Characteristic analysis on temporal evolution of floc size and structure in low-shear flow

A series of flocculation tests were performed to investigate the effect of low-shear rates (G = 3-16 s⁻¹) on flocculation of kaolin suspension by polyaluminum chloride (PACl), with the goal of understanding floc growth mechanisms. Results were reported in terms of floc average size (d_p) and boundary fractal dimension (D_pf), derived from a non-intrusive optical sampling and digital image analysis technique. As expected, the rate of floc aggregation increased with increasing G, resulting in faster changes in aggregate size and structure in the initial stage of flocculation. Nevertheless, steady state was attained faster for D_pf than for d_p at the same shear rates, possibly due to the self-similarity of fractal aggregates. An interesting finding was that at G = 3 s⁻¹, an obvious plateau was observed for the average-size evolution at steady state; for shear rates of 6 and 7 s⁻¹, the flocs exhibited some decrease after reaching the peak of size, mainly as a result of floc settling at steady state; and for G = 11-16 s⁻¹, a decrease in floc size was possibly attributed to the irreversibility of PACl-floc breakage. The process of floc growth was described using a fractal growth model, which defined flocculation as the result of the combined processes of aggregation and restructuring. The conceptual model could effectively characterize temporal changes in floc size and structure, and found that fragmentation followed by reformation seemed to be more effective in forming larger and more compact aggregates than the restructuring process due to erosion and reformation, which may provide useful insights for the design of flocculation reactors.     

Application of fractal dimensions to study the structure of flocs formed in lime softening process

The use of fractal dimensions to study the internal structure and settling of flocs formed in lime softening process was investigated. Fractal dimensions of flocs were measured directly on floc images and indirectly from their settling velocity. An optical microscope with a motorized stage was used to measure the fractal dimensions of lime softening flocs directly on their images in 2 and 3D space. The directly determined fractal dimensions of the lime softening flocs were 1.11-1.25 for floc boundary, 1.82-1.99 for cross-sectional area and 2.6-2.99 for floc volume. The fractal dimension determined indirectly from the flocs settling rates was 1.87 that was different from the 3D fractal dimension determined directly on floc images. This discrepancy is due to the following incorrect assumptions used for fractal dimensions determined from floc settling rates: linear relationship between square settling velocity and floc size (Stokes’ Law), Euclidean relationship between floc size and volume, constant fractal dimensions and one primary particle size describing entire population of flocs. Floc settling model incorporating variable floc fractal dimensions as well as variable primary particle size was found to describe the settling velocity of large (>50 μm) lime softening flocs better than Stokes’ Law. Settling velocities of smaller flocs (<50 μm) could still be quite well predicted by Stokes’ Law. The variation of fractal dimensions with lime floc size in this study indicated that two mechanisms are involved in the formation of these flocs: cluster-cluster aggregation for small flocs (<50 μm) and diffusion-limited aggregation for large flocs (>50 μm). Therefore, the relationship between the floc fractal dimension and floc size appears to be determined by floc formation mechanisms.     

吸附架桥机理主导下APAM的多级絮凝效能

对吸附架桥机理主导下阴离子聚丙烯酰胺(APAM)的絮凝过程进行了研究,通过改变絮凝剂投加工况,对比分析常规絮凝与多级絮凝在污染物去除效果、絮体性能、絮体生长动力学与污泥调理能耗等方面的差异。结果表明,相同投药量下,两级絮凝的出水浊度低于三级絮凝和常规絮凝,两级絮凝在最少的APAM投加量(2 mg/L)下达到最低的出水浊度(19.53 NTU);与常规絮凝相比,两级絮凝的絮体成长速率、平均粒径和沉降速率分别增加12.67%、30μm、36.74%。两级絮凝在投加间隔为240 s、投配比为1∶1条件下絮凝效能最优,出水浊度为15.34 NTU,絮体沉降速率为1.1 NTU/s,絮体密度达到1.123 4 g/cm³。絮体破碎再絮凝过程中,两级絮凝与常规絮凝破碎后均能恢复至破碎前水平,但破碎后均出现不可逆的絮体结构破损,粒径在0~100μm的絮体颗粒增多,粒径>400μm的絮体减少,破碎后两级絮凝的絮体强度因子(68.15%)高于常规絮凝(41.63%),两级絮凝的絮体强度和抗破碎剪切能力更高。在剩余污泥调理方面,两级絮凝产生的污泥只需要投加40mg/L的APAM就可以达到最低的滤饼含水率(75.5%)。因此,两级絮凝可以显著提升除浊效能与絮体性能,是强化絮凝的发展方向。     

Strength of ferric hydroxide flocs

Strength and break-up of flocs produced in flocculation of water and effluent with ferric chloride were studied. Floc size was determined by a photographing technique and area and perimeter measurements by a Quantimet apparatus.The experimental results obeyed the expression d_max = GC⁻²γ with γ = 0.3 for effluent and γ = 0.5 for water indicating both viscous and inertial effects in break-up. Floc strength parameter C increased with polymeric coagulant aid addition, higher C values were obtained in water than in effluent.Floc break-up seems to take place by erosion of particles and flocs once disrupted do not grow again.     

A study of titanium sulfate flocculation for water treatment

There are limited studies available on titanium salt flocculation. In this research, coagulation experiments of titanium sulfate were conducted using both distilled water and kaolin clay suspension. Results showed that titanium sulfate flocculation was most effective in the pH range 4-6, and negligible concentrations of titanium were found in the well-flocculated water. The floc isoelectric point (IEP) was found to be near pH 5. Measurements showed that the titanium flocs possessed greater density, diameter and settling velocity than the aluminum flocs. The titanium flocs were composed of TiO(OH)₂, which would change from the amorphous phase into anatase titanium dioxide under elevated temperatures. Floc images showed the structural similarity of titanium and aluminum flocs. Laboratory results and a pilot experiment showed that titanium sulfate could be an alternative coagulant for water and wastewater treatment.     

Size and structure evolution of kaolin-Al(OH)3 flocs in the electroflocculation process: a study using static light scattering

Electroflocculation (EF) is gaining recognition as an alternative process to conventional coagulation/flocculation. The electrical current applied in EF that generates the active coagulant species creates a unique chemical/physical environment in which competing redox reactions occur, primarily water electrolysis. This causes a transient rise in pH, due to cathodic formation of hydroxyl ions, which, in turn, causes a continuous shift in coagulation/flocculation mechanisms throughout the process. This highly impacts the formation of a sweep floc regime that relies on precipitation of metal hydroxide and its growth into floc. The size and structural evolution of kaolin-Al(OH)₃ flocs was examined using static light scattering techniques, in aim of elucidating kinetic aspects of the process. An EF cell was operated in batch mode and comprised of two concentric electrodes - a stainless steel cathode (inner electrode) and an aluminum anode (outer electrode). The cell was run at constant current between 0.042 A and 0.22 A, and analyses performed at pre-determined time intervals. The results demonstrate that EF is able to generate a range of flocs, exhibiting different growth rates and structural characteristics, depending on the conditions of operation. Growth patterns were sigmoidal and a linear correlation between growth rate and current applied was observed. The dependency of growth rate on current can be related to initial pH and aluminum dosing, with a stronger dependency apparent for initial optimal sweep floc regime. All flocs exhibited a fragile nature and undergo compaction and structural fluctuations during growth. This is the first time size and structural evolution of flocs formed in the EF process is reported.     

Compaction of flocculated material

The device used in the experiment consists of a flat-bottomed graduated cylinder and a coaxial plunger. A suspension flocculated with chemicals is sedimented after being mechanically worked within the graduate, and the supernatant water is removed with a pipette. The plunger is thrust into the sludge at a constant speed. The sludge is not only compressed but also flows into the annular gap between the plunger and the graduate, resulting in liberation of water. The liberated water is accumulated on the sludge in the annular gap. The “sludge bulkiness” β is used to describe the volumetric proportion of sludge and solids in it. The sludge bulkiness values before and after the “plunger test” are denoted as β_i and β_f, respectively. The values of β_i and β_j have been explored as a function of the time of the mechanical working. As a result, there is a definite time lag between the maximum value of β_i and the minimum value of β_f. The minimum value of β_j is obtained when the sludge consists of “pelleted flocs”.     

Structure of hydroxide flocs

A survey of the literature on floc structure demonstrates that no good structural model for gelatinous hydroxide flocs exists. In this investigation hydrolysing metal salts were used during the coagulation-flocculation of very dilute kaolinite suspensions.The influence of kinetic process parameters on the floc strength is used to prove the validity of a four level organization of hydroxide floc aggregates. The different levels of organization are: primary particles, flocculi, flocs and floc aggregates. The bonds between the particles of the different levels are elastic.     

A comprehensive study on the biological treatabilities of phenol and methanol—I. Analysis of bacterial growth and substrate removal kinetics by a statistical method

An unbiassed statistical method was developed to evaluate kinetic parameters in the biological oxidation of wastewaters. Through the statistical analyses of the biological oxidation kinetics, it was shown that the kinetic equations satisfactorily described the bacterial growth and substrate removal kinetics where X is biomass concentration, S is substrate concentration, t is time, a is cell yield coefficient, k_d is cell decay coefficient, K_s is Michaelis-Menten constant, and k is substrate removal rate coefficient. The coefficients K_s and a changed with temperature insignificantly while k and k_d were closely related to it. The temperature independent coefficients K_s and a were estimated to be 236 mg 1⁻¹ (standard deviation, σ = 70 mg 1⁻¹) and 1.21 (σ = 0.06) respectively for phenol, and 2330 mg 1⁻¹ (σ = 1410 mg 1⁻¹) and 1.25 (σ = 0.45) respectively for methanol based on total organic carbon (TOC) and volatile suspended solids (VSS). The oxygen utilization rate can be formulated as where Rr is the oxygen utilization rate (mg 1⁻¹ O₂ time⁻¹), as′ is a coefficient designating oxygen requirement per substrate utilized, and b′ is a coefficient designating oxygen requirement per biomass for endogeneous respiration. The coefficient a′ was 1.39 for phenol and 2.23 for methanol, and b′ was 1.42 k_d for both substances based on TOC and VSS.     

The extent of reversibility of polychlorinated biphenyl adsorption

The extent of reversibility of PCB bonding to sediments has been characterized in studies on the partitioning behavior of a hexachlorobiphenyl isomer. Linear non-singular isotherms have been observed for the adsorption and desorption of 2.4.5.2′,4′,5′ hexachlorobiphenyl (HCBP) to 1100 ppm sediment suspensions. Partition coefficients, π(1 kg−1), for desorption from lake sediments (Saginaw Bay. Lake Huron. Michigan) are substantially greater (π_d 20.000–35.000) than those obtained for adsorption (π₄ 9000–14,000). HCBP was found to be more weakly adsorbed to montmorillonite (π_a − 3000, π_d 9000) and kaolinite (π_a 1000, π_d 3000) clay samples than to the natural sediment samples. Desorption results (π_d) for Saginaw Bay sediments were quite similar to π values (15,000–35.000) calculated from field measurements of aqueous and particulate PCB concentrations. For Saginaw Bay sediments and clay minerals partitioning appeared to be correlated both to sediment surface area and to sediment organic content. A regression analysis using both of these variables explained 90% of the observed variations. HCBP adsorption at 40 C (π_a 14,000) was significantly greater than at 1° C (π_a 6500) resulting in a calculated enthalpy of adsorption of +3.3 kcal mol⁻¹. Non-singular isotherm behavior was not found to be readily attributable to microbiological, kinetic or experimental effects. Evidence from consecutive desorption studies suggests that while HCBP adsorption may ultimately be reversible. release from sediments appeared to involve desorption along two distinct isotherms. These results have been interpreted in terms of possible similarities between the sorption properties observed in the distilled water systems of the present study and PCB bonding processes in natural water systems.     

混凝剂加注量的自动控制新方法

报导了净水过程中使用计算机实时采集和定量分析絮凝池絮体图像,算出絮体沉淀“等效直径”作为控制混凝剂加注率的目标值,并用进水流量和沉淀水浊度信号自动修正目标设定植,加注量为进水流量与加注率之积。实验数据表明,该方法能适应水质和其他因素的变化自动调整加注量,达到了稳定沉淀水浊度的目的。     

Breakage and re-growth of flocs: effect of additional doses of coagulant species

Several polyaluminum chloride (PACl) coagulants were prepared, with different OH/Al ratios (B values), and characterized by Ferron assay. These were used in studies of floc formation, breakage and re-growth with kaolin suspensions under controlled shear conditions, using a continuous optical monitoring method. Particular attention was paid to the effect of small additional coagulant dosages, added during the floc breakage period, on the re-growth of broken flocs. The results showed that the re-growth ability was greatly dependent on the nature of the PACl species added as second coagulant. The re-growth ability of broken flocs was greatest when the second coagulant was PACl₀ (i.e. AlCl₃, with B = 0) and least with PACl₂₅ (B = 2.5). In the latter case there was no effect on floc re-growth, irrespective of the initial coagulant used. PACls with intermediate B values gave some improvement in floc re-growth, but less than that with PACl₀. Additional dosage of PACl₀ gave re-grown flocs about the same size or even larger than those before breakage. The re-growth of broken flocs is significantly correlated with the species Al_a (monomeric) and Al_b (polymeric), as determined by Ferron assay. The amorphous hydroxide precipitate formed from PACl₀, (mainly Al_a) can greatly improve the adhesion between broken flocs and give complete re-growth. However, for PACl₂₅, mostly composed of Al_b, the nature of the precipitate is different and there is no effect on floc re-growth.     

Floc settling characteristics of turbid water coagulated with moringa oleifera seeds

The results of studies into the particle aggregations and settling rates of flocs from turbid water (kaolin suspension) with turbidities varying from 50 to 550 NTU coagulated with Moringa oleifera seeds are presented. The results of the laboratory based study showed that the maximum value of the “apparent aggregation rate”, K _app,increased with increase in initial turbidity. K _app was found to be 0.000778 for low turbidity (50 NTU) and 0.00654 for high turbidity (550 NTU). The velocity gradient for rapid mix at the maximum K _app was found to be constant at 443/sec for all turbidities. Settling rate of floc coagulated with Moringa oleifera seed was dependent on the initial turbidity of the water sample. For water with initial turbidity of 50 NTU, 30% to 70% turbidity was removed between 60 and 210 minutes, while for high turbidity of 400 to 550 NTU, 80% to 95% turbidity removal occurred between 60 and 150 minutes.     

The impact of pH on floc structure characteristic of polyferric chloride in a low DOC and high alkalinity surface water treatment

The adjustment of pH is an important way to enhance removal efficiency in coagulation units, and in this process, the floc size, strength and structure can be changed, influencing the subsequent solid/liquid separation effect. In this study, an inorganic polymer coagulant, polyferric chloride (PFC) was used in a low dissolved organic carbon (DOC) and high alkalinity surface water treatment. The influence of coagulation pH on removal efficiency, floc growth, strength, re-growth capability and fractal dimension was examined. The optimum dosage was predetermined as 0.150 mmol/L, and excellent particle and organic matter removal appeared in the pH range of 5.50-5.75. The structure characteristics of flocs formed under four pH conditions were investigated through the analysis of floc size, effect of shear and particle scattering properties by a laser scattering instrument. The results indicated that flocs formed at neutral pH condition gave the largest floc size and the highest growth rate. During the coagulation period, the fractal dimension of floc aggregates increased in the first minutes and then decreased and larger flocs generally had smaller fractal dimensions. The floc strength, which was assessed by the relationship of floc diameter and velocity gradient, decreased with the increase of coagulation pH. Flocs formed at pH 4.00 had better recovery capability when exposed to lower shear forces, while flocs formed at neutral and alkaline conditions had better performance under higher shear forces.     

Determination of low-density Escherichia coli and Helicobacter pylori suspensions in water

Determination of low-density of bacteria, especially those of pathogenic strains in water, has proven difficult and challenging. Here, we developed and evaluated a lanthanum-based concentration method coupled with quantitative real-time PCR to concentrate and detect selected bacteria (Escherichia coli and Helicobacter pylori) in water. To improve qPCR efficiency, the flocs with enmeshed bacteria after chemical flocculation need to be dissolved before PCR detection. Ethylenediaminetetraacetic acid (EDTA) salt successfully dissolved the flocs from a lanthanum-based flocculation process, but not those from the traditional processes using chemicals such as FeCl₃ or Al₂(SO₄)₃. Lanthanum-based concentration coupled with real-time PCR successfully determined E. coli at a concentration of 15 cells/mL in raw and finished water and H. pylori at a concentration of about 1 cell/mL in the finished water prior to disinfection. The H. pylori detection sensitivity could be easily increased to 60 cells/L by reducing the final volume of the DNA samples from 3 mL to 60 μL. With the elimination of membrane-clogging problem that is often encountered in direct membrane filtration, the lanthanum-based chemical flocculation coupled with qPCR is a promising method for determination of low-density of microbial suspensions in water.     

Evaluation of the flocculation performance of carboxymethyl chitosan-graft-polyacrylamide, a novel amphoteric chemically bonded composite flocculant

In the present work, a novel amphoteric chemically bonded composite flocculant (carboxymethyl chitosan-graft-polyacrylamide, denoted as CMC-g-PAM) was successfully prepared and used to flocculate the kaolin suspension. The flocculation performance of CMC-g-PAM in acidic, neutral, and alkaline conditions was systematically evaluated by light scattering in combination with fractal theory, as well as by traditional turbidity and zeta potential measurements. Based on the experimental facts from in situ size and fractal dimension measurements, different flocculation mechanisms play key roles at various pH levels, resulting in substantially varied flocculation kinetic processes under three pH conditions. In acidic condition, patching was the main mechanism involved in the opposite zeta potential between CMC-g-PAM and the kaolin suspension. A flat configuration was favored when the polymeric flocculant was adsorbed onto the particle surface, leading to a slower initial floc growth rate but larger and denser flocs. Bridging was the dominant mechanism in neutral and alkaline conditions. A faster initial rate of bridging resulted in smaller and more open floc structures. A rearrangement process in neutral pH subsequently led to more compact flocs, whereas no restructuration of flocs occurred in alkaline conditions because of the electrostatic repulsion of the same negative charges on the flocculant and particles.     

Strength of natural soil flocs

To obtain the strength of flocs against breakup is crucial for controlling flocculation in water treatment and predicting transport of colloidal particles in aqueous environments. Recently, the author reported a method to obtain floc strength from a simple experiment of floc breakup subjected to a laminar converging flow. In this study, this method was applied to natural soil flocs. The flocs were formed by coagulation with 0.5 M NaCl (pH 5.4-5.5, pH 6.6) solutions, 0.1M CaCl2 (pH 6.4-6.9) solutions, or acidified distilled water with dilute HCl (pH 5.6). Obtained floc strengths were 0.3, 0.7 and 4 nN for Na-, Ca-, and H-coagulated flocs, respectively. Also, floc strength did not change with floc size. These values of floc strengths were 1-3 orders smaller than those of flocs formed with polymer flocculants and/or precipitated ferric or aluminum coagulants.