Coagulation behavior of Al(13) aggregates

The coagulation behavior of Al₁₃ aggregates formed in coagulation of kaolin was investigated by small angle static light scattering (SASLS), solid-state ²⁷Al NMR and tapping mode atomic force microscope (TM-AFM). A kaolin suspension was coagulated by PACl containing high content of Al₁₃ polycation (PACl-Al₁₃). The results indicated that Al₁₃ was predominant in destabilizing kaolin particles for PACl-Al₁₃ coagulation even though at alkaline pH (pH 10). At such high pH, Al₁₃ aggregates were observed when the dosage of PACl-Al₁₃ was increased. In addition, the mechanism of coagulation by PACl-Al₁₃ at alkaline pH was affected by dosage. When the dosage was insufficient, coagulation was caused by electrostatic patch, which led to compact flocs with high fractal dimension (D_f). Interparticle bridging dominated the coagulation when the coagulant dosage approached the plateau of adsorption, which caused the looser flocs with low D_f. The in-situ AFM scanning in liquid system proved that the existence of linear Al₁₃ aggregates composed of a chain of coiled Al₁₃ in coagulation by PACl-Al₁₃ at a high dosage and alkaline pH. Meanwhile, several coiled Al₁₃ aggregates with various dimensions were observed at such condition.     

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.     

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 structural characteristics using conventional coagulation for a high doc, low alkalinity surface water source

Removal of natural organic matter (NOM) is well established using metal salt coagulants. In addition, flocculant aids are also commonly used to improve solid removal. The objectives of this paper is to describe the impacts of both NOM and polymer on floc structure. The study offers a comparison of floc physical characteristics for coagulant precipitate flocs, organic-coagulant flocs and organic-coagulant-polymer flocs for optimum coagulant and polymer doses. A ferric sulphate-based coagulant was used as the primary coagulant and the polymer selected was a high molecular weight (MW) cationic polydiallyldimethylammonium chloride (polyDADMAC). Floc size, breakage, re-growth and settling characteristics were measured. Precipitate flocs were larger than organic flocs and had better settling characteristics when compared to NOM-coagulant flocs. When polymer was added, floc size and compaction was seen to further reduce. An explanation was offered in terms of the mode of flocculation involved. Floc breakage behaviour showed that polymer reduced the rate of floc degradation but did not greatly improve floc re-growth potential after breakage, which was generally poor for all of the suspensions.     

Using magnetic seeds to improve the aggregation and precipitation of nanoparticles from backside grinding wastewater

Backside grinding (BG) wastewater treatment typically requires large quantities of chemicals, i.e. polyaluminum chloride (PAC) coagulant and produces considerable amounts of sludge, increasing the loading and cost of subsequent sludge treatment and disposal processes. This study investigated the effects of the addition of magnetic seeds (FeO*Fe₂O₃) of selected particle sizes and of optimized combinations of magnetic seeds and PAC on the aggregation of silica nanoparticles from BG wastewater and on the sedimentation time at various pH values (5-9). The results show that the turbidity of BG wastewater was significantly reduced by the magnetic aggregation treatment. The dosage of PAC combined with 2.49 g L⁻¹ or 1.24 g L⁻¹ of magnetic seeds was reduced by 83% (from 60 to 10 mg L⁻¹) compared to the conventional process of using only PAC as a coagulant. The turbidity of the BG wastewater, initially 1900-2500 NTU, could also be successfully decreased about to 23 NTU by the addition of 3.74 g L⁻¹ magnetite (FeO*Fe₂O₃) only at pH 5 with an applied magnetic field of 1000 G. Different coagulation conditions using magnetic seeds combined with coagulant resulted in different aggregation performances. The treatment performance was more effective by using two-stage dosing, in which magnetic seeds and PAC were added separately, than that with one-stage dosing, where the magnetic seeds and PAC were added simultaneously during rapid mixing. The two-stage dosing allowed for a reduction in the optimum dosage of magnetic seeds from 3.74 g L⁻¹ to 2.49 g L⁻¹ or 1.24 g L⁻¹ without affecting performance when coupled with 0.01 g L⁻¹ of PAC coagulant. The developed method effectively reduced the production of waste sludge.     

Undrained shear strength of clays as modified by pH variations

The undrained shear strength of clays is an important geotechnical parameter used during construction processes. Several laboratory tests were performed on kaolinite and smectite mixed with pore fluids with different pH values. Vane shear tests were carried out and it was found that the undrained shear resistance for clays increased considerably if the pore fluid had a high or a low pH. A possible explanation could be the dissolution of Al³⁺ which acts as a coagulant, increasing the internal shear resistance. Geochemical computations, Al measurements and ζ-potential experiments were performed to confirm this theory. The research suggests varying the pH may make a useful contribution to soil improvement techniques.     

Synergetic effect between photocatalytic degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater

The photocatalytic degradation of two phenolic compounds, p-coumaric acid and caffeic acid, was performed with a suspended mixture of TiO₂ and powdered activated carbon (PAC) (at pH = 3.4 and 8). Adsorption, direct photolysis and photocatalytic degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV lamps). The potential for reusing this catalyst mixture in sequential photocatalytic runs was examined as well. Quantum yields for the direct photolysis of caffeic acid under solar and artificial 365 nm light were calculated (for the first time) as 0.005 and 0.011, respectively.A higher removal rate of contaminants by either adsorption or photocatalysis was obtained at a low pH (pH 4). Furthermore, the addition of PAC increased the removal efficiency of the phenolic compounds. Fast removal of the pollutants from the solution over three sequential runs was achieved only when both TiO₂ and PAC were present. This suggests that at medium phenolic concentrations, the presence of PAC as a co-sorbent reduces surface poisoning of the TiO₂ catalyst and hence improves photocatalysis degradation of phenolic pollutants.The adsorption equilibrium of caffeic acid or p-coumaric acid on TiO₂, PAC and the combined mixture of TiO₂ and PAC follows the Langmuir isotherm model. Experiments with PAC TiO₂ mixture and olive mill wastewater (anaerobically treated and diluted by a factor of 10) showed higher removal of polyphenols than of chemical oxygen demand (COD). 87% removal of total polyphenols, compared to 58% of COD, was achieved after 24 h of exposure to 365 nm irradiation (7.6 W/m²) in the presence of a suspended mixture of TiO₂ and PAC, indicating “self-selectivity” of polyphenols.     

Polyaluminum chloride with high Al30 content as removal agent for arsenic-contaminated well water

Polyaluminum chloride (PACl) is a well-established coagulant in water treatment with high removal efficiency for arsenic. A high content of Al₃₀ nanoclusters in PACl improves the removal efficiency over broader dosage and pH range. In this study we tested PACl with 75% Al₃₀ nanoclusters (PACl_Al30) for the treatment of arsenic-contaminated well water by laboratory batch experiments and field application in the geothermal area of Chalkidiki, Greece, and in the Pannonian Basin, Romania. The treatment efficiency was studied as a function of dosage and the nanoclusters’ protonation degree. Acid-base titration revealed increasing deprotonation of PACl_Al30 from pH 4.7 to the point of zero charge at pH 6.7. The most efficient removal of As(III) and As(V) coincided with optimal aggregation of the Al nanoclusters at pH 7-8, a common pH range for groundwater. The application of PACl_Al30 with an Al_tot concentration of 1-5 mM in laboratory batch experiments successfully lowered dissolved As(V) concentrations from 20 to 230 μg/L to less than 5 μg/L. Field tests confirmed laboratory results, and showed that the WHO threshold value of 10 μg/L was only slightly exceeded (10.8 μg/L) at initial concentrations as high as 2300 μg/L As(V). However, As(III) removal was less efficient (<40%), therefore oxidation will be crucial before coagulation with PACl_Al30. The presence of silica in the well water improved As(III) removal by typically 10%. This study revealed that the Al₃₀ nanoclusters are most efficient for the removal of As(V) from water resources at near-neutral pH.     

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.     

A review of floc strength and breakage

The main focus of the paper is to review current understanding of floc structure and strength. This has been done by reviewing current theoretical understanding of floc growth and breakage and an analysis of different techniques used for measuring floc strength. An overview has also been made of the general trends seen in floc strength analysis. The rate of floc formation is a balance between breakage and aggregation with flocs eventually reaching a steady-state size for a given shear rate. The steady-state floc size for a particular shear rate can, therefore, be a good indicator of floc strength. This has resulted in the development of a range of techniques to measure floc size at different applied shear levels using a combination of one or more of the following tools: light scattering and transmission; microscopy; photography; video and image analysis software. Floc strength may be simply quantified using the initial floc size for a given shear rate and the floc strength factor. More complex techniques have used theoretical modelling to determine whether flocs break by large-scale fragmentation or smaller-scale surface erosion effects, although this interpretation is open to debate. Impeller-based mixing, ultrasound and vibrating columns have all been used to provide a uniform, accurate and controllable dissipation of energy onto a floc suspension to determine floc strength. Other more recent techniques have used sensitive micromanipulators to measure the force required to break or compress individual flocs, although these techniques have been limited to the measurement of only a few hundred flocs. General trends emerge showing that smaller flocs tend to have greater strength than larger flocs, whilst the use of polymer seems to give increased strength to only some types of floc. Finally, a comparison of the strength of different types of floc (activated sludge flocs, organic matter flocs, sweep flocs and charge neutralised flocs) has been made highlighting differences in relative floc strength.     

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.     

Improvement of activated sludge dewaterability by mild thermal treatment in CaCl2 solution

Activated sludge dewatering is of great importance in sludge treatment and disposal. To enhance the dewaterability, a novel method was performed by treating the sludge under mild temperature (50-90 °C) in CaCl₂ solution (3.7-1110.0 mg/g dry sludge). The capillary suction time, zeta potential, Fourier-transformed infrared spectra, concentration of soluble protein and carbohydrates were employed to characterize the dewaterability and influencing mechanism. The sludge dewaterability was deteriorated with single thermal treatment, but significantly promoted in CaCl₂ solution and advanced further together with thermal treatment. An increasing CaCl₂ dosage reduced the surface charge remarkably, and a higher temperature could strengthen this impact. The spectra indicate that Ca²⁺ could interact with the protein, phenols and O-H functional group in the flocs. The thermal treatment could cause the solubilization of protein and carbohydrates, providing more binding sites for Ca²⁺ to establish a strong bridging among the flocs. As CaCl₂ dosage elevated, the soluble carbohydrates showed a reduction trend, while the soluble protein lowered firstly and then bounced back except that remained unchanged at room temperature. A bridging equilibrium is presumed to exist between Ca²⁺ and the soluble protein. And the bridging between Ca²⁺ and the soluble carbohydrates plays a more important role in the dewatering. The sludge dewaterability was successfully and economically improved by thermal treatment in CaCl₂ solution.     

Shear-induced flocculation: The evolution of floc structure and the shape of the size distribution at steady state

The flocculation of polystyrene particles in a stirred tank was studied at various shear rates (63–129 s⁻¹) and aluminum sulfate, Al₂(SO₄)₃ 16H₂O, flocculant concentrations. The competition between coagulation and fragmentation during shear-induced flocculation determined the equilibrium or steady state particle (floc) structure and size distribution. The evolution of the floc structure with time was monitored by image analysis of digitized floc images. The average floc structure became less open or irregular as the floc size distribution attained steady state as a result of shear-induced breakage/restructuring. At high alum (flocculant) concentrations, the steady state floc size distribution appeared to be self-preserving with respect to shear rate. In contrast, at lower flocculant concentrations, the steady state floc size distribution narrowed with increasing shear rate as the large tail of the distribution was pushed to smaller particle sizes by shear-induced fragmentation.     

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.     

复合混凝剂PTA-CPAM的形貌结构与净水性能

以聚合氯化铝(PAC)、四氯化钛(TiCl_4)、阳离子聚丙烯酰胺(CPAM)为原料成功制备无机-有机复合混凝剂聚钛氯化铝-阳离子聚丙烯酰胺(PTA-CPAM),采用红外光谱(IR)、扫描电镜(SEM)、能谱分析(EDS)与差热热重(TG-DTA)对产物的结构、组成及热稳定性进行分析。此外,对PTA-CPAM的混凝性能进行研究。结果表明:当m(CPAM)/m(PTA)=0.4、PTA-CPAM投加量为9.0mg/L、pH为9.0的条件下,混凝剂的净水效果最优,且PTA-CPAM对不同初始浊度的水样都有较优的除浊能力;协同增效作用使PTA-CPAM具备更强的吸附电中和与吸附架桥网捕能力,表现出优异的除浊性能。     

Preparation and characterisation of new-polyaluminum chloride-chitosan composite coagulant

In this study, the formulation of a novel polyaluminum chloride-chitosan composite coagulant that improves the coagulation process for natural organic matter (NOM) removal was investigated. The performance of the composite coagulant was tested using two water sources (synthetic and natural water) to develop a better understanding on the behaviour of the composite coagulant. Fourier Transform-Infra red (FT-IR) spectroscopy, ferron analysis and zeta potential studies were performed to characterise the composite coagulant. FT-IR analysis showed that there is an intermolecular interaction between Al species and chitosan molecules, while ferron analysis indicated that the distributions of Al_a, Al_b, and Al_c in PACl-chitosan are different from those in PACl. At a low Al dosage (2.16 mg L⁻¹), a much higher removal of NOM from synthetic water, as evidenced from UV₂₅₄ and Dissolved Organic Carbon (DOC) measurements, was achieved by the composite coagulants in comparison to that removed by PACl or PACl and chitosan added separately. For natural water from the Myponga Reservoir, both polyaluminum chloride (PACl) and PACl-chitosan composite coagulants demonstrated similar dissolved organic carbon (DOC) percentage removal, whereas PACl-chitosan gave a slight improvement in removing the UV₂₅₄ absorbing components of NOM.     

Enhanced efficiencies of sludge dewatering and domestic wastewater treatment by using the bioflocculant from rice stover

Potential of a bioflocculant from rice stover was studied in sludge dewatering and domestic wastewater treatment. Production of this bioflocculant showed good correspondence to cell growth, after fermentation for 60 h, the fermentation liquor was obtained, from 1.0 L of which a value of 2.37 g bioflocculant can be extracted, and the main backbone of this bioflocculant was polysaccharides. Without adjusting the sludge's initial pH value of 6.5, when incubated with 18 mg/L of this bioflocculant, dry solids (DS) and specific resistance to filtration (SRF) of the typical wastewater activated sludge reached 18.5% and 4.7 × 10¹² m/kg, respectively, which was better than the ones achieved by Al₂(SO₄)₃ and FeCl₃ flocculants. For domestic wastewater treatment, after treated by 12 mg/L of this bioflocculant at pH value of 7.5, removal efficiencies of chemical oxygen demand (COD) and turbidity can reach 91.8 and 89.7%, respectively, which were better than the ones achieved by the traditional flocculants such as Al₂(SO₄)₃, FeCl₃, and polyaluminum chloride (PAC). This study suggested that the bioflocculant from rice stover has great potentials as an alternative flocculant to conventional flocculants in sludge dewatering and domestic wastewater treatment.     

Study of polymeric aluminium(III) hydroxide solutions for application in waste water treatment. Properties of the polymer and optimal conditions of preparation

The optimal conditions for the preparation of polymeric aluminium(III) hydroxide species for water treatment has been described. The partially hydrolysed aluminium(III) solutions were characterized by ultrafiltration method, ferron assay, ²⁷Al n.m.r. measurements, high pressure anion exchange chromatography and precipitation of polymeric aluminium hydroxo species with sodium sulphate. The results of these tend to suggest that the polymeric aluminium(III) hydroxide species have a size between 10–20 Å; these have an average residual positive charge of 0.54, and constitute about 80% of the total aluminium in the hydrolysed solution. They are retained by UM05 membrane. ²⁷Al measurements indicate that Al₁₃O₄(OH)₂₄^7? ion are the predominant polymeric species in these solutions. In addition to these the hydrolysed aluminium(III) solutions contain low proportions of monomeric aluminium hydroxo species and inert micro-crystalline aluminium hydroxide. The effect of ageing, dilution and pH on the stability and characteristics of the aluminium hydroxide polymer were also studied in detail.     

The effect of bed age and shear stress on the particle morphology of eroded cohesive river sediment in an annular flume

Erosion experiments were conducted in an annular flume to determine the effect of bed age and shear stress on the particle morphology (fractal dimensions D, D(1), and D(k)) of eroded cohesive river sediment. Sediment beds were deposited under low shear and left to consolidate for one, two and seven days. Fractal data and photomicrographs show particle morphology changed with shear stress and bed age. During the one-day experiment, flocs were highly branched and particle geometry became more complex with increasing shear. Microflocs present in suspension at low shear, formed larger more loosely bound flocs at moderate shear due to flocculation. At higher shear, larger flocs were less prevalent due to particle breakup. As bed age increased, less sediment was eroded and particles appeared less porous and more angular in shape for a given shear stress. Changes in floc morphology and eroded sediment mass at various shear stresses may be related to bed age-associated biostabilization of bed deposits.