三种常见混凝机理为主导条件下絮体特性研究

以模拟低浊微污染水为原水,硫酸铝[Al2 (SO4)3]为混凝剂,考察了3种常见混凝机理(电性中和、吸附架桥和网捕卷扫)为主导条件下絮体的成长过程、二维边界分形维数(Dpf)和比表面积及其与混凝效果的相关性.结果表明:吸附架桥为主导机理下絮体最大增长速率S (0.951)最快,达到稳定后絮凝指数FI最大(3.7%),二维边界分形维数Dpf最大(1.587),絮体呈块状且絮体间出现孔状间隙,比表面积介于网捕卷扫和电性中和之间[网捕卷扫(83.646m2/g)>吸附架桥(98.808m2/g)>电性中和(116.046m2/g)];FI值、S及Dpf变化与浊度去除率相关性较好,其相关系数分别达0.979、0.982和0.963,同时比表面积大的絮体吸附容量大,有机物的去除率高.     

低温条件下絮体破碎再絮凝去除水中颗粒的研究

为了了解低温条件下絮体的形成/破碎/再絮凝过程在适当条件下对絮凝去除水中颗粒物的强化效果,采用PDA2000透光率脉动检测仪对絮凝破碎再絮凝过程进行了在线监测.研究结果表明,当电中和机理占主导作用时(混凝剂投加量小于0.1 mmol·L-1),絮体破碎后能重新絮凝,絮体大小能恢复到破碎之前;而当网捕卷扫机理占主导作用时(混凝剂投加量大于0.2 mmol·L-1),絮体的恢复情况不如电中和条件,再絮凝能力降低.投加适量的腐殖酸会增加絮体破碎前后的分形维数,但过量的腐殖酸则会降低破碎前后絮体的分形维数.絮体破碎再絮凝后其分形维数比破碎前高.腐殖酸的投加量并不会明显影响絮凝和破碎后再絮凝的FI指数.电中和絮体破碎前初始絮凝时间越长破碎后沉后水浊度越低,破碎后其浊度会比破碎前显著减小.较低投量的铝盐就能使得沉后水浊度降到很低,因此可以降低混凝剂投量而达到更好的水处理效果.     

聚合氯化铝（PACl）混凝絮体的破碎与恢复

通过烧杯实验以及在线粒度监测考察了聚合氯化铝（PACl）混凝所生成絮体的破碎以及随后絮体的恢复情况.结果发现,絮体的破碎以及恢复情况因混凝区域的不同而呈现不同的规律.在稳定区,絮体的强度较大,不易破碎,且破碎后的絮体可进一步增长,其恢复因子高达259%;在电中和混凝区,絮体的强度最小,易于破碎,但破碎后可完全恢复;在再稳区和卷扫混凝区,絮体的强度较大,不易破碎,但破碎后不能完全恢复,其中后者的恢复因子仅为18.6％.再搅拌强度越大,对絮体的破碎及恢复程度的影响越大.对于卷扫混凝,经再搅拌破碎后而得到部分恢复的絮体,相对于未经再搅拌的絮体而言,其絮体层与水体间界面的沉降高度及平均沉降速率均较低,且在絮凝沉降区和区域沉降区,该絮体界面的瞬时沉降速率在同一絮体浓度下均较低,但在压缩沉降区,二者的瞬时沉降速率相同.     

Hydrolysis of polyaluminum chloride prior to coagulation: Effects on coagulation behavior and implications for improving coagulation performance

The effects of polyaluminum chloride (PACl) hydrolysis prior to coagulation on both the coagulation zone and coagulation performance of a kaolin suspension were investigated by a novel jar test named the “reversed coagulation test”. The tests showed that PACl hydrolysis prior to coagulation decreased the performance of charge neutralization coagulation in the case of short-time slow mixing (10 min; G = 15 sec ?1 ) and increased the optimal dosage for charge neutralization and sweep coagulation. Moreover, the hydrolysis time had insignificant effects on the size and zeta potential of PACl precipitates and the residual turbidity of the raw water. However, PACl hydrolysis prior to coagulation and the size of PACl precipitates had a negligible effect on the performance of sweep coagulation.The results imply that, in practice, preparing a PACl solution with deionized water, rather than tap water or the outlet water from a wastewater treatment unit, can significantly save PACl consumption and improve the performance of charge neutralization coagulation,while preparing the PACl solution with tap or outlet water would not affect the performance of sweep coagulation. In addition, the optimal rapid mixing intensity appears to be deter-mined by a balance between the degree of coagulant hydrolysis before contacting the primary particles and the average size of flocs in the rapid mixing period. These results provide new insights into the role of PACl hydrolysis and will be useful for improving coagulation efficiency.     

复合生物絮凝剂CBF-1的絮凝作用机理研究

采取PAC+絮凝剂的复配方式开展高岭土悬浊液烧杯实验,考察了复合生物絮凝剂CBF-1、CBF-1溶解物及微生物絮凝剂MBF8的絮凝特性,并借助iPDA仪分析和扫描电镜、光学显微镜观察等手段,比较分析了絮凝过程及絮体特性的差异.结果表明,各复配絮凝的浊度去除效果排序为CBF-1＞ CBF-1溶解物＞MBF8,CBF-1投加量1 mg·L-1时,浊度去除率可达到97.5％;絮体强度排序为CBF-1＞ CBF-1溶解物＞MBF8,絮体恢复因子排序为MBF8＞CBF-1溶解物＞CBF-1,絮体大小排序为CBF-1＞ CBF-1溶解物＞MBF8.单独投加PAC或投加PAC+MBF8的情况下,形成的絮体形态相对规整、密实;投加PAC+ CBF-1溶解物或投加PAC+ CBF-1形成的絮体则相对无序、疏松,CBF-1作用下絮体大、沉降快.CBF-1中高电荷MBF8组分及大分子羧甲基纤维素、羧甲基多聚糖等组分具有强的电荷中和与桥联协同增效作用;CBF-1还含有纤维素、木质素等大分子量且带多种官能团的不溶性组分,在桥联和吸附过程中也起着重要作用.     

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.     

Removal of total cyanide in coking wastewater during a coagulation process：Significance of organic polymers

Whether a cationic organic polymer can remove more total cyanide （TCN） than a non-ionic organic polymer during the same flocculation system has not been reported previously. In this study, the effects of organic polymers with different charge density on the removal mechanisms of TCN in coking wastewater are investigated by polyferric sulfate （PFS） with a cationic organic polymer （PFS-C） or a non-ionic polymer （PFS-N）. The coagulation experiments results show that residual concentrations of TCN （Fe（CN）6^3-） after PFS-C flocculation （TCN 〈 0.2 mg/L） are much lower than that after PFS-N precipitation. This can be attributed to the different TCN removal mechanisms of the individual organic polymers. To investigate the roles of organic polymers, physical and structural characteristics of the floes are analyzed by FT-IR, XPS, TEM and XRD. Owing to the presence of N＋ in PFS-C, Fe（CN）3- and negative flocs （Fe（CN）63- adsorbed on ferric hydroxides） can be removed via charge neutralization and electrostatic patch flocculation by the cationic organic polymer. However, non-ionic N in PFS-N barely reacts with cyanides through sweeping or bridging, which indicates that the non-ionic polymer has little influence on TCN removal.     

混凝过程中流场结构的PIV测量与表征

采用粒子成像速度场仪(PIV)在不投加专用示踪粒子的条件下,以混凝絮体为示踪粒子,对Taylor-Couette反应器内的絮凝反应流场进行测量与表征.结果表明,内筒旋转雷诺数Re在900~2900时,流场中产生的涡具有相似的特殊波状涡结构,相邻涡旋形态大小发生周期性变化,涡间存在主流液体的移动,这种涡结构有利于絮体结合生长成较大的絮体颗粒,便于沉降而导致较高的絮凝沉淀去除率.这也证实PIV技术能够在进行混凝反应的同时,用混凝过程中的微絮体为示踪粒子对混凝过程进行流场测量,不必再额外添加示踪粒子,就能较好地反映混凝过程中涡旋的形态变化特征,从而实现对絮凝过程的同步测量与表征.     

聚硅酸铁混凝剂絮凝与破碎的定量研究

以水玻璃、硫酸亚铁及氯酸钠为原料,应用共聚工艺制备聚硅酸铁(PSF)混凝剂,采用搅拌实验和颗粒计数法对比研究PSF与复合铝铁(PFA)的混凝性能,絮凝阶段残余粒子分布及紊流剪切力对絮体的影响.结果表明,高投药量时PSF去除高锰酸盐指数的性能优于PFA.PSF处理地表水时不宜采用过高或过低的絮凝速度,絮凝速度与絮凝时间应紧密配合才能提高混凝性能,即提高絮凝速度则需要减少絮凝时间.增加紊流剪切力时,PSF絮体的破碎程度远远小于PFA,被打碎的PSF絮体其再结合能力大于PFA.在数量级上,PSF的絮凝系数KA为10-2～10-3,破碎系数KB为10-7～10-8.对于粒径＜2 μm的颗粒,PSF的KA比PFA大4个数量级,KB与PFA相近,而其余粒径范围PSF的KA比PFA大近2个数量级,KB比PFA小近10多倍.     

利用小角度激光光散射研究阳离子有机高分子絮凝剂的絮体粒径和絮体结构

利用小角度激光光散射在线监测技术研究了不同阳离子有机高分子絮凝剂对带负电荷的高岭土颗粒体系的絮凝动力学和絮体结构.对于高电荷密度的聚二甲基二烯丙基氯化铵(PDADMAC),由于分子量低其初始絮凝反应速度较慢,最终形成的絮体也较小.絮凝过程中,其絮体结构发生重组和排列,分形维数从1.83升高到2.09,所形成的絮体密实.对于低电荷密度的2种阳离子聚丙烯酰胺(CPAM),因其分子量大投药量高,絮凝反应速度较快;但其絮体的分形维数较小且在絮凝反应中基本保持不变,形成的絮体结构开放和松散.基于有机高分子对高岭土体系浊度和zeta电位的影响,结合絮凝动力学和絮体结构分析,结果表明,PDADMAC絮凝机理是电中和作用,而随着分子量的增加和电荷密度的降低,CPAM则主要通过吸附架桥作用产生絮凝.     

混凝过程中絮体形貌的PIV成像观测与表征

采用粒子成像速度场仪(PIV)对Taylor-Couette反应器内的混凝过程中絮体的微观形貌进行了观测与表征.结果表明,内筒转速在20～60r/min范围内,生成的絮体颗粒较大,粒径分布均匀,絮凝沉淀效果最好.由于内筒旋转速度的变化直接导致混凝流场形态的变化,所以混凝过程中流场形态的变化对絮体生长过程有重要影响,进而直接影响到混凝效果.混凝过程中流场的周期性变化、涡间存在液体传递的波状涡结构有利于絮体颗粒的结合生长,并导致较高的絮凝沉淀去除率.这也说明PIV技术能够在测量流场的同时较好地反映混凝过程中微絮体的形貌变化特征,从而实现对絮凝过程的原位观测与表征.     

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.     

聚合硫酸铁(PFS)混凝腐殖酸(HA)的过程中典型操作因素的影响研究

针对聚合硫酸铁（PFS）混凝-沉淀去除腐殖酸（HA）水样的过程,通过测定典型操作因素（PFS投加量、原水pH和搅拌方式）下微絮体的zeta电位、上清液的浊度、UV254、pH值及电导率和絮体沉降体积变化,探讨了这些因素对该过程的影响.结果表明：在原水pH=6.00时,PFS混凝HA的主要机制为电中和作用,搅拌方式对PFS的最佳投加范围没有明显的影响,但单一搅拌方式下HA的去除效果更好;在原水pH=8.00时,吸附络合-卷扫絮凝成为主要的混凝机制,复合搅拌方式下PFS的最佳投加量范围大于单一搅拌方式,且前者的HA去除效果更好.整体而言,几种混凝条件下PFS最佳投药量对应的微絮体zeta电位均在-12.00mV左右;原水pH=6.00时PFS混凝-沉淀去除HA的效果比原水pH=8.00时的好,且前者形成的PFS-HA沉淀絮体体积较小,但单一搅拌方式下絮体结构的重组过程并不是影响絮体体积的主要因素.复合搅拌方式中开始阶段的高强度搅拌有助于PFS组分在HA水样中的分散而有利于其电中和作用的发挥,但对PFS的水解过程影响不大.     

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（1.16 μm/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,pH=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pH=9的条件下进行老化则会涉及溶解-沉淀-结晶反应.     

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.     

Effect of in-situ formed Al hydrates through long-term aging on enhanced particle destabilization by PACl coagulation

Aging of polyaluminum chloride (PACl) coagulants could significantly influence hydrolyzed Al speciation ruling coagulation performance. The goal of this study was to investigate Al species transformation through long-term aging and its impact on coagulation performance. Two kinds of commercial coagulants (PACl-1 and PACl-2) were stored for in-situ aging tests in six months to evaluate Al species variation with time and the performance of coagulation with natural turbid waters. The results showed that CaSO₄ precipitation easily occur in a commercial PACl coagulant with time as it contains SO₄^2? and Ca²⁺. It also activates the precipitation of gibbsite Al(OH)₃ in PACl with aging. Through 180 days aging, both monomeric Al (Al_a) and polymeric Al (Al_b) substantially transform into colloidal Al (Al_c) and precipitated for both PACl coagulants. At low turbidity (10 NTU), PACl-1 has a superior turbidity reduction rate than PACl-2, while PACl-2 performs a little better turbidity reduction at high turbidity (1000 NTU) regardless of aging time. With aging time, an obvious decrease in turbidity reduction for PACl-1 coagulation is observed at low turbidity of 10 NTU, while the improvement in turbidity reduction for PACl-2 coagulation by enhanced sweep flocculation can be achieved as Al_b mostly transform into Al_c after 150 days aging. It is concluded that dominant in-situ formed Al_c after a long time hydrolysis can improve PACl coagulation efficiency in turbidity reduction by enhanced sweep flocculation, especially for low turbidity water, but the increase in preformed Al_c in PACl would worsen particle destabilization after aging.     

Characterization of cake layer structure on the microfiltration membrane permeability by iron pre-coagulation

A cake layer is formed by coagulation aggregates under certain transmembrane pressure in the coagulation-microfiltration (MF) process. The characteristics of humic acid aggregates coagulated by different iron-based coagulants, such as charge, size, fractal dimension and compressibility, have an effect on the cake layer structure. At the optimum iron dose of 0.6 to 0.8 mmol/L for ferric chloride (FC) and polymer ferric sulfate (PFS) pre-coagulation, at the point of charge neutralization for near zero zeta potential, the aggregate particles produced possess the greatest size and highest fractal dimension, which contributes to the cake layer being most loose with high porosity and low compressibility. Thus the membrane filterability is better. At a low or high iron dose of FC and PFS, a high negative or positive zeta potential with high charge repulsion results in so many small aggregate particles and low fractal dimension that the cake layer is compact with low porosity and high compressibility. Therefore the membrane fouling is accelerated and MF permeability becomes worse. The variation of cake layer structure as measured by scanning electric microscopy corresponds with the fact that the smaller the coagulation flocs size and fractal dimension are, the lower the porosity and the tighter the cake layer conformation. This also explains the MF membrane flux variation visually and accurately.     

HCA强化混凝预处理生活污水的效能及机理

通过单因素及正交试验,以聚二甲基二烯丙基氯化铵（HCA）为混凝剂对模拟农村生活污水进行强化混凝预处理,考察了影响HCA混凝去除SS、TP及有机物的主要因素及其主次顺序,并以Zeta电位及分形维数对HCA的混凝机理进行了分析.结果表明,影响HCA处理效果的因素顺序为初始pH值值 > HCA投加量 > 絮凝搅拌时间 > 混合搅拌速度梯度 > 混合搅拌时间 > 絮凝搅拌速度梯度,在优化条件下HCA混凝对SS、TP及COD去除率最高分别达94.1%、74.9%及61.1%;当HCA投加量为15mg/L时,Zeta电位与絮体分形维数分别为-2.03mv及1.0149.试验表明HCA对生活污水具有较好的处理效果,强化混凝去除污染物的机理主要是电性中和作用.     

阳离子聚电解质聚二甲基二烯丙基氯化铵的絮凝机理初探

以聚二甲基二烯丙基氯化铵PDADMAC(特性粘度分别为2.7,1.4,0.7)为絮凝剂,对比PAC和PFC,通过残余浊度、Zeta电位、FI絮凝指数的测定,研究了PDADMAC对高岭土悬浊体系(浊度分别为6000,1000,200和10 NTU)的絮凝特性,并对其絮凝作用机理进行了探讨.结果表明,PDADMAC的吸附构型决定其絮凝机理在较低初始悬浊物浓度下(200 NTU)为单个颗粒物表面吸附覆盖及其"吸附电中和"絮凝模型;在高浊条件下(＞1000 NTU)为单颗粒表面(Monomer)部分吸附覆盖及其"吸附架桥"絮凝模型.     

海藻酸钠对改性黏土絮凝特征的影响

以海藻酸钠为藻源有机质的模式化合物,考察了赤潮水体中藻源有机化合物对改性黏土絮凝速率及絮凝体特征的影响;并利用图像分析法,测定了絮凝体的分形维数Df,借助分形维数对改性黏土的絮凝形态学特征进行了半定量化分析.结果表明:当海藻酸钠浓度在10~100mg/L范围内时,可以提高改性黏土絮凝的速率,絮凝体的分形维数Df、絮凝体强度呈现出先增大后减小的规律;其中,最佳浓度为50mg/L,其最大絮凝速率达到44.13、Df 为1.6823.低浓度(100mg/L)海藻酸钠能促进改性黏土的絮凝效率,但促进作用呈现减小的趋势,表现为最大絮凝效率减小,Df降低、絮凝体的空隙率增大.