Al Flocs Research Articles

An overlooked crystallization effect during the O3 participated coagulation improves the performance of dual-membrane process

Till now, the transformation of amorphous flocs formed during the hydrolysis stage of coagulation has not been fully addressed. In this work, by using a conventional coagulant (alum), the transformation process was explored by observing the interactions between O3 and the amorphous alum flocs formed during flocculation at neutral pH. It was found that O3 promoted the transition of the in-situ formed alum flocs from tetrahedral Al (Al(O)4) to octahedral Al (Al(O)6) structures, through an accelerated dehydroxylation process, and therefore facilitated the crystallization process to form boehmite. During this process, the surface functional groups of amorphous Al flocs (Al–H2O and Al–OH) were observed to take part in the O3 catalytic oxidation with the generation of hydroxyl radicals (OH). This synergistic effect significantly favored the performance of the subsequent dual-membrane (UF-NF) process in terms of both fouling alleviation (1.78 and 1.60 times higher flux of UF and NF, respectively) and final effluent quality improvement, including the reduction in disinfection byproduct (DBP) formation potential (48.1% and 22.4% lower generation of total trihalomethanes and total haloacetic acid, respectively) and the corresponding calculated toxicity. The results obtained here provide a greater understanding of the transformation of amorphous Al flocs formed during flocculation with O3, and valuable information regarding its practical application in membrane filtration process with greater treatment performance.

Behavior of iron and other heavy metals in passivated sediments and the coupling effect on phosphorus

In situ passivation, which is easy to operate and affordable, is one of the most commonly used methods for sediment phosphorus (P) remediation. Understanding the behavior of iron and other heavy metals in passivated sediments is important for alleviating lake eutrophication and for ensuring drinking water safety. In this study, we investigated the behavior of P, Fe, Mn, Cd, Co, and Pb in lanthanum modified bentonite (LMB, Phoslock®) and polyaluminum chloride (PAC)-passivated sediments using intact sediment cores. Rhizon sampler and diffusive gradients in thin films technology (DGT) were respectively used to collect soluble and labile substances in sediment; a modified sequential selective extraction method was used to characterize metal forms. Results showed that LMB reduced soluble reactive phosphorus (SRP) at sediment depths of 0 ~ −15 mm and DGT-labile P flux at 0 ~ −50 mm. Correlation between DGT-labile P and Fe (R2 = 0.71) indicated that P mobility in the LMB group was affected by the behavior of Fe. PAC decreased SRP at sediment depths of 0, −5, −10, −15, −20, −25, and −50 mm with removal rates of 100%, 90%, 45%, 35%, 81%, 89%, and 100%, respectively. DGT-labile P flux was decreased by PAC at 0 ~ −10 mm and −50 ~ −110 mm, but increased at −10 ~ −50 mm; this is a result of synthetical effect by Al flocs adsorption and Fe(III) reductive dissolution. LMB decreased Cd, Co, and Pb in LMB layer in carbonate, reducible, and oxidizable forms. PAC decreased Cd mobility but caused the transformation of Co and Pb from reducible to other forms because of Fe(III) reductive dissolution. Those results indicate that sedimentary Fe plays an important role in in situ passivation. We suggest modifying passivators to Fe(II) adsorbents and increasing DO permeability of sediment to promote the formation of an Fe(III) passivation layer and hence the effectiveness of P control.

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 (Df), 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 Df 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 Df value of the flocs compared to P, and Df 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.

Fluoride removal from water by electrocoagulation: Effect of the type of water and the experimental parameters

Contamination of the ground water with fluoride is a great problem worldwide. Removal of fluoride (F−) ions from simulated natural waters containing fluoride by electrocoagulation (EC) using aluminum electrodes, has been investigated in a discontinuous lab cell. Two types of water have been studied: local tap water and deionized water-based luoride solutions of sodium fluoride with addition of sodium chloride to reach the desired conductivity. The effect of four operating parameters has been followed for a current density fixed at 5 mA/cm2 within the following ranges: fluoride concentration (5–50 mg/L), temperature (25–55 °C), conductivity (1–6 mS/cm) and initial pH (4–8.5). In accordance with published data, the presence of 61 mg/L buffering hydrogencarbonate ions in the tap water was found to substantially reduce the Al(III) amount required for a given abatement in comparison with deionized water. Performance comparison of the discontinuous electrocoagulation treatment between the two types of water has been discussed for 90% abatement of F− introduced, in terms of the amount of Al(III) dissolved over the initial fluoride concentration, the parameters of a previous adsorption model and the fraction of Al(III) flocs not involved in the adsorption. EC performances were shown to be governed by the solution pH for the two types of water, with little effect of the other operating conditions: at initial pH 6, F− abatement was found to require two or three times less trivalent aluminium than at initial pH 8.5.

Membrane fouling reduction through electrochemically regulating flocs aggregation in an electro-coagulation membrane reactor

Coupling coagulation and applied electric field is an efficient method to regulate cake layer porosity and hydrophilicity for alleviating ultrafiltration membrane (UF) fouling. However, the Al/Fe flocs aggregation behavior are induced from electric field and determine the cake layer structure, which has not been studied comparatively yet. Herein, the anti-fouling performance in an efficient electro-coagulation membrane reactor (ECMR, in which UF membrane modules are placed between electrodes) was investigated with Al/Fe anode and various electrochemical parameters from the viewpoint of regulating flocs aggregation. Both the cake layers formed from Al and Fe flocs under an electric field were more porous and hydrophilic in comparison with that formed without electric fields, resulting in an enhanced water flux under higher electric field strength. Comparing with Fe flocs, Al flocs had a faster growth rate and larger size, facilitating membrane pore block resistant, which was more pronounced in a higher current density. Furthermore, the cake layer formed from Al flocs was more porous than that formed from Fe flocs. Therefore, the anti-fouling performance of ECMR with Al anode was superior to that of ECMR with Fe anode. When the electric field strength increased from 0 to 10 V/cm, the normalized specific flux was improved from 71.2% to 89.4% for ECMR (Al) and from 48.1% to 70.1% for ECMR (Fe) at 30 min.

Removal of heavy metals by electrocoagulation from hydrogenocarbonate-containing waters: Compared cases of divalent iron and zinc cations

Divalent iron and zinc cations can be removed from water by electrocoagulation (EC) with aluminium electrodes in a discontinuous system: the effect of hydrocarbonate HCO3- ion often present in liquid waste and in groundwater on the EC process has been investigated. For the two ions, the presence of hydrocarbonate strongly limits the pH variations by its buffering properties and reduces the rates of Al dissolution by corrosion. Removal of the two cations was then shown to require longer treatment times and larger amounts of dissolved aluminium. Whereas the local pH gradients near the electrode surface with HCO3− free water was previously shown to allow local formation of stable Zn and Fe hydroxides, which actively contribute to their elimination, the presence of hydrocarbonate nearly suppresses this positive phenomenon, resulting in far less efficient EC treatment. Whereas removal of zinc cations from carbonated water can be considered as their simple adsorption on the Al flocs, Fe2+ ions are oxidized to Fe(OH)3 by air oxidation after their adsorption. Use of an overall adsorption model allowed quantitative comparison of the EC treatments, with very different adsorption parameters for the two metal studied.

Iron removal from waters by electrocoagulation: Investigations of the various physicochemical phenomena involved

Abstract Electrocoagulation (EC) is an electrochemical technique for removal of various pollutants – in particular metal cations – from waste or groundwaters. In comparison with other metal cations, iron can be under divalent and trivalent forms, with different physicochemical properties, so various physicochemical phenomena are to occur for its removal. For the case of Fe2+ ions removal from a synthetic aqueous solution by EC with aluminium electrodes, we investigated both occurrence and significance of the various phenomena encountered e.g. formation of divalent iron hydroxide, adsorption of Fe species on Al(III) flocs formed and oxidation phenomena. Designed experiments have been conducted with an electrochemical cell at various current densities below 10 mA cm−2 and pH, and depending on the nature of the gaseous atmosphere, or in an electroless stirred vessel. Analysis of the data showed that, in addition to direct Fe2+ adsorption on generated solid aluminium hydroxide, Fe(II) hydroxide formed near the cathode surface, precipitates jointly on the Al flocs. Fe(II) oxidation by air oxygen in the liquid phase in EC runs was predicted to be little significant, whereas solid Fe(OH)2 is oxidized more efficiently to Fe(OH)3. However, Fe(II) oxidations improve only little its removal from the water treated by electrocoagulation, as shown by EC tests in anoxic conditions.

Regrowth of Broken Hydroxide Flocs: Effect of Added Fluoride.

Hydrous oxides of Al(III) and Fe(III) play a large part in environmental processes and in the action of coagulants used in water and wastewater treatment. Aggregates (flocs) of hydroxide precipitates can be rather weak and are easily broken by applied shear. It is usually found that broken flocs do not fully regrow under low-shear conditions, and this could be a serious disadvantage in practical applications. The irreversible nature of floc breakage suggests that some form of specific, chemical interaction between precipitate particles must be at least partly responsible. On the basis of experiments reported here and elsewhere, we propose that hydroxyl bridges between particles play a part. When these are broken, there is a reduction in the number of "active" surface groups that are able to form new bridges. When small amounts of fluoride are added during breakage of Al flocs, there can be significant improvement in floc regrowth, although this depends on a number of factors, especially pH. With Fe flocs, fluoride has no noticeable effect. These results can be explained by the formation of soluble Al-F complexes and some dissolution of the Al(OH)3 precipitate. This creates a new surface with more "active" groups that can form new hydroxyl bridges.

수계 내 조류 제거를 위한 전기응집 운전 특성 평가

Abstract Electro-coagulation experiments were conducted with aluminum (Al) or iron (Fe) electrode in order to determine the optimal electrode material and operation conditions for algae removal. Al electrode showed higher removal rate of algae than Fe electrode because Al flocs have positive surface charges which electrostatically attract algae species having negative surface charges. Removal rate of algae and total phosphorous (T-P) was increased as current density and electrode area increases. It was also found that initial pH with neutral range was optimum for T-P removal by electro-coagulation. Bench-scale continuous flow experiments consisted of electro-coagulation reactor, agitation tank and settling tank were conducted. In electro-coagulation reactor, a large fraction of Al flocs were distributed to scum layer, due to the gas bubbles generated by electrolysis reaction. In agitation tank, most of Al flocs were settled and the optimal mixing intensity was found to be 50 rpm to achieve good settleability. The removal rate of algae was about 90-95%. Additionally, the removal rate of the T-P and COD was observed to be 73.8±8.0% and 75.0±3.8%, respectively. Meanwhile, the removal rate of total nitrogen (T-N) was relatively low at only 24%.

Electrocoagulation of colloidal biogenic selenium.

Colloidal elemental selenium (Se(0)) adversely affects membrane separation processes and aquatic ecosystems. As a solution to this problem, we investigated for the first time the removal potential of Se(0) by electrocoagulation process. Colloidal Se(0) was produced by a strain of Pseudomonas fluorescens and showed limited gravitational settling. Therefore, iron (Fe) and aluminum (Al) sacrificial electrodes were used in a batch reactor under galvanostatic conditions. The best Se(0) turbidity removal (97 %) was achieved using iron electrodes at 200 mA. Aluminum electrodes removed 96 % of colloidal Se(0) only at a higher current intensity (300 mA). At the best Se(0) removal efficiency, electrocoagulation using Fe electrode removed 93 % of the Se concentration, whereas with Al electrodes the Se removal efficiency reached only 54 %. Due to the less compact nature of the Al flocs, the Se-Al sediment was three times more voluminous than the Se-Fe sediment. The toxicity characteristic leaching procedure (TCLP) test showed that the Fe-Se sediment released Se below the regulatory level (1 mg L(-1)), whereas the Se concentration leached from the Al-Se sediment exceeded the limit by about 20 times. This might be related to the mineralogical nature of the sediments. Electron scanning micrographs showed Fe-Se sediments with a reticular structure, whereas the Al-Se sediments lacked an organized structure. Overall, the results obtained showed that the use of Fe electrodes as soluble anode in electrocoagulation constitutes a better option than Al electrodes for the electrochemical sedimentation of colloidal Se(0).

Mechanisms of Boron Removal with Electrocoagulation

Environmental Context. Various environmental regulation organizations have set up standards or guidelines to regulate the boron concentration in drinking water, as a result of concern for human and animal health. In 2004, the World Health Organization Guidelines for Drinking Water Quality recommended boron values of no more than 0.5 mg L–1 in drinking water. Preliminary studies on boron removal with electrocoagulation have been carried out. However, in order to enhance boron removal using this method, and to meet the stringent guidelines set in place by the World Health Organization, there is a need to obtain a better understanding of how boron is removed from water by electrocoagulation. Abstract. This study aims to explore the mechanisms of boron removal by electrocoagulation (EC). The results demonstrate that adsorption and precipitation of boron by Al flocs are dominant mechanisms in boron removal using EC. The Al flocs that result from the EC process are found to be mainly composed of polymeric Al13 polymers (43%) and to have a long-lasting positive charge. These characteristics of the flocs contribute to the high levels of boron removal observed using EC. The maximum boron adsorption of the Al flocs is 200 mg g–1 and the solubility product constant (Ksp), which represents the boron precipitate Al(OH)2BO2·nH2O, is 2.6 × 10−40 (at 20°C).

Cadmium adsorption on hydrous aluminium (III) oxide: effect of adsorbed polyelectrolyte

Freshly precipitated hydrous oxides of Al (flocs) are important sorbents of heavy metal ions and are used in water treatment processes. The addition of chelating agents or polyelectrolytes can increase the efficiency of heavy metal removal by flocs. The polymer polyethylenimine is commonly used as a flocculant aid in water treatment and has been modified with phthalic acid. Adsorption studies have shown that the addition of millimolar concentrations of polyelectrolyte increases the removal of Cd ions from a 29.7 μM aqueous solution by aluminium flocs from ca. 40% to up to 75%. Experiments in which the pH was varied demonstrated that the observed enhancement of Cd adsorption is caused by a shift of the pH edge to lower pH values in the presence of polyelectrolyte. Maximum polyelectrolyte adsorption occurs between pH 6 and pH 7, corresponding to the point of enhanced Cd adsorption in the presence of polyelectrolyte. The enhancement of Cd adsorption observed below pH 7 is therefore likely to be due to the formation of a ternary surface complex. At pH values above pH 8 the polyelectrolyte forms a stable complex with Cd and Al ions in solution causing floc dissolution and decreased Cd adsorption.