生物质炭强化FeOOH类芬顿催化性能及其机制

采用醇助水热法制备了新型生物质炭修饰的α-FeOOH类芬顿催化剂（BC-FeOOH）,并通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）对催化剂进行了表征,证明生物质炭（BC）成功引入到α-FeOOH中.以罗丹明B（RhB）为目标污染物,考察了BC修饰量、催化剂及H₂O₂投加量对其催化效率的影响.结果表明,BC的引入可以极大地提高FeOOH的类芬顿催化性能.在pH中性、催化剂投加量0.6 g·L^-1、H₂O₂初始浓度10 mmol·L^-1的条件下,BC-FeOOH（22.2% BC）对RhB的降解率可达到90%,重复利用5次活性仍可保持在80%左右,且铁离子溶出浓度仅为0.08 mg·L^-1.进一步通过ESR在不同体系中的测试结果表明,BC的引入不仅可促进H₂O₂有效还原分解产生更多的羟基自由基（·OH）,而且增强了催化剂与污染物RhB的相互作用,促使污染物失电子氧化降解,从而提高了FeOOH的催化活性及催化稳定性.     

Revealing the changes of bacterial community from water source to consumers tap: A full-scale investigation in eastern city of China

This study profiled the bacterial community variations of water from four water treatment systems, including coagulation, sedimentation, sand filtration, ozonation-biological activated carbon filtration (O₃-BAC), disinfection, and the tap water after the distribution process in eastern China. The results showed that different water treatment processes affected the bacterial community structure in different ways. The traditional treatment processes, including coagulation, sedimentation and sand filtration, reduced the total bacterial count, while they had little effect on the bacterial community structure in the treated water (before disinfection). Compared to the traditional treatment process, O₃-BAC reduced the relative abundance of Sphingomonas in the finished water. In addition, ozonation may play a role in reducing the relative abundance of Mycobacterium. NaClO and ClO₂ had different effects on the bacterial community in the finished water. The relative abundance of some bacteria (e.g. Flavobacterium, Phreatobacter and Porphyrobacter) increased in the finished water after ClO₂ disinfection. The relative abundance of Mycobacterium and Legionella, which have been widely reported as waterborne opportunistic pathogens, increased after NaClO disinfection. In addition, some microorganisms proliferated and grew in the distribution system, which could lead to turbidity increases in the tap water. Compared to those in the finished water, the relative abundance of Sphingomonas, Hyphomicrobium, Phreatobacter, Rheinheimera, Pseudomonas and Acinetobacter increased in the tap water disinfected with NaClO, while the relative abundance of Mycobacterium increased in the tap water disinfected with ClO₂. Overall, this study provided the detailed variation in the bacterial community in the drinking water system.     

聚合氯化铝与有机高分子复合絮凝剂的形态分布研究——AlFerron和~(27)AlNMR相结合

主要研究了Ａｌ－Ｆｅｒｒｏｎ逐时络合比色法和＾２７Ａｌ－ＮＭＲ法应用于聚合铝与有机高分子复合絮凝剂形态分布的测定，结果表明，两种方法分别测定的Ａｌｂ和Ａｌ１３的结果具有一定的相关性；聚合铝与有机高分子复合后其形态分布发生了一定的变化，Ａｌｂ（或Ａｌ１３）的含量有所降低，但仍是优势形态，Ａｌａ（或Ａｌ单）的含量基本保持不变。     

微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的研究之二——以聚合氯化铁(PFC)为絮凝剂

试验研究了微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果.试验结果表明,微涡旋絮凝-逆流气浮工艺去除水中腐殖酸时,在聚合氯化铁(PFC)的最佳投药点0.62 mmol·L-1(Fe3 )下,出水水质符合纳滤膜系统预处理单元的要求,而且该工艺需要PFC絮凝剂的量较低.该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸有机物浓度大大降低,且含TQ56-36FC型纳滤膜的流程1比含M-N1812A型纳滤膜的流程2效果好.前者出水的TOC值可达0.48 mg·L-1,CODMn值为0.64～0.69mg·L-1,UV254值为0,且有95%以上的脱盐率.后者出水的TOC值为0.61～1.00mg·L-1,CODMn值为0.72～0.97mg·L-1,UV254值为0～0.0109,脱盐率很低.另外,尽管保安过滤/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱的存在也降低了纳滤膜对有机物的去除率.动态实验结果表明,该集成工艺在本试验中运行周期为72h.水中颗粒物粒度分布表明,原水、絮凝后和气浮出水中颗粒物粒度分布的中位直径(d50)分别为2～5 μm、21 μm和16μm;经过保安过滤器或保安过滤器/活性炭柱,水样中的颗粒物的d50为0到几个μm;经过纳滤膜后,出水基本无颗粒物.初步研究表明,微涡旋絮凝过程中投药量对絮体的分形维数有着显著影响.     

粉末活性炭粒径对水中菲吸附动力学的影响效应研究

以菲为目标污染物,研究了粉末活性炭(PAC)在微尺度(1～ 100.Μm)下的粒径效应对多环芳烃吸附性能的影响.实验中按照中值粒径将研磨后得到的粉末活性炭划分为:PAC-1 (19 μm)、PAC-2(46μm)、PAC-3(76 μm).通过比表面积及孔隙度自动分析仪、原位拉曼光谱、扫描电镜等手段对PAC物化性质进行表征,发现粒径减小使PAC的BET比表面积和总孔容增加了10％ ～20％左右,而对PAC表面化学性质的影响较小.PAC的粒径分布对其吸附性能有显著影响,这种影响主要体现为吸附速率成倍的增加,其次是吸附容量有30％ ～36％的增幅.分别用3种动力学模型对吸附过程进行拟合,结果表明,伪二级动力学方程的拟合程度最高,PAC-1有最大的吸附速率常数k,并且随着粒径的减小,k值逐渐增大.     

Polymer hydrogels with enhanced stability and heterogeneous Fenton activity in organic pollutant removal

Polymer hydrogel-based materials have been shown to act as novel Fenton catalysts for water treatment, but the rational design of hydrogel-based catalysts with good stability has been a great challenge. To increase the stability and activity of polymer-based Fenton catalysts, uniform urchin-like α-Fe_2O_3 was grown in situ in a PVA carrier matrix here. PVA molecules promoted the growth of urchin-like α-Fe_2O_3, and then the PVA hydrogel acted as a barrier and carrier to reduce agglomeration. Through coordination by hydroxyl groups,PVA had good combination with Fe ions and α-Fe_2O_3. The formation of Fe–O–C bonds between iron oxides and polymers was reported for the first time, enhancing the material stability during catalysis. Under higher PVA concentrations, the resulting composite hydrogel could generate more ˙OH due to the increase in the number of active sites because of the hairy urchin-like structure. In tetracycline degradation through a heterogeneous Fenton reaction, the resulting material had good catalytic activity from pH 2 to pH 10 with low iron leaching, good reusability and remained at a level of nearly 90%after five consecutive cycles. Density functional theory calculations were used to further prove the mechanism of structural change of the iron oxides. The HOMO and LUMO energies of the iron oxides changed from 5.428 and 4.899 eV to 5.926 and 5.310 eV,indicating that the presence of PVA could influence the charge of the iron atom. The results provide new insights into the preparation of polymer hydrogel-based heterogeneous Fenton catalysts with enhanced stability for water treatment.     

Fe(Ⅲ)/Fe(Ⅱ)铁氧体工艺原位处理PVA废水及其沉淀物回收利用

为了评价Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺对PVA（聚乙烯醇）废水处理的可行性,采用Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺原位处理PVA模拟废水,考察不同作用时间、总铁投加量、初始ρ（PVA）和废水硬度对该工艺处理效果的影响.利用XRD（X射线衍射）、FT-IR（傅里叶转换红外光谱）、BET比表面积、VSM（磁滞回线测试）对沉淀物进行表征,解析该工艺原位处理PVA模拟废水的主要机理,并以该工艺沉淀物为吸附剂,通过锑吸附试验,探讨该工艺沉淀物的回用性.结果表明:①Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺对PVA模拟废水具有良好的处理能力,初始ρ（PVA）为1 000 mg/L时,该工艺在20 min以内即可达到80%以上的去除率,并且基本没有金属铁的残余,该工艺对PVA的去除率随总铁投加量的增加而提高且基本不受水体硬度影响. ②在Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺对PVA的原位去除过程中,PVA作为一种反应物参与沉淀物Fe₃O₄的生成,并促进纳米Fe₃O₄比表面积增大,最终形成一种类似于凝胶的Fe₃O₄聚合物. ③Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺可高效处理模拟PVA-MB（亚甲基蓝）染料废水.对于含有100 mg/L MB（亚甲基蓝三水）和500 mg/L PVA的混合溶液,MB和COD_Cr去除率在1 min时分别达到97.37%和89.47%.沉淀物通过磁分离、乙醇和水清洗后,在水中浸出的ρ（TOC）和ρ（COD_Cr）很低,分别为0.86和2 mg/L,可作为吸附剂直接使用,得益于其具有较高的比表面积,对金属锑的拟合吸附量可达71.94 mg/g. ④Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺具有一定的实际应用价值.对东莞某实际印染废水处理5 min,COD_Cr和染料的去除率分别为85.71%和98.98%.研究显示,Fe（Ⅲ）/Fe（Ⅱ）铁氧体工艺可高效去除PVA,沉淀物为易回收的磁性Fe₃O₄,可作为吸附剂直接使用.      

沉积物颗粒表面分形特征的研究

通过一阶分子连接性指数^1X与分子表面积TSA之间的相关性计算出吸附分子的尺度，采用分形吸附等温线法计算出妫河沉积物的Ds为2．379，官厅沉积物的Ds为2．836．基于沉积物对N2的吸附．脱附等温线数据，采用FHH(Frenkel-Halsey-Hill)方程计算出两种沉积物的表面分形维数Ds，发现官厅沉积物与妫河沉积物的Ds相差不大；温度影响Ds主要是由于升温改变了沉积物的组成与结构．在本实验中采用热力学模型(thenmodynamic model)计算出的Ds值大都超过3．此外，沉积物的Ds与其比表面积、矿物含量、CEC、有机质的相关性差．以萘、菲、芘作为码尺计算出的Ds并不完全是表面空间填充能力的客观表现，而是表面吸附过程的一个重要的综合性特征参数．     

多相催化技术的固液微界面调控原理及应用进展

多相催化氧化是一种很有前景的水深度处理技术,实际水环境中微量难降解有机污染物的去除通常受到水中共存物质如天然有机物（NOM）的影响.因此,在多相催化体系中,基于污染物与氧化媒介在催化剂表面的作用及转化过程调控催化剂的表面性质,对于复杂环境中污染物的高效靶向去除至关重要.本文主要综述了以过氧化氢、臭氧和光为媒介的多相催化氧化技术的固液微界面调控原理,以及基于固液微界面调控的水处理应用进展.重点阐述了催化剂表面性质对氧化媒介和目标污染物在表面分解和转化的影响,以及不同类型有机污染物在催化剂表面的作用原理.在此基础上,我们提出通过不同的手段极化催化剂表面,使表面电子分布不均匀,形成氧化位点和还原位点,使目标污染物失电子氧化同时活化表面吸附氧化媒介形成更多吸附态·OH,是促进复杂水环境中目标污染物高效去除的关键途径.     

磁性高分子复合水凝胶的制备及其对水中铜离子的吸附性能

以海藻酸钠和聚乙烯醇为骨架负载磁性纳米Fe_3O_4颗粒合成了两种磁性高分子复合水凝胶材料:一种是以Ca~(2+)交联制备的磁性海藻酸钙单网络水凝胶(SAPFe),另一种是以海藻酸钙和聚乙烯醇经循环冷冻解冻制成的磁性双网络水凝胶(DAPFe).利用SEM、FTIR、BET对合成的材料进行表征,并研究了SAPFe和DAPFe对Cu~(2+)的吸附性能.结果表明,DAPFe比表面积达89.01 m~2·g~(-1),平均孔径为2.2 nm,DAPFe比SAPFe具有更低的含水率、更高的交联程度、更发达的孔隙结构和更高的比表面积.DAPFe对Cu~(2+)的最大吸附量可达207.01 mg·g~(-1),远大于SAPFe(173.01 mg·g~(-1)).SAPFe和DAPFe对Cu~(2+)的吸附等温线均符合Langmuir模型,吸附动力学符合准二级吸附动力学模型.通过分析SAPFe和DAPFe吸附Cu~(2+)前后官能团的变化,发现磁性高分子复合水凝胶具有丰富的羧基和羟基功能性官能团,并通过与Cu~(2+)产生螯合作用实现去除.