Mechanism of natural organic matter removal by polyaluminum chloride: effect of coagulant particle size and hydrolysis kinetics

The mechanism of natural organic matter (NOM) removal by AlCl(3) and polyaluminum chloride (PACl) was investigated through bench-scale tests. The fraction distributions of NOM and residual Al after coagulation in solution, colloid and sediment were analyzed as changes of coagulant dosage and pH. The influence of NOM, coagulant dose and pH on coagulation kinetics of AlCl(3) was investigated using photometric dispersion analyzer compared with PACl. Monomeric Al species (Al(a)) shows high ability to satisfy some unsaturated coordinate bonds of NOM to facilitate particle and NOM removal, while most of the flocs formed by Al(a) are small and difficult to settle. Medium polymerized Al species (Al(b)) can destabilize particle and NOM efficiently, while some flocs formed by Al(b) are not large and not easy to precipitate as compared to those formed by colloidal or solid Al species (Al(c)). Thus, Al(c) could adsorb and remove NOM efficiently. The removal of contaminant by species of Al(a), Al(b) and Al(c) follows mechanisms of complexation, neutralization and adsorption, respectively. Unlike preformed Al(b) in PACl, in-situ-formed Al(b) can remove NOM and particle more efficiently via the mechanism of further hydrolysis and transfer into Al(c) during coagulation. While the presence of NOM would reduce Al(b) formed in-situ due to the complexation of NOM and Al(a).     

Effect of shear force and solution pH on flocs breakage and re-growth formed by nano-Al13 polymer

The breakage and re-growth of flocs formed by polyaluminum chloride (PAC) and the Al₁₃O₄ (OH)₂₄⁷⁺ (Al₁₃ for short) polymer were comparatively evaluated for the coagulation of humic acid (HA). A series of jar experiments were conducted to investigate the impacts of shear rate and solution pH on flocs breakage and re-aggregation potential. Results indicated that the responses of flocs to the increasing shear force and solution pH depend on the coagulant used. The ability of flocs to resist breakage decreased with the increasing shear rate. For all levels of shear force investigated in this study, the flocs formed by Al₁₃ polymer were weaker than those of PAC, whereas Al₁₃ polymer displayed a better recoverability than PAC. The similar results were obtained when pH of solution was changed. The flocs generated in acidic conditions were stronger and more recoverable than those generated in alkaline conditions no matter which coagulant was used.     

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.     

Optimalization of coagulant dose in coagulation-flocculation of sewage

This article describes how the optimal coagulant dose in chemical treatment can be calculated from a limited number of raw sewage characteristics. Ferric chloride and aluminium sulphate were used as coagulants. In jar tests ten characteristics were determined in the sewage and for each separate sample of wastewater “optimal” coagulant doses were determined. There was a very high correlation between the “optimal” coagulant dose of aluminium sulphate and ferric chloride and one or two quality parameters of the influent. A comparison was made between aluminium sulphate and ferric chloride as coagulant. The findings were verified in two pilot plants. In one a constant coagulant dose m⁻³ influent was set; in the other plant the coagulant dose was also related to the orthophosphate content of the sewage. By this means a reduction of the coagulant dose was obtained of 35%, while on average the removal percentage of TOC was the same.     

Physico-chemical treatment of municipal wastewater. Coagulation-flocculation

This article traces the possibilities of physico-chemical treatment of domestic sewage with particular attention to coagulation-flocculation processes. As coagulants the following have been used: ferric chloride, hydrated lime and alum. Different types of coagulant aids have been used too. Besides pilot-plant experiments, a large number of batch experiments has been carried out in order to determine the range of optimal doses of coagulants/coagulant aids/pH and so on. The fate of specific organic and inorganic components (proteins, detergents, low organic acids, phosphorus, nitrogen) as well as TOC, BOD and COD in this chemical treatment have been studied. The suspended and most of the colloidal fractions have efficiently been removed. A considerable fraction, which is defined as soluble, has been removed too. The significance of the findings for wastewater treatment processes have been discussed.     

纳米SiO_2用于含表面活性剂原水的处理

在含表面活性剂十二烷基硫酸钠(SDS)的低浊(6 NTU)高岭土原水中,投加纳米SiO_2进行动态混凝与静沉试验,借助图像分析技术与定量控制参数,探讨了纳米SiO_2的作用效果与形态学特性.结果表明:絮体的形成与生长具有分形特征,分形结构是影响颗粒混凝、絮团密实度与沉降特性的主要因素;SDS的存在对絮凝初期絮体的形成起阻碍作用,随后SDS与混凝剂的混合体共同对粒子作用,促进絮凝,絮体变大且密实,沉降性能改善;SDS和SiO_2对高岭土粒子存在竞争吸附;单独投加纳米SiO_2时形成的絮体小而脆弱,而以纳米SiO_2为助凝剂能促使PAC絮体结构向更密实的构型转变,对浊度和SDS的去除率提高.     

混凝剂中的铝形态对藻类混凝过程的影响

为了考察混凝剂中的铝形态对藻类混凝过程的影响,使用3种具有不同铝形态分布的混凝剂对含藻水进行了混凝试验。结果表明,硫酸铝由于具有较低含量的Alb,电中和能力较差,故需要较大的投量才能去除藻类,形成絮体;含藻水体系中的有机物主要是腐殖酸及富里酸类物质,微生物代谢产物(SMP)在硫酸铝作混凝剂时得到较好的去除,而腐殖酸及富里酸的去除率较低可能是造成硫酸铝混凝效果较差的原因; Alc(Al(30))在混凝中的作用机理主要是吸附架桥作用,可有效去除水体中的有机物,Al₁₃的主要作用机理是电中和作用,可以有效去除水体中的颗粒物;Al₁₃与Al₃₀由于具有形态的稳定性,其混凝过程受pH值的影响较小。絮体强度因子随着pH值的升高先增大后减小,Al₁₃作混凝剂时絮体恢复因子随pH值的升高先增大后减小,而其他两种混凝剂所形成絮体的恢复因子随pH值的升高而增大。     

Optimization of the coagulation-flocculation process for pulp mill wastewater treatment using a combination of uniform design and response surface methodology

Pulp mill wastewater was treated using the coagulation-flocculation process with aluminum chloride as the coagulant and a modified natural polymer, starch-g-PAM-g-PDMC [polyacrylamide and poly (2-methacryloyloxyethyl) trimethyl ammonium chloride], as the flocculant. A novel approach with a combination of response surface methodology (RSM) and uniform design (UD) was employed to evaluate the effects and interactions of three main influential factors, coagulant dosage, flocculant dosage and pH, on the treatment efficiency in terms of the supernatant turbidity and lignin removals as well as the water recovery. The optimal conditions obtained from the compromise of the three desirable responses, supernatant turbidity removal, lignin removal and water recovery efficiency, were as follows: coagulant dosage of 871 mg/L, flocculant dosage of 22.3 mg/L and pH 8.35. Confirmation experiments demonstrated that such a combination of the UD and RSM is a powerful and useful approach for optimizing the coagulation-flocculation process for the pulp mill wastewater treatment.     

The origin of Al(OH)3-rich and Al13-aggregate flocs composition in PACl coagulation

The composition of hydrolyzed Al species is essential for the understanding of coagulation with Al-based coagulants. Surface characteristics of flocs formed by coagulation with two distinct polyaluminum chloride (PACl) coagulants were identified. One commercial coagulant (PACl-C) with voluminous monomeric Al and colloidal Al(OH)₃ and a custom-made PACl (PACl-Al₁₃) containing high Al₁₃ content were applied to destabilize kaolin particles. The flocs formed by PACl-C and PACl-Al₁₃ at neutral and alkaline pH ranges, respectively, were observed by FE-SEM and HR-TEM. In addition, the Al composition of these flocs was characterized by XPS and HR-XRD, and the imaging of Al(OH)₃ precipitates and Al₁₃ aggregates were conducted by SEM as well as tapping mode AFM in liquid system. The observations of flocs indicate that the morphology of Al(OH)₃-rich flocs are fluffy and porous around the edge of flocs, while the Al₁₃-aggregate flocs have a glossy contour and irregular structure. Both Al(OH)₃-rich and Al₁₃-aggregate flocs do not possess well-formed crystalline structure except for the Al₁₃-like crystal exists in the Al₁₃-aggregate flocs. Among Al(OH)₃ precipitates, colloidal Al(OH)₃ is micro-scale in size, while amorphous Al(OH)₃ is nano-scale. During the formation of Al₁₃ aggregates, some coiled and clustered Al₁₃ aggregates with smoother surface were observed. The XPS study on floc surface showed that tetrahedral (Al^IV) /octahedral (Al^VI) Al ratio on the surfaces of PACl-C and PACl-Al₁₃ flocs is 1:1.6 and 1:9.9, respectively. Of the in situ formed Al₁₃, almost half of Al-hydroxide precipitates on the surface of Al(OH)₃-rich flocs possess the Al^IV center. It also found that the irregularly aggregated Al₁₃ with a similar Al₁₃ crystalline structure subsists on the surface of Al₁₃-aggregate flocs.     

Coagulation dynamics of fractal flocs induced by enmeshment and electrostatic patch mechanisms

The size and structure of flocs during floc formation were monitored for various coagulation mechanisms. Two distinctive mechanisms, namely, enmeshment and electrostatic patch, govern the dynamics of kaolin particles coagulation by polyaluminum chloride (PACl). They were investigated by small angle static light scattering (SASLS) and solid-state ²⁷Al NMR. In addition, a novel wet SEM (WSEM) was used in-situ to image the morphology of the aggregate in aqueous solution. Synthetic suspended particles were coagulated by two PACl products, a commercial product (PACl) and one laboratory product (PACl-E). The PACl-E contained more than 60% Al₁₃ while the PACl contained only 7% Al₁₃, with large percentage of colloidal Al. For coagulation by PACl at neutral pH and high dosage where the strong repulsion between particles occurs, the enmeshment ruled by reaction-limited aggregation (RLA) results in larger sweep flocs as well as higher fractal dimensional structure. For coagulation by PACl-E at alkaline pH and low dosage, the flocs were coagulated predominately by electrostatic patch with Al₁₃ aggregates. At such condition, it is likely that diffusion-limited aggregation (DLA) predominately rule PACl-E coagulation. The fractal dimension (D_s) values of PACl and PACl-E flocs formed at enmeshment and electrostatic patch increased with dosage, respectively. When breakage of flocs occurs, the breakage rate of PACl-E flocs is slower than that of sweep flocs. By WSEM imaging, the adsorption of spherical Al precipitates onto the particles was observed to form sweep flocs with a rough and ragged contour, while the PACl-E flocs were formed with a smooth and glossy structure.     

The stabilization of “dissolved” iron in freshwaters

Laboratory experiments have been conducted to see what substances are capable of holding iron at a concentration of about 1 ppm in a “dissolved” form (i.e. will pass through a 0.45 μm pore size filter) in oxygenated water. The results show that reagents capable of doing this include humic and tannic acids, surfactants such as sodium dodecyl sulphate and sodium dodecylbenzene sulphonate, and the inorganic ions silicate and phosphate. In contrast, the synthetic polymer polyvinylpyrrollidone and the simple ions Cl⁻, HCO₃⁻, SO₄⁻ and NO₃⁻ showed no ability to stabilise iron. The efficiency of phosphate at keeping iron in the “dissolved” state was found to decrease in the presence of cations, particularly divalent ones, but increased with rise in water pH in the range 6–11.It seems unlikely that much of the stabilization observed for any of the reagents tested is due to their forming complexes with the iron. A much more likely explanation is that the substances for which positive results were obtained are able to stabilize fine colloidal iron particles and inhibit them from forming larger aggregates.     

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.     

Fate and transport of elemental copper (Cu0) nanoparticles through saturated porous media in the presence of organic materials

Column experiments were performed to assess the fate and transport of nanoscale elemental copper (Cu⁰) particles in saturated quartz sands. Both effluent concentrations and retention profiles were measured over a broad range of physicochemical conditions, which included pH, ionic strength, the presence of natural organic matter (humic and fulvic acids) and an organic buffer (Trizma). At neutral pHs, Cu⁰ nanoparticles were positively charged and essentially immobile in porous media. The presence of natural organic matter, trizma buffer, and high pH decreased the attachment efficiency facilitating elemental copper transport through sand columns. Experimental results suggested the presence of both favourable and unfavourable nanoparticle interactions causes significant deviation from classical colloid filtration theory.     

Competition between kaolinite flocculation and stabilization in divalent cation solutions dosed with anionic polyacrylamides

Divalent cations have been reported to develop bridges between anionic polyelectrolytes and negatively-charged colloidal particles, thereby enhancing particle flocculation. However, results from this study of kaolinite suspensions dosed with various anionic polyacrylamides (PAMs) reveal that Ca²⁺ and Mg²⁺ can lead to colloid stabilization under some conditions. To explain the opposite but coexisting processes of flocculation and stabilization with divalent cations, a conceptual flocculation model with (1) particle-binding divalent cationic bridges between PAM molecules and kaolinite particles and (2) polymer-binding divalent cationic bridges between PAM molecules is proposed. The particle-binding bridges enhanced flocculation and aggregated kaolinite particles in large, easily-settleable flocs whereas the polymer-binding bridges increased steric stabilization by developing polymer layers covering the kaolinite surface. Both the particle-binding and polymer-binding divalent cationic bridges coexist in anionic PAM- and kaolinite-containing suspensions and thus induce the counteracting processes of particle flocculation and stabilization. Therefore, anionic polyelectrolytes in divalent cation-enriched aqueous solutions can sometimes lead to the stabilization of colloidal particles due to the polymer-binding divalent cationic bridges.     

The mechanism of dissolved air flotation for potable water: basic analysis and a proposal

The principal mechanism of flotation of suspended solids in natural waters is by collision of free micro-bubbles with flocs and attachment at hydrophobic sites. Such sites are formed by adsorption of naturally-occurring organic compounds on to the precipitated alumina (or ferric “hydroxide”) derived from the coagulant added.Although effective, the current flotation process uses supersaturated water inefficiently, mainly because the average bubble size obtained is above the optimum. Unfortunately, no method is known for generating a dense cloud of micro-bubbles (< 50 μm) without adding surfactants.A more economical procedure might be based on mixing bubble-free super-saturated water with the chemically treated water, followed by conditioning in a flocculator under moderate shear. Under these conditions bubbles grow from nuclei within the flocs, which can subsequently be floated in a quiescent tank. Bench tests indicated that the method is feasible, the growth time of the bubbles being comparable with that needed for good flocculation.     

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.     

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.     

Colour and turbidity removal with reusable magnetic particles—I. Use of magnetic cation exchange resins to introduce aluminium ions

Clarification of hard, turbid surface water by Al³⁺ ions introduced on a sulphonic acid ion exchanger is described. If the resin beads are sufficiently fine, they act as nuclei for floc formation and accelerate the subsequent settling of the flocs. Incorporation of magnetic iron oxide in the resin beads enables them to be conveniently separated from the clarified water. Acidification of the resin-containing sludge then results in partial reloading of the resin with Al³⁺ ions. However, the regenerated resin proved ineffective as a coagulant, a result attributed chiefly to hydrolysis of Al³⁺ ions within the resin. The findings of this work are significant for the theory of coagulation and also suggested the possibility of enhancing clarification by adding fine particles with an absorbing surface.     

Optimisation of combined coagulation and microfiltration for water treatment

The effect of upstream coagulant dosing for full-flow microfiltration of an upland-reservoir water has been investigated. The process, run under conditions of constant flux and pH and based on a ferric salt, is compared with a published study of another full-flow process based on alum dosing and operated at constant pressure and coagulant concentration. The current study includes data for the residual deposit remaining following backflushing by reverse flow. Results are presented in terms of the specific-cake resistance (R'o, m(-2)) as a function of pH or coagulant dose. Reasonable correlation with classical cake filtration theory was obtained, such that R' was assumed to be independent of run time and cake thickness. The following trends have been noted: The optimum pH for the alum-based system appears to be between 7.5 and 8 on the basis of cake resistance. The effect of coagulant dose between 18 and 71 microM Fe3+ is much more significant than a change in pH between 5 and 9 for the alum system: a 53-fold increase in specific flux compared with a 7-fold increase with reference to the limiting R'o values at pH 4.8 and 7.7. A low coagulant dose (0.018mM, 1.0 mg l(-1) Fe3+) appears to have a slightly detrimental effect on downstream microfiltration operation. The low coagulant doses apparently cause incomplete aggregation of colloidal particles such that internal fouling of the membrane takes place. The residual (cleaning cycle) deposit resistance followed roughly the same trend as the backflush cycle-cake resistance with coagulant concentration, but with a much reduced value (about 16 times lower, on average). An optimum coagulant dose of 0.055 mM (3.1 mg/l) Fe3+ can be identified on the basis of operational cost based on coagulant cost and cake resistance, all other aspects of the system being substantially unchanged. It is concluded that coagulation with downstream microfiltration offers a cost-effective means of removing natural organic matter, achieving a THMFP removal of around 80% at the optimum dose.