铝的水溶液化学特征及其聚合物生成机制

聚合氯化铝（PACl）是水处理中应用较广泛的絮凝剂。研究表明,PACl中各种铝聚合物的含量直接影响其絮凝效率。本文综述铝的水解聚合特性以及制备絮凝剂过程中的铝聚合物生成机制,着重介绍了Al13聚合物的结构特性、生成机制以及制备过程中各种因素的影响,为Al13絮凝剂的进一步研究奠定了基础。     

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.     

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.     

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.     

Floc morphology and cyclic shearing recovery: comparison of alum and polyaluminum chloride coagulants

This study investigated the floc formation and re-aggregation potential for alum, polyaluminum chloride (PACl) and a blend of these coagulants. Bench-scale testing included floc morphology characterization for well-developed floc, post-shear floc, and non-settleable (filter influent) floc. Different applications of coagulants were observed to produce non-settleable floc that was morphologically different. The alum treatment had a decrease in average floc size from coagulated to non-settleable conditions, whereas the PACl and PACl/alum treatments resulted in similar sized floc between these processes. Zeta potential distribution measurements showed that the alum treatment resulted in a negative shift from coagulated to non-settleable conditions whereas the PACl and PACl/alum treatments had no significant shift. A photometric dispersion analyzer (PDA) was employed to compare the differences between coagulant treatments with respect to shear induced aggregate breakup and recovery. The PDA allowed a dynamic monitoring of initial floc aggregation and measured the degree of recovery from cyclic shearing. The degree of recovery from shearing was greatest for the PACl/alum treatment likely as a result of increased collision efficiency due to more effective charge neutralization.     

Comparable evaluation of various commercially available aluminium‐based coagulants for the treatment of surface water and for the post‐treatment of urban wastewater

In this study the efficiency of various commercially‐available coagulants, ie alum and poly‐aluminium chlorides (PACls), for the treatment of surface (river) water, or for the post‐treatment of biologically pretreated urban wastewater were investigated. The different coagulants were comparatively evaluated, considering the removal of suspended solids (SS), natural organic matter (NOM), as well as the residual aluminium concentration, and the removal of phosphates (inorganic phosphorus), in the case of urban wastewater treatment. The dynamics of flocculation were also studied using a Photometric Dispersion Analyser (PDA) in order to compare the flocculation rates and the strength of different coagulant flocs. Finally, the optimum operational conditions, ie coagulant dosage, pH, temperature, duration and intensity of (initial) rapid‐mixing rate, were determined for the examined cases. It can be generally supported that PACl coagulants were superior to alum, as they presented higher SS and NOM removal, stronger and larger flocs, higher flocculation rates and lower residual aluminium concentration, which is a very important factor, especially for the treatment of surface water destinated for potable use. Copyright © 2005 Society of Chemical Industry     

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.     

Comparison of Efficiency between Poly‐aluminium Chloride and Aluminium Sulphate Coagulants during Full‐scale Experiments in a Drinking Water Treatment Plant

Abstract

The efficiency of poly‐aluminium chloride (PACl) and of aluminium sulphate (alum), two commonly applied coagulant agents, was studied comparatively in this work, during full‐scale experiments in a drinking water treatment plant. The removal of suspended solids (turbidity) and the residual aluminium concentrations were carefully monitored and they were used for the evaluation of effectiveness for each coagulant, as well as for the determination of optimal operative conditions. Two alternative treatment processes were examined:

• (a) the conventional coagulation‐flocculation‐sedimentation process, followed by gravity filtration through sand filter beds, and

• (b) the direct filtration process, i.e., coagulation‐flocculation and sand filtration, but without the intermediate sedimentation step.

PACl proved to be a more efficient coagulant than alum, as lower dosages of PACl, about 1.35 mg Al/L in this case, resulted to the production of treated water with low turbidity and residual aluminium content. In addition, the direct filtration process through dual sand‐anthracite filter beds was found to be equally sufficient, as the conventional one, i.e., when applying the sedimentation step; in this case, 0.70 mg Al/L of PACl resulted in low turbidity water (around 0.1 NTU) and residual aluminium content (lower than 150 µg/L). In addition, the operation time of filters was extended to more than 24 hours.     

Novel ferromagnetic nanoparticle composited PACls and their coagulation characteristics

Effects of magnetic nanoparticles on inorganic coagulants and their coagulation performances were studied in the present work. The Fe₃O₄-SiO₂ core-shell particle (FSCSP) and superfine iron (SI), were compounded with polyaluminium chloride of basicity 2.0 (PACl2.0), providing magnetic PACl2.0s (MPACl2.0s). The physiochemical properties of ferromagnetic nanoparticles were investigated using transmission electron microscopy (TEM), the BET method and a zeta potentiometric analyzer. The Al species distributions of the MPACl2.0s and PACl2.0 were examined by liquid ²⁷Al NMR. Jar tests were employed to evaluate the coagulation performances. Floc properties were assessed by use of the electromotive microscope (EM) and small angle laser light scattering (SALLS). The results showed that modified layers of nanoparticles mitigated agglomeration. FSCSP had a larger specific area and pore volume than SI. The addition of ferromagnetic nanoparticles obviously increased the content of Al_un. MPACl2.0s performed better than PACl2.0 in turbidity removal and DOC removal when dosed less than 0.06 mmol/L as Al. Generally, PACl2.0 + FSCSP (50 mg/L) performed best. Large, loose and weak flocs were produced by MPACl2.0s, which were preferred for the magnetic powder recycling. A plausible structure, Al species-nanoparticles cluster, contributing to the unique properties of MPACl2.0 flocs, was proposed.     

Mechanistic Difference of Coagulation of Kaolin Between PACl and Cationic Polyelectrolytes: A Comparative Study on Zone 2 Coagulation

A comparative study on zone 2 coagulation between polyaluminum chloride (PACl) and cationic polyelectrolytes was conducted by applying a sensitive monitoring technique coupling with the conventional jar test. The effect of coagulant dosage and mixing were examined. The experimental results show that there exists both difference and similarity of coagulation between PACl and cationic polyelectrolytes. Being molecularly small, coagulation with PACl is achieved typically through adsorption charge-neutralization mechanism. Only PACl₂₅ with presence of large particle size species, Al_c, does an electrostatic patch effect appear. However, the mechanism of coagulation with cationic polyelectrolytes is both through charge neutralization and patch coagulation. The effect of electrostatic patch is increased with the increase of molecular size. Mixing exhibits a similar effect both on PACl and cationic polyelectrolytes after dosing, while floc breakage and regrowth is different significantly depending on the coagulant applied.