絮体分形结构对沉淀速度影响研究

利用基于微天平的质量-粒径法和基于改进粒子图像测速技术的自由沉淀法对高岭土、腐殖酸絮体的分形结构进行了研究.结果表明,质量-粒径法得到的铁盐絮体三维分形维数为2.14~2.28,明显大于铝盐絮体的1.75~1.83,铁盐絮体结构更为致密,而铝、铁-腐殖酸絮体比相应的高岭土絮体分形维数要小.絮体分形维数与沉淀速度具有良好的对应关系,分形维数越大,絮体沉淀速度越大.质量粒径法与自由沉淀法求出的絮体分形维数相吻合,分形絮体沉淀速度不再满足Stokes沉淀速度公式.     

引入分形维数的混凝动力学方程数值求解

运用Smoluchowskj基本原理,建立了引入絮凝体分形维数的混凝动力学模型.该模型在絮凝过程中考虑了不同时刻形成的絮凝体中引入的初始颗粒数目和空隙率,并以此来推求不同时刻形成的絮凝体所对应的分形维数.采用有限差分法对建立的混凝动力学模型进行了数值计算.结果表明,初始颗粒的结构特征和碰撞效率是影响絮凝体粒径分布的主要因素.初始颗粒的分形维数和碰撞效率越大,絮凝体粒径分布越宽泛,大尺寸的颗粒所占的份额越多.同时计算结果表明,絮凝体的分形维数有随其粒径增大而逐渐降低的趋势,其原因是絮凝体的成长粒径与絮凝体中所包含的初始颗粒增长速度不成比例.以腐殖酸为混凝对象,采用硫酸铝作为混凝剂进行混凝实验,并以其初始絮凝条件作为数值计算初始条件,研究表明数值计算分析结果和模拟结果吻合较好.     

腐殖酸絮凝体形成过程中初期搅拌条件对其形态结构的影响

以腐殖酸为研究对象,采用硫酸铝为混凝剂进行混凝杯罐实验,借助PDA在线监测系统、图像解析法及粒子图像测速技术分析评价絮凝体的构造特征,着重探讨了混凝过程中初期快速搅拌条件对絮凝体形态结构的影响.结果表明,快速搅拌条件对腐殖酸絮凝体的形成过程及形态结构有着显著影响.最佳快速搅拌条件为:搅拌历时l min,搅拌强度300 r·min-,此时形成的絮凝体结构密实,抗剪切能力强,整体性能最优,絮凝体分形维数、强度及平均粒径分别为1.8842、0.164 N·m-2、0.43 mm.腐殖酸絮凝体的形成包括不溶性微粒的产生及初期颗粒的形成与结合等过程,其中,不溶性微粒的形成及初期颗粒的致密化过程是决定最终絮凝体形态构造的重要环节,而快速搅拌条件影响着混凝剂扩散混合效果和初期颗粒的形成速率与致密化程度,这也是初期快速搅拌条件对于腐殖酸混凝过程有显著影响的一个重要因素.     

加载絮体形态对短流程超滤膜污染影响效应

以聚硫酸铁（PFS）为混凝剂,微砂为载体颗粒,系统考察了采用加载絮凝-超滤联用工艺净化含高岭土、腐植酸和锑[Sb（Ⅲ）]的模拟原水过程中,不同PFS和微砂投加量条件下加载絮体形态特性以及其对超滤膜通量衰减、膜污染可逆性和宏观出水水质等的影响,并分析了膜污染机理.结果表明,PFS投加量对絮体形态及膜滤效能和膜污染影响显著,且投加量过少或过多均会产生不利影响,以30mg/L为宜;与不投加微砂的工况相比,加入微砂更易于形成大而结构较为松散的絮体,可有效削弱不可逆膜污染,并获得较为稳定的超滤出水水质;超滤末端膜比通量与絮体平均粒径呈良好的正相关性（R²=0.8774）,但因加载絮凝体系中引起分形维数变大的不同类型颗粒（包括小粒径范围絮体和未被加载絮体捕获的微砂）对超滤净水过程产生的影响各异,致使膜通量与分形维数的负相关性较差（R²=0.5760）.     

超声空化及絮体破碎过程的模拟与试验分析

为探究利于空化效应的超声条件及超声波破碎絮体机理,基于Matlab平台建立空化气泡模型及2种简化的有限扩散聚集(DLA)絮体破碎模型,进行计算机仿真,并通过试验分析得到实际絮体破碎模式.结果表明:随着超声频率的增加,空化效应减弱;声能密度的增加导致空化气泡振幅增大,声能密度为7W/mL时气泡振幅可达初始半径的200倍,空化效果较好.低声能密(0.03~3W/mL)和低超声频率(25~40kHz)处理絮体时,剥蚀作用为主导作用,超声后絮体粒径减小,分形维数增大;声能密度超过3W/mL或频率大于40kHz,大规模破碎占主导作用,实际絮体粒径减幅小且结构散.40kHz的超声频率更利于絮体的破碎,作用10min后,絮体粒径减幅达9.8%,分形维数为1.394,结构更加密实.     

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.     

微絮凝对腐殖酸超滤过程膜污染的减缓特性

以硫酸铝[Al_2(SO_4)_3·18H_2O]为絮凝剂,腐殖酸(humic acid,HA)和高岭土(Kaolin)水溶液为原水,研究微絮凝过程产生的不同絮体形态,对自制聚偏氟乙烯(PVDF)超滤膜过滤过程的影响.主要考察了微絮凝过程中絮体的特性(粒径大小及分布,分形维数)以及不同条件下形成的絮体形态对膜通量的影响,利用扫描电镜(SEM)和原子力显微镜(AFM)对污染膜的表面形貌进行表征,并测定了PVDF膜与有机污染物之间黏附力大小,来解析不同絮体形态对超滤膜的膜污染影响机制.结果表明,Al~(3+)以电性中和作用水解去除有机物,随着絮凝剂投加量的增加,絮体粒径不断增大,絮体的分形维数减小.膜通量衰减速率与絮体的粒径呈负相关,絮体粒径越大,膜通量衰减速率越小,超滤过程中形成的滤饼层越疏松,同时,较小分形维数的絮体引起的膜污染较轻,其膜通量恢复率也较高.PVDF-有机污染物之间的相互作用力大小与运行初期相应污染膜通量衰减速率呈正相关.当Al~(3+)投加量为5 mg·L~(-1),初始pH=7时,HA去除率为96.7%,膜通量衰减最小,通量恢复率达到88%.     

絮体老化与调节对回流进水及混凝的影响机制

为探索絮体老化与pH值调节对回流进水颗粒组成及混凝的影响,采用激光粒度仪进行了絮体粒径分析并通过Al(OH)₃胶体(Al-gel)的老化实验探究了老化与pH值调节对絮体形态及性质的内在影响机制.结果表明,原水颗粒物粒径呈现单峰分布,絮体回流进水颗粒物粒径呈现双峰分布,并且回流进水颗粒d₅₀随着絮体老化时间的增加而减小;由于絮体回流提高了颗粒物与混凝剂接触机率和碰撞效率,因此加快了絮体的生长;絮体在pH=5的环境下老化12h后进行回流混凝的絮体粒径生长速率最高(1.16μm/s)并且生成的絮体具有较大的分形维数(2.35).Al-gel的老化实验结果表明,絮体老化过程会涉及羟桥反应和结晶反应并导致絮体的表面活性基团数量减少,从而不利于与原水颗粒物的相互作用.pH值调节对絮体产生不同的影响,p H=5的条件下进行老化会加速絮体的羟桥反应和结晶反应,而p H=9的条件下进行老化则会涉及溶解-沉淀-结晶反应.     

聚硅酸金属盐复合絮凝剂形貌结构及性能研究

以硅酸钠、硫酸和硫酸盐为原料制备聚硅酸金属盐(PSMS)复合絮凝剂,通过红外光谱研究了金属元素与聚硅酸(PS)的相互作用情况,采用电子显微镜观察了PS、PSMS和相应简单金属盐(MS)的形貌,利用激光粒度分析仪分析了絮体粒径变化及破碎与恢复情况,并考察了PSMS在不同投加量下处理腐植酸模拟废水的效果。结果表明:PSMS的红外光谱图中有M—O—Si振动峰出现,扫描电镜显示PSMS的聚集单元表面异于PS的平滑,为细小不规整的晶体颗粒,并与相应硫酸盐(MS)形貌有一定关联。此外,无论是所形成絮体的粒径还是对腐植酸的去除效果,聚硅酸硫酸铝(PSAlS)和聚硅酸硫酸铁(PSFeS)均优于其它聚硅酸金属盐,PSFeS的絮体虽易破碎但破碎后恢复能力最好,且粒径最大而容易沉降。     

腐殖酸铝盐絮凝体的动态特性

通过显微摄影分析研究了腐殖酸铝盐絮凝体成长的动态过程以及在混凝过程中絮凝体构造(分形维数)的变化规律.结果表明,在腐殖酸混凝过程中,随搅拌历时延长,絮凝体粒径不断成长变大,最终达到平衡状态.随着絮凝体的成长,其构造呈现由密实逐渐向疏松过渡的过程,空隙率变大,二维分形维数由初期的1.8左右下降到1.4左右.絮凝体分形维数D_f和粒径d_f之间具有D_f=Ad_f^-     

基于光学在线监测及形态学研究的絮凝体强度分析方法

以PDA在线监测混凝过程和絮凝体形态学分析为基础,建立了絮凝体强度的分析评价方法.为了计算某一特定絮凝条件下形成絮凝体的黏结力,进行混凝实验并运用图像解析法及粒子图像测速技术研究絮凝体形态学特征.实验过程中将水样引入与光散射颗粒分析仪(PDA2000)相连的透明橡胶管内,并通过准确控制橡胶管内的水流速度梯度来改变作用于絮凝体上的剪切力,这样就可以在线监测絮体的破碎情况,然后根据PDA输出的FI曲线来确定絮凝体的临界破碎条件.根据临界破碎条件下剪切力、破碎力和黏结力的等量关系,确定黏结力系数k1,进而计算出可以表征絮凝体强度的黏结力B.该方法的有效性已经被大量以硫酸铝为混凝剂的腐殖酸混凝实验所证实.     

引入分形维数的絮体粒径分布规律及其守恒关系

采用显微摄影技术,通过混凝实验分析了腐植酸絮凝体的粒径分布规律.结果表明,腐植酸絮体的粒径呈现对数正态分布.从混凝动力学基本方程出发,考虑到腐植酸絮体构造的不规则性(分形维数),分析了颗粒数量、颗粒平均体积和标准偏差之间存在的守恒关系,该守恒关系可以大大简化基本方程的求解,更简便地预测混凝过程中絮体的粒径分布.     

超滤的预处理工艺对比研究:化学混凝与电絮凝

对比研究了化学混凝(chemical coagulation,CC)与电絮凝(electrocoagulation,EC)作为超滤膜分离的预处理工艺,在死端过滤条件下与超滤膜的作用机制以及对膜污染的减缓效果.主要研究了Al3+投加量对膜通量、絮体性质(粒径、强度系数、恢复系数、分形维数)、以及滤饼层性质的影响.结果表明,EC作为预处理时,生成的絮体强度大且结构紧实,在膜表面堆积形成的滤饼层具有疏松多孔、亲水性强的性质;而CC作为预处理时,生成的絮体强度低且比较松散,在膜过滤过程中容易被压力压碎压实,导致滤饼层比较密实、亲水性低.因此,EC作为预处理工艺对膜污染的减缓效果好,在运行过程中可以保持较高的膜通量,膜通量较CC高约5.57%.     

絮体性能及其工艺调控的研究与进展

絮体结构和强度特征是絮凝过程的重要参数.在简要回顾絮体分形结构研究的基础上,对絮体结构与强度的测定方法、絮体结构形成的影响因素及其工艺调控的研究进展进行了概括性介绍.结合部分实验研究,着重讨论了水力条件对于絮体性能的影响和絮体重组、历史的演化机理,结果表明,逐步增强的水力剪切条件有助于改善絮体的结构和强度.     

Fractal analysis of polyferric chloride-humic acid （PFC-HA） flocs in different topological spaces

The fractal dimensions in different topological spaces of polyferric chloride-humic acid (PFC-HA) flocs, formed in flocculating different kinds of humic acids (HA) water with different initial pH (9.00, 7.00, 5.00) and PFC dosages, were calculated by effective density-maximum diameter, image analysis, and N2 absorption-desorption methods, respectively. The mass fractal dimensions (Df) of PFC-HA flocs, being more than 2.0, calculated by bi-logarithm relation of effective density-maximum diameter and Logan empirical formula at initial pH of 7.00 had 11-13 percentage greater than those at pH 9.00 and 5.00, indicating the most compact flocs formed in flocculated HA water at initial pH of 7.00. The image analysis for those flocs indicates that after flocculating the HA water at initial pH greater than 7.00 with PFC flocculant, the fractal dimensions of D2 (logA vs. logdL) and D3 (logVsphere vs. logdL) of PFC-HA flocs decreased with the increase of PFC dosages, and PFC-HA flocs showed a gradually looser structure. At the optimum dosage of PFC, the D2 (logA vs. logdL) values of the flocs show 14%--43% difference with their corresponding Df, and they even had different tendency as the change of initial pH values. However, the D2 values of the flocs formed at three different initial pH in HA solution, calculated from the horizontal projected images with magnification about 9, had a same tendency with the corresponding Df. Based on fractal Frenkel-Halsey-Hill (FHH) adsorption and desorption equations, the pore surface fractal dimensions (Ds) for dried powders of PFC-HA flocs formed in HA water with initial pH 9.00 and 7.00 were all close to 2.9421, and the Ds values of flocs formed at initial pH 5.00 were less than 2.3746. It indicated that the pore surface fractal dimensions of PFC-HA flocs dried powder mainly show the irregularity from the mesopore-size distribution and some marcopore-size distribution.     

聚合氯化铁-腐殖酸(PFC-HA)絮体的粒度和分形维数的动态变化

通过采集PFC-HA絮体的单个样品和拍摄它们的二维图像,研究了在不同混凝条件下絮体的粒度和分形维数的变化.结果表明,原水pH的下降滞后了PFC-HA絮体的出现.原水pH≥7.0时,随着投药量的增加,PFC-HA絮体的分形维数D2(lgA-lgdL)和D3(lgV1-lgdL)随之降低,表明絮体的结构越来越疏松;而原水pH=5.0时,PFC-HA絮体的分形维数存在波动.在PFC的最佳投药量时,水力条件的优化可以提高HA的去除效果,但随着原水pH的下降,HA去除效果的提高程度也随之减小.在最佳水力条件下,PFC-HA絮体的粒度为数百微米,其分形维数值较大,表明絮体的结构较为密实.此外,PFC-HA絮体的粒度分布具有(类)分形特征,最佳水力条件下正的D.值表明絮体的粒度分布趋向平稳.在整个混凝搅拌过程中,PFC-HA絮体的分形维数的变化是与混凝的溶液化学条件、搅拌时间和分形维数类型有关,其D2具有先上升后下降的趋势,这一过程中絮体结构先趋向密实,然后趋向疏松.而且慢速搅拌过程中絮体的尺度也是先增加后下降.     

铜绿微囊藻对混凝除氟的促进作用及机理分析

以铜绿微囊藻、氯化铝（AlCl₃·6H₂O）为研究对象,通过三维荧光、场发射扫描电镜等表征,探究了藻类对氟化物混凝去除机制的影响.结果表明,在pH值为7.0,8.0,9.0,Al投加量在20.0~80.0mg/L的条件下,铜绿微囊藻对混凝除氟有明显的促进作用,其促进作用主要在于藻絮体对氟的表面吸附.铜绿微囊藻与氯化铝水解产物通过吸附架桥和网捕卷扫作用,聚集成较大较多的絮体.絮体粒径越大,除氟率越高.pH值为7.0,Al投加量为40.0mg/L时,絮体粒径达到最大值500μm,此时氟去除率最高,为77.37%;当Al投加量为80.0mg/L时,藻细胞破损严重,有机物过多释放,对混凝除氟起阻碍作用.絮体破碎吸附实验结果表明,对絮体进行一定强度破碎可以增加吸附位点,从而提高氟的去除率;但破碎强度过大,絮体粒径过小,对氟的吸附效率亦会降低.     

The influence of particle size and concentration combined with pH on coagulation mechanisms

In order to evaluate the influence of particle size and particle concentration on the coagulation process, two kinds of particle suspensions, nanoparticles and microparticles,were employed to investigate the effect of particle size on coagulation mechanisms with varying coagulation parameters. Results showed that it is easier for nanoparticles to cause self-aggregation because of Brownian motion, while interception and sedimentation are the mainly physical processes affecting particle transport for microparticles, so they are more stable and disperse more easily. The particle size distribution and particle concentration had distinct influence on the coagulation mechanisms. Under neutral conditions, as the amount of coagulant increased, the coagulation mechanism for nanoparticles changed from charge neutralization to sweep flocculation and the nanoparticles became destabilized, re-stabilized and again destabilized. For microparticles, although the coagulation mechanism was the same as that of nanoparticles, the increased rate of aluminum hydroxide precipitation exceeded the adsorption of incipiently formed soluble alum species, resulting in the disappearance of the re-stabilization zone. Under acidic conditions, Brownian motion dominates for nanoparticles at low particle concentrations, while sweep flocculation is predominant at high particle concentrations. As for microparticles, charge neutralization and sweep flocculation are the mechanisms for low and high particle concentrations respectively.Under alkaline condition, although the mechanisms for both nano-and microparticles are the same, the morphology of flocs and the kinetics of floc formation are different. At low particle concentrations, nanoparticles have larger growth rate and final size of flocs, while at high particle concentrations, nanoparticles have higher fractal dimension and recovery factors.     

活性污泥絮体粒径分布与分形维数的影响因素

絮体粒径分布和分形维数是活性污泥的重要参数.应用激光粒度仪测量了好氧活性污泥絮体在絮凝过程的粒径分布,研究了速度梯度、VSS/SS、EPS含量及Zeta电位对絮体粒径分布的影响.结果表明,絮体平均粒径与速度梯度显著负相关(R2>0.80),与Kolmogorov尺度数量级基本相当,其间差异性与污泥VSS/SS、絮体强度等有关;相同的速度梯度下,絮体平均粒径与VSS/SS或EPS含量显著正相关(R2>0.85),与Zeta电位负相关.有机质和EPS在活性污泥絮凝中作用明显,会增强絮体强度,提升絮凝效果;EPS中蛋白质比多糖对絮凝的促进作用更明显.基于显微图像分析方法,得到了好氧活性污泥絮体二维分形维数为1.28~1.72,三维分形维数为1.70~2.69.絮体分形维数随VSS/SS或EPS含量的增加而减小;对于相同的活性污泥,絮体三维分形维数随粒径增大而减小,符合幂函数关系式.     

Coagulation behavior and floc properties of compound bioflocculant-polyaluminum chloride dual-coagulants and polymeric aluminum in low temperature surface water treatment

This study was intended to compare coagulation behavior and floc properties of two dualcoagulants polyaluminum chloride–compound bioflocculant(PAC–CBF)(PAC dose first) and compound bioflocculant–polyaluminum chloride(CBF–PAC)(CBF dose first) with those of PAC alone in low temperature drinking water treatment. Results showed that dualcoagulants could improve DOC removal efficiency from 30% up to 34%. Moreover, CBF contributed to the increase of floc size and growth rate, especially those of PAC–CBF were almost twice bigger than those of PAC. However, dual-coagulants formed looser and weaker flocs with lower breakage factors in which fractal dimension of PAC–CBF flocs was low which indicates a looser floc structure. The floc recovery ability was in the following order:PAC–CBF PAC alone CBF–PAC. The flocculation mechanism of PAC was charge neutralization and enmeshment, meanwhile the negatively charged CBF added absorption and bridging effect.