水中含有较高浓度的Br-(45.6~50.9 mg·L-1)和较多的芳香类化合物[比紫外吸收值SUVA为3.6~6.0 L·(mg·m)-1];色氨酸类芳香族蛋白质、富里酸类有机物和溶解性微生物代谢产物是海水中主要的荧光特征有机物.UF-RO工艺进水海水经Na Cl O消毒后,DBPs的种类和浓度显著增加,且增加的主要为Br-DBPs,其中三溴甲烷(CHBr3)占总三卤甲烷(THMs)的70.48%~91.50%,二溴乙酸(Br2CHCO2H)占总卤乙酸(HAAs)的81.14%~100%,二溴乙腈(C2HBr2N)占总卤乙腈(HANs)的83.77%~87.45%.UF膜对THMs、HAAs和HANs的去除率分别为36.63%~40.39%、73.83%~95.38%和100%.RO膜可以完全去除HAAs,但是对THMs不能完全去除.进水海水的抗雌激素活性为0.35~0.44 mg·L-1,氯消毒后增加了32%~69%.海水淡化UF-RO系统生成的DBPs和其他生物毒性物质最终被截留到了UF浓水和RO浓水中.     

包裹石煤固氟燃料固氟效果的中试

选择陕西紫阳蒿坪镇相同条件地炉16户,其中8户烧用当地高氟块状石煤、石灰、粘土和低氟无烟煤粉制备的包裹石煤燃料,8户燃烧未处理的石煤,进行了中试研究.结果表明,包裹石煤组本身煤氟与渣氟比较,固氟率平均75.0%;室内空气,与普通块石煤组比较,包裹石煤燃料组氟下降了85.7%,硫下降75.0%,烟尘下降55.3%.