Influential factors of formation kinetics of flocs produced by water treatment coagulants

The growth rate and size of floc formation is of great importance in water treatment especially in coagulation process.The floc formation kinetics and the coagulation efficiency of synthetic water were investigated by using an on-line continuous optical photometric dispersion analyze and the analysis of water quality.Experimental conditions such as alum dosage,pH value for coagulation,stirring intensity and initial turbidity were extensively examined.The photometric dispersion analyze results showed that coagulation of kaolin suspensions with two coagulants(alum and polyaluminium chloride) could be taken as a two-phase process:slow and rapid growth periods.Operating conditions with higher coagulant doses,appropriate pH and average shear rate might be particularly advantageous.The rate of overall floc growth was mainly determined by a combination of hydraulic and water quality conditions such as pH and turbidity.The measurement of zeta potential indicates that polyaluminium chloride exhibited higher charge-neutralizing ability than alum and achieved lower turbidities than alum for equivalent Al dosages.Under the same operating conditions,the alum showed a higher grow rate,but with smaller floc size.     

Advanced lignin-acrylamide water treatment agent by pulp and paper industrial sludge：Synthesis, properties and application

A novel flocculant LA （lignin-acrylamide polymer）, which was used as aid for aluminum sulfate and polyaluminum chloride in this study, was prepared by grafting acrylamide onto lignin that deriving from pulp and papermaking sludge. Physicochemical properties of LA were measured by X-ray photoelectron spectroscopy and scanning electron microscopy. The experimental outcome indicated acrylamide was grafted onto the lignin backbone successfully. The effects of LA addition were evaluated on coagulation performance and floc characteristics as a function of aluminum （Al） dosage, such as floc size, growth rate, strength and recoverability. Effects of different dosing sequences, Al dosed first and LA dosed first, were also investigated. LA used as coagulant aid markedly enhanced the removal efficiency of turbidity and dissolved organic carbon, especially at low Al dosages. The dissolved organic carbon removal efficiencies of aluminum sulfate and polyaluminum chloride at the Al dosage range selected in this study were improved more than 30% and 5% by LA, respectively. LA dramatically enlarged floc size and it was in the order： Al dosed first 〉 LA dosed first 〉 Al. Floc strength and recoverability were also improved by LA. LA played a significant role in charge neutralization, adsorption and bridging in floc formation.     

Influence of COM-peptides/proteins on the properties of flocs formed at different shear rates

Coagulation followed by floc separation is a key process for the removal of algal organic matter(AOM) in water treatment. Besides optimizing coagulation parameters,knowledge of the properties of AOM-flocs is essential to maximizing AOM removal.However, the impact of AOM on the floc properties remains unclear. This study investigated how peptides/proteins derived from the cellular organic matter(COM) of the cyanobacterium Microcystis aeruginosa influenced the size, structure, and shape of flocs formed at different shear rates(G). Flocs formed by kaolinite, COM-peptides/proteins and a mixture of the same were studied, and the effect of intermolecular interactions between floc components on floc properties was assessed. The coagulation experiments were performed in a Taylor–Couette reactor, with aluminum(Al) or ferric sulphate(Fe) utilized as coagulants. Image analysis was performed to gauge floc size and obtain data on fractal dimension. It was found that floc properties were affected by the presence of the COM-peptides/proteins and the coagulant used. COM-peptides/proteins increased floc size and porosity and widened floc size distributions. The Fe coagulant produced larger and less compact flocs than Al coagulant. Moreover, the decrease in floc size that occurred in parallel with increase in shear rate was not smooth in progress. A rapid change for the kaolinite-coagulant suspension and two rapid changes for the suspensions containing COM were observed. These were attributed to various intermolecular interactions between floc components participating in coagulation at different G. Based on the results obtained, shear rates suitable for efficient separation of flocs containing COM were suggested.     

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.     

Effects of ionic strength and temperature on the aggregation and deposition of multi-walled carbon nanotubes

The aggregation and deposition of carbon nanotubes(CNTs) determines their transport and fate in natural waters.Therefore,the aggregation kinetics of humic-acid treated multi-walled carbon nanotubes(HA-MWCNTs) was investigated by time-resolved dynamic light scattering in NaCl and CaCl_2 electrolyte solutions.Increased ionic strength induced HA-MWCNT aggregation due to the less negative zeta potential and the reduced electrostatic repulsion.The critical coagulation concentration(CCC) values of HA-MWCNTs were 80 mmol/L in NaCl and 1.3 mmol/L in CaCl_2 electrolyte,showing that Ca~(2+) causes more serious aggregation than Na~+.The aggregation behavior of HA-MWCNTs was consistent with Derjaguin-Landau-Verwey-Overbeek theory.The deposition kinetics of HA-MWCNTs was measured by the optical absorbance at 800 ran.The critical deposition concentrations for HA-MWCNT in NaCl and CaCl_2 solutions were close to the CCC values,therefore the rate of deposition cannot be increased by changing the ionic strength in the diffusion-limited aggregation regime.The deposition process was correlated to the aggregation since larger aggregates increased gravitational deposition and decreased random Brownian diffusion.HA-MWCNTs hydrodynamic diameters were evaluated at 5,15 and 25℃.Higher temperature caused faster aggregation due to the reduced electrostatic repulsion and increased random Brownian motion and collision frequency.HA-MWCNTs aggregate faster at higher temperature in either NaCl or CaCl_2electrolyte due to the decreased electrostatic repulsion and increased random Brownian motion.Our results suggest that CNT aggregation and deposition are two correlated processes governed by the electrolyte,and CNT transport is favored at low ionic strength and low temperature.     

Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

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.     

Analysis of floc morphology in a continuous-flow flocculation and sedimentation reactor

The floc morphology was investigated in a continuous-flow reactor, in order to understand the evolution of flocs in practical flocculation and sedimentation processes in water utilities. Kaolin-humic acid suspension was used as the test water, and polyaluminum chloride was chosen as the coagulant. An in-situ recognition system was applied to analyze the floc size, boundary fractal dimension, and eccentricity ratios. Particle numbers and turbidity were also determined in the sedimentation stage. At a coagulant dose of 1 mg/L as Al, the average floc size increased from 62 to 78 μm and the boundary fractal dimension was around 1.14, suggesting that flocs were compact and continuously grew during the entire flocculation process. However, with the dose increased to 5 mg/L, the average floc size decreased and stabilized at around 65 μm, with the fractal dimension of 1.20. It can be concluded that the excess coagulant doses resulted in the formation of chain-shaped, lower density, and more branched structure flocs, thereby restricting flocs' further growth in the subsequent flocculation. Floc morphology analysis suggested that charge neutralization dominated in the initial flocculation stage, then the bridge and sweep mechanisms were dominant in the subsequent flocculation. In addition, compared with the traditional inclined plate settler, a novel V-shaped plate settler introduced in this study had an advantage in small size floc(less than 5 μm) removal. The V-shaped region could promote aggregate restructuring and re-flocculation; therefore, the V-shaped plate settler provides an alternative method for sedimentation.     

The influence of various additives on coagulation process at different dosing point: From a perspective of structure properties

Structure properties of flocs (size, fractal dimension (D_f), etc.) have a high impact on coagulation efficiency. In this work, the influences of three different additives (ferric salt (Fe), phosphate (P), and citric acid (CA)) on coagulation process/efficiency were investigated. Results showed that a small amount of extra Fe can facilitate the growth of Al flocs by providing more ‘active sites’. Although zeta potential and D_f showed a limited change, the average floc size increased apparently and the increment was more obvious when Fe was added after the formation of the flocs. In contrast, P addition during the rapid mixing period will decrease the final average floc size, while the influence is less significant when P was added after the growth of the flocs. In terms of CA, a more striking negative effect on the growth ability of the flocs was observed compared to P. The strong complexing/coordination interactions between CA and aluminum hydroxide is the main reason behind the influence. CA also significantly decreased the D_f value of the flocs compared to P, and D_f showed a comparatively higher decrease when P or CA was added during the rapid mixing stage compared to the addition after the flocs formation. These results indicated that the addition of CA or P during the rapid mixing stage ‘inactivated’ or occupied more ‘active sites’ on the preliminarily formed Al NPs during the hydrolysis process, and therefore presented stronger impact on the morphology/size of the formed flocs.     

Influence of coagulation mechanisms and floc formation on filterability

Minimizing particles in water is a key goal for improving drinking water quality and safety.The media filtration process,as the last step of the solid–liquid separation process,is largely influenced by the characteristics of flocs,which are formed and controlled within the coagulation process.In a laboratory-based study,the impacts of the physical characteristics of flocs formed using aluminum sulfate on the filtration treatment of two comparative water samples were investigated using a photometric dispersion analyzer and a filterability apparatus.In general,the optimum dosage for maximizing filterability was higher than that for minimizing turbidity under neutral p H conditions.For a monomeric aluminum-based coagulant,the charge neutralization mechanism produced better floc characteristics,including floc growth speed and size,than the sweep flocculation mechanism.In addition,the charge neutralization mechanism showed better performance compared to sweep flocculation in terms of DOC removal and floc filterability improvement for both waters,and showed superiority in turbidity removal only when the raw water had high turbidity.For the different mechanisms,the ways that floc characteristics impacted on floc filterability also differed.The low variation in floc size distribution obtained under the charge neutralization mechanism resulted in the flocs being amenable to removal by filtration processes.For the sweep flocculation mechanism,increasing the floc size improved the settling ability of flocs,resulting in higher filter efficiency.     

On-line optical determination of floc size of Fe( Ⅲ ) coagulants

This study investigated the floc aggregation, average floc size, floc size variance and floc growth velocity when ferric chloride (FeCl3) and polyferric chloride (PFC) were used to treat the simulated water samples. The factors including coagulant dose, ionic strength and solution pH, which affect the floc aggregation, were studied. Experiments were carried out in a bench-scale reactor using photometric dispersion analyzer (PDA). Results showed that there were great differences between the floc aggregation of PFC and FeCl3.The average floc size and floc growth velocity of PFC were much larger than those of FeCl3. Compared with FeCl3, PFC gave a better coagulation performance in wider range of pH, dosage and ionic strength. It was also found that the coagulation efficiency of PFC did not depend on average floc size but on floc growth velocity.     

冷融技术联合化学调理对污泥脱水性能的影响及其机理

实验对比了常温(25℃)下阳离子聚丙烯酰胺(CPAM)、FeCl3/CaO、加酸及阳离子表面活性剂(CTAC)4种处理方式对污泥的调理效果.结果表明,CTAC对污泥的调理效果最好,可使污泥滤饼含水率降至68%.0℃时,未经处理(原泥)、CPAM、FeCl3/CaO、加酸处理条件下污泥脱水效果较常温时都有不同程度的提高,效果最好的为未经处理(原泥)和pH=2条件下的泥样;-15℃时,CTAC条件下滤饼含水率较常温下降了约6%,达到62.8%.污泥胞外聚合物(EPS)含量和污泥絮体结构对污泥脱水性能有一定影响.测定发现,EPS的溶出提高了絮体可压缩性,使污泥絮体内部结合水流出,从而改善污泥的脱水性能.电镜扫描(SEM)和粒径分析结果表明,经过FeCl3/CaO、加酸、CTAC和冷融处理后污泥表面结构和颗粒大小变化明显,脱水效果较原泥均有不同程度的提高.     

无机絮凝剂对SBR系统中活性污泥的影响研究

采用序批式活性污泥法（SBR）反应器进行模拟实验,系统地探究了聚合氯化铝（PAC）和聚合氯化铁（PFC）对活性污泥产生的影响.结果表明,PAC、PFC会使得污泥絮体变得紧实且边缘化,絮体中值粒径较未添加时分别增加了34.78%、12.90%.污泥的沉降性能和污泥活性随着PAC、PFC的积累而变差.微生物分泌的EPS含量降低,是因为添加PAC、PFC后微生物活性降低并导致微生物多样性降低.     

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.     

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.     

聚合氯化铁在微絮凝-深床过滤工艺中的应用

以聚铝(PAC)为参照比较研究了聚合氯化铁(PFC)在微絮凝深床过滤工艺中的应用效果.结果表明PFC投药量少(Fe:Al=3:5),其水头滤程可达63h,周期产水率可达1504m³/m²,而PAC的水头滤程为53h,周期产水率为1266 m³/m²;PFC表现出利于延长运行周期,提高产水率等优势.通过截污机理研究表明,PFC具有形成絮体快,与滤料作用迅速,脱水性能好等特点,与PAC相比PFC更适用于微絮凝-深床过滤工艺.     

混凝-吸附处理黄河水及对氯消毒中氯衰减的影响

选用2种无机高分子混凝剂聚合氯化铁(PFC)和聚合氯化铝(PAC)处理黄河水,考察了混凝剂的投加量对浊度、UV254、DOC和高锰酸盐指数的去除效果,并结合混凝出水的Zeta电位分析其混凝机制.选择粉末活性炭与混凝联用,研究了混凝剂和吸附剂投加量以及二者的投加顺序对有机物去除效果的影响,并对混凝吸附后出水进行加氯消毒,考察水中残余氯随时间的变化.结果表明,2种混凝剂均有较高的浊度去除率(﹥90%).PAC对UV254、高锰酸盐指数和DOC的去除率分别为29.2%、26.1%和27.9%;PFC对三者的去除率分别为32.3%、23.3%和32.9%.PAC在混凝过程中,电中和作用占主导地位;PFC在混凝过程中,吸附架桥和电中和同时发挥作用.混凝-吸附联用处理黄河水样时,有机物的去除率随混凝剂和吸附剂投加量的增加而升高.先混凝后吸附工艺对UV254和DOC的去除效果优于先吸附后混凝工艺.先使用PAC混凝后吸附对UV254和DOC的去除率分别为95.2%和99.9%;对于PFC,先混凝后吸附对UV254和DOC的去除率分别为90.1%和99.9%.但是先投加粉末活性炭能提高矾花的沉降性能,且处理出水在保持持续消毒效果方面优于前者.     

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.