微米级负载型 TiO2催化剂在光催化-膜分离反应器中的应用简

基于光催化-膜分离三相流化床反应器的结构特点及膜分离特性，以微米级MCM-41分子筛为载体，采用原位生成法制备微米级负载型TiO₂催化剂。针对微米级负载型TiO₂催化剂在光催化-膜分离反应器中的分布特性、悬浮特性、分离特性及膜污染特性进行研究。结果表明，曝气量一定的情况下，微米级负载型TiO₂催化剂在光催化-膜分离反应器中具有良好的悬浮特性，且优于纳米TiO₂。随着催化剂投加量的增加，悬浮浓度也随之增加。光催化反应器底部曝气0.3 m³/h、催化剂投加量为1 g/L时为宜。膜分离器中催化剂悬浮浓度明显低于光催化反应器；该微米级催化剂与纳米TiO₂相比具有不粘附、不堵塞膜孔等优良特性，能够有效降低膜污染，延长分离膜使用寿命。膜底曝气为0.1 m³/h时，反应器连续运行5 h（未加反冲洗）后，微米级负载型TiO₂催化剂和纳米TiO₂对膜组件的污染程度分别为膜通量衰减率4.3%和37.4%。反应器连续运行72 h，膜组件依然具有很好的分离特性。     

TiO2光催化复合分离膜对水中天然有机物的去除

在水源污染越来越严重、水质标准日益严格的背景下，超滤（UF）已逐渐成为替代饮用水常规处理技术的最佳选择之一。本研究中采用相转化法，将聚偏氟乙烯（PVDF）、聚乙二醇（PEG）和二氧化钛（TiO2）共混制得光催化复合分离膜并对其进行扫描电子显微镜（SEM）、原子力显微镜（AFM）和X射线能谱仪（EDS）等相应的表征。比较了有无光照条件下，PVDF-PEG和PVDF—PEG—TiO2膜对腐殖酸（HA）的截留和超滤过程中的膜污染情况。研究结果表明，TiO2光催化复合分离膜能提高对水中天然有机物的去除并同时降低膜污染。紫外光照强度越强，PVDF-PEG—TiO2膜的抗污染性能越好。另外，光催化能更有效地减少超滤初始浓度较低的腐殖酸溶液过程中的膜通量衰减。     

微乳法制备Fe-TiO2纳米晶复合体及光催化性能

采用微乳法制备铁掺杂TiO₂纳米晶(Fe-TiO₂)复合体, 通过热重-差热(TG-DTA)、X射线衍射(XRD)、扫描电镜（SEM）和紫外漫反射光谱(DRS)等对其结构和形态进行表征; 以亚甲基蓝溶液(MB)为标准模拟降解物, 对Fe-TiO₂, 纯TiO₂和P25光催化降解性能进行评价。结果表明，Fe-TiO₂的光催化活性明显＞P25，原因是Fe掺杂不仅能抑制TiO₂晶粒     

La2O3/ZnO/TiO2光催化降解活性艳红K-2BP的研究

采用溶胶-凝胶法制备了La₂O₃/ZnO/TiO₂复合光催化剂,以紫外灯为光源,活性艳红K-2BP为模型降解物,研究了La₂O₃/ZnO/TiO₂的光催化性能。结果表明：当锌和镧的掺杂量w(ZnO)=20%, w(La₂O₃)=0.5%, 煅烧温度为500℃时,La₂O₃/ZnO/TiO₂复合光催化剂的光催化活性最高；当催化剂投加量4 g/L,通气量800 mL/min,初始pH值3.12时,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解效果最好。实验证明,La₂O₃/ZnO/TiO₂对活性艳红K-2BP的降解遵从Langmuir-Hinshelwood动力学模型,测得其反应速率常数k＝11.5 mg/(L·min)；吸附常数K＝2.88×10^-2 L/mg。     

TiO2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料，采用微波辐射法制备TiO₂/AC复合光催化剂，并对制备的催化剂进行了表征；采用该催化剂对六氯苯进行光催化降解，确定了六氯苯降解的最佳工艺条件，并就几种外加试剂对TiO₂/AC光催化降解六氯苯的强化作用进行了探讨。结果表明，制备的催化剂中TiO₂均匀分布在活性炭表面、呈单一的锐钛矿晶型，晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO₂负载量为18.2%、TiO₂/AC投加量为0.4 g/L、反应时间为60 min。在此条件下，六氯苯降解效率达90.3%。添加适量的H₂O₂、AgNO₃、K₂S₂O₈、KIO₄和KMnO₄均能提高TiO₂/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L，对TiO₂/AC光催化效率的强化作用大小顺序为：H₂O₂＞AgNO₃＞K₂S₂O₈＞KMnO₄＞KIO₄。     

TiO_2光催化对微滤去除腐殖酸的膜污染控制研究

着重研究了不同紫外灯光源和照射时间条件下,TiO_2光催化(PCO)对微滤去除腐殖酸过程中的膜污染控制,并探讨了膜污染的控制机理。研究结果表明,TiO_2光催化能有效提高微滤对腐殖酸的去除,同时降低膜通量的下降,起到有效控制膜污染的作用。进一步的实验分析表明,TiO_2光催化控制膜污染的主要机理在于将腐殖酸降解为易于被TiO_2吸附的小分子量物质,吸附腐殖酸降解产物后的TiO_2聚合颗粒粒径增大,易于在膜表面形成更为松散的沉积层,并使膜污染从以膜孔堵塞和沉积层污染为主转化为以沉积层污染为主的可逆性污染。     

TiO2/GeO2复合膜光催化氧化降解农药废水的研究

提出了一种新的TiO₂/GeO₂复合膜圆形光催化氧化反应器，研究了该反应器对经物化处理后的农药废水进行降解的过程。研究表明，光催化氧化的最佳条件是锌片镀TiO₂/GeO₂复合膜、pH=6.7、过氧化氢（H₂O₂）浓度为400 mg/L。并对其他氧化剂对该过程的影响进行了探讨。有机废水通过该反应器处理后，其COD值降为57mg/L。能使有机污染物全部降解为小分子无机物，废水达到国家一级排放标准。     

模拟可见光下掺杂TiO2对甲醛溶液光催化降解

模拟自然条件下的可见光，以甲醛的光催化降解为探针反应，评价了通过溶胶凝胶法分别制备的8种（银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S、氯Cl）掺杂TiO₂纳米晶体的光催化活性及对甲醛水溶液的去除效果。用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂纳米TiO₂的微晶尺寸、晶体结构与光学性能。结果表明：Ce离子尽管有较大的半径但是主要还是掺杂到晶格中，Ce掺杂可以促进TiO₂由非正分锐钛矿相向锐钛矿相和金红石相的转变，抑制载流子复合，使TiO₂的光吸收带边发生红移且有利于对可见光的吸收，从而使Ce掺杂TiO₂在模拟可见光下光催化甲醛水溶液的能力得到明显提高。     

V/Ce共掺杂TiO2光催化降解甲醛的实验研究

采用溶胶凝胶法制备了不掺杂、V 掺杂、Ce掺杂、V/Ce共掺杂纳米TiO₂光催化剂，并将其分别负载于瓷砖上，利用X射线衍射分析（XRD）和扫描电镜分析（SEM）技术对薄膜样品的结构和形貌进行了表征。通过对甲醛的降解实验评价光催化剂的光催化活性。实验结果表明，光催化剂的负载量、共掺杂离子的掺杂量、掺杂配比、煅烧温度影响纳米TiO₂的光催化活性。V/Ce共掺杂TiO₂光催化剂产生了协同效应，其光催化活性优于纯TiO₂和单掺杂TiO₂样品。     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料，空心微珠为载体，采用溶胶凝胶法制备TiO₂/beads光催化剂载体，然后浸渍法制备出H₄SiW₁₂O₄₀/TiO₂/beads表面负载修饰型复合光催化剂，并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H₄SiW₁₂O₄₀/TiO₂/beads对亚甲基蓝降解的光催化活性，考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明，在中性条件下，H₄SiW₁₂O₄₀/TiO₂/beads催化剂的投加量为0.25 g/L，浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

Fouling mitigation and cleanability of TiO<Subscript>2</Subscript> photocatalyst-modified PVDF membranes during ultrafiltration of model oily wastewater with different salt contents

In the present study, TiO₂-coated ultrafiltration membranes were prepared and used for oily water filtration (droplet size <?2 μm). The aim of this work was to investigate the effect of different salt contents on fouling and filtration properties of neat and TiO₂-coated membranes during oil-in-water emulsion filtration. The effect of the TiO₂ coating on the flux, surface free energy, and retention values was measured and compared with the neat membrane values. The cleanability of the fouled TiO₂-coated membranes by UV irradiation was also investigated by measuring flux recovery and contact angles, and the chemical changes during cleaning were characterized by ATR-IR. It was found that increasing the salt content of the model wastewaters, oil-in-water emulsions, increased the zeta potential and the size of the droplets. The presence of the TiO₂ coating decreases the membrane fouling during oily emulsion filtration compared to the neat membrane, due to the hydrophilicity of the coating regardless of the salt content of the emulsions. The neat and coated membrane oil retention was similar, 96?±?2%. The coated membrane can be effectively cleaned with UV irradiation without additional chemicals and a significant flux recovery can be achieved. Monitoring of the cleaning process by following the membrane surface wettability and ATR-IR measurements showed that the recovery of flux does not mean the total elimination of the oil layer from the membrane surface.     

Photocatalytic degradation of gaseous toluene over Ag-doping TiO₂ nanotube powder prepared by anodization coupled with impregnation method

In this work, Ag-doping TiO₂ nanotubes were prepared and employed as the photocatalyst for the degradation of toluene. The TiO₂ nanotube powder was produced by the rapid-breakdown potentiostatic anodization of Ti foil in chloride-containing electrolytes, and then doped with Ag through an incipient wetness impregnation method. The samples were characterized by scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, surface photovoltage measurements, X-ray photoelectron spectroscopy and N₂ adsorption. The nanotubular TiO₂ photocatalysts showed an outer diameter of approximately 40 nm, fine mesoporous structure and high specific surface area. The photocatalytic activity of Ag-doping TiO₂ nanotube powder was evaluated through photooxidation of gaseous toluene. The results indicated that the degradation efficiency of toluene could get 98% after 4 h reaction using the Ag-doping TiO₂ nanotubes as the photocatalyst under UV light illumination, which was higher than that of the pure TiO₂ nanotubes, Ag-doping P25 or P25. Benzaldehyde species could be observed during the photocatalytic oxidation monitored by in situ FTIR, and the formed benzaldehyde intermediate during reaction would be partially oxidized into CO₂ and H₂O.     

高效聚合氯化铝对超滤膜污染影响的中试研究

针对某水厂以超滤为核心的短流程水处理工艺,在通过聚氯乙烯(PVC)超滤膜之前选择不同投加量(5、10、15和20 mg/L)的高效聚合氯化铝(HPAC)对长江下游原水进行混凝处理。通过跨膜压差(TMP)增长趋势、CODMn的去除率以及混凝后的水质,可知HPAC的最优投加量为15 mg/L。在此投加量下,运用体积排阻色谱法分析原水、膜前水、膜后水中各相对分子质量有机物的变化,可以发现混凝去除有机物的效果要优于超滤截留的。继而将HPAC与另外4种常用混凝剂:硫酸铝(分析纯)、氯化铁(化学纯)、聚合氯化铝(PAC)、聚合硫酸铁进行对比,结果表明,在它们各自最优投加量下,HPAC能够更有效地减缓超滤膜TMP的增长率,从而降低膜污染。因此,认为HPAC是与PVC超滤合金膜契合效果最佳的混凝剂。     

Photocatalytic Degradation of the Herbicide Erioglaucine in the Presence of Nanosized Titanium Dioxide: Comparison and Modeling of Reaction Kinetics

The present work mainly deals with photocatalytic degradation of a herbicide, erioglaucine, in water in the presence of TiO₂ nanoparticles (Degussa P-25) under ultraviolet (UV) light illumination (30 W). The degradation rate of erioglaucine was not so high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. We have studied the influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time and initial concentration of erioglaucine on the photodegradation efficiency of erioglaucine. A kinetic model is applied for the photocatalytic oxidation by the UV/TiO₂ system. Experimental results indicated that the photocatalytic degradation process could be explained in terms of the Langmuir–Hinshelwood kinetic model. The values of the adsorption equilibrium constant, K, and the second order kinetic rate constant, k, were 0.116 ppm^{? 1} and 0.984 ppm min^{? 1}, respectively. In this work, we also compared the reactivity between the commercial TiO₂ Degussa P-25 and a rutile TiO₂. The photocatalytic activities of both photocatalysts were tested using the herbicide solution. We have noticed that photodegradation efficiency was different between both of them. The higher photoactivity of Degussa P-25 compared to that of rutile TiO₂ for the photodegradation of erioglaucine may be due to higher hydroxyl content, higher surface area, nano-size and crystallinity of the Degussa P-25. Our results also showed that the UV/TiO₂ process with Degussa P-25 as photocatalyst was appropriate as the effective treatment method for removal of erioglaucine from a real wastewater. The electrical energy consumption per order of magnitude for photocatalytic degradation of erioglaucine was lower with Degussa P-25 than in the presence of rutile TiO₂.     

不同超滤膜过滤天然有机物的膜污染特性研究

超滤膜的截留分子量、天然有机物的分子量分布以及两者之间的相对关系对于膜污染以及过滤阻力的组成有很大的影响。MWCO140kDa、70kDa、30kDa、10kDa、4kDa和1kDa的超滤膜过滤10mg/L腐殖酸溶液和未名湖湖水的试验结果表明,在过滤初始时刻就发生了膜污染,膜的截留分子量越大,膜污染越显著。在长期过滤的过程中,截留分子量>10kDa的超滤膜的过滤阻力受到膜污染的控制,膜孔堵塞和膜面形成凝胶层是造成膜污染的主要原因;当膜的截留分子量≤10kDa时,过滤阻力主要由膜本身固有的阻力决定,膜污染影响较小。不同浓度、类型的腐殖酸溶液和不同种类的超滤膜过滤试验数据分析表明,当膜对腐殖酸分子的截留率超过40%时,膜污染的程度会逐渐减小,过滤阻力将由膜本身固有的阻力控制。     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

TiO2膜降解水中污染物的稳定性考察与再生方法研究

针对实际水处理中对催化剂性能的要求，以光催化降解苯酚溶液作为探针反应，考察了玻璃纤维网上负载的TiO₂膜催化剂长期使用条件下的稳定性，研究了催化剂在自来水中使用失活后的再生方法。结果表明，经过50次使用之后，膜催化剂120 min反应对苯酚的降解率从100%下降至83%，总体上看，所制催化剂还是具有相当好的稳定性；在反应器中用蒸馏水浸泡配合光催化反应对TiO₂膜催化剂进行原位再生是一种可行的再生途径。