Influential factors of formation kinetics of flocs produced by water treatment coagulants

The growth rate and size of floc formation is of great importance in water treatment especially in coagulation process.The floc formation kinetics and the coagulation efficiency of synthetic water were investigated by using an on-line continuous optical photometric dispersion analyze and the analysis of water quality.Experimental conditions such as alum dosage,pH value for coagulation,stirring intensity and initial turbidity were extensively examined.The photometric dispersion analyze results showed that coagulation of kaolin suspensions with two coagulants(alum and polyaluminium chloride) could be taken as a two-phase process:slow and rapid growth periods.Operating conditions with higher coagulant doses,appropriate pH and average shear rate might be particularly advantageous.The rate of overall floc growth was mainly determined by a combination of hydraulic and water quality conditions such as pH and turbidity.The measurement of zeta potential indicates that polyaluminium chloride exhibited higher charge-neutralizing ability than alum and achieved lower turbidities than alum for equivalent Al dosages.Under the same operating conditions,the alum showed a higher grow rate,but with smaller floc size.     

Coagulation behavior and floc properties of compound bioflocculant-polyaluminum chloride dual-coagulants and polymeric aluminum in low temperature surface water treatment

This study was intended to compare coagulation behavior and floc properties of two dualcoagulants polyaluminum chloride–compound bioflocculant(PAC–CBF)(PAC dose first) and compound bioflocculant–polyaluminum chloride(CBF–PAC)(CBF dose first) with those of PAC alone in low temperature drinking water treatment. Results showed that dualcoagulants could improve DOC removal efficiency from 30% up to 34%. Moreover, CBF contributed to the increase of floc size and growth rate, especially those of PAC–CBF were almost twice bigger than those of PAC. However, dual-coagulants formed looser and weaker flocs with lower breakage factors in which fractal dimension of PAC–CBF flocs was low which indicates a looser floc structure. The floc recovery ability was in the following order:PAC–CBF PAC alone CBF–PAC. The flocculation mechanism of PAC was charge neutralization and enmeshment, meanwhile the negatively charged CBF added absorption and bridging effect.     

Disinfection byproduct precursor removal by enhanced coagulation and their distribution in chemical fractions

Raw water from the Songhua River was treated by four types of coagulants, ferric chloride(FeCl3), aluminum sulfate(Al2(SO4)3),polyaluminum chloride(PACl) and composite polyaluminum(HPAC), in order to remove dissolved organic matter(DOM). Considering the disinfection byproduct(DBP) precursor treatability, DOM was divided into five chemical fractions based on resin adsorption.Trihalomethane formation potential(THMFP) and haloacetic acid formation potential(HAAFP) were measured for each fraction. The results showed that hydrophobic acids(HoA), hydrophilic matter(HiM) and hydrophobic neutral(HoN) were the dominant fractions.Although both HoN and HoA were the main THM precursors, the contribution for THMFP changed after coagulation. Additionally,HoA and HiM were the main HAA precursors, while the contribution of HoN to HAAFP significantly increased after coagulation.HoM was more easily removed than HiM, no matter which coagulant was used, especially under enhanced coagulation conditions.DOC removal was highest for enhanced coagulation using FeCl3 while DBPFP was lowest using PACl. This could indicate that not all DOC fractions contained the precursors of DBPs. Reduction of THMFP and HAAFP by PACl under enhanced coagulation could reach51% and 59% respectively.     

Influence of COM-peptides/proteins on the properties of flocs formed at different shear rates

Coagulation followed by floc separation is a key process for the removal of algal organic matter(AOM) in water treatment. Besides optimizing coagulation parameters,knowledge of the properties of AOM-flocs is essential to maximizing AOM removal.However, the impact of AOM on the floc properties remains unclear. This study investigated how peptides/proteins derived from the cellular organic matter(COM) of the cyanobacterium Microcystis aeruginosa influenced the size, structure, and shape of flocs formed at different shear rates(G). Flocs formed by kaolinite, COM-peptides/proteins and a mixture of the same were studied, and the effect of intermolecular interactions between floc components on floc properties was assessed. The coagulation experiments were performed in a Taylor–Couette reactor, with aluminum(Al) or ferric sulphate(Fe) utilized as coagulants. Image analysis was performed to gauge floc size and obtain data on fractal dimension. It was found that floc properties were affected by the presence of the COM-peptides/proteins and the coagulant used. COM-peptides/proteins increased floc size and porosity and widened floc size distributions. The Fe coagulant produced larger and less compact flocs than Al coagulant. Moreover, the decrease in floc size that occurred in parallel with increase in shear rate was not smooth in progress. A rapid change for the kaolinite-coagulant suspension and two rapid changes for the suspensions containing COM were observed. These were attributed to various intermolecular interactions between floc components participating in coagulation at different G. Based on the results obtained, shear rates suitable for efficient separation of flocs containing COM were suggested.     

Fractionation of residual Al in natural water treatment from reservoir with poly-aluminum-silicate-chloride (PASiC): Effect of OH/Al, Si/Al molar ratios and initial pH

An aluminum fractionation study was conducted for a surface reservoir water treatment to understand the performance of poly-aluminum-silicate-chloride (PASiC) in terms of the residual Al fractions as a function of initial pH. The coagulation performance expressed as turbidity and organic matter removal was established as supporting data. Some extra data were evaluated in terms of the residual Al ratio of the composite PASiC coagulant. The main residual Al sources were the Al fractions derived from the use of PASiC. The turbidity and organic matter removal ability was optimal at initial pH 6.00-7.00, while the concentrations of various residual Al species and the residual Al ratio of PASiC were minimal at an initial pH range of 7.00-8.00. Under the conditions of OH/Al molar ratio = 2.00 and Si/Al molar ratio = 0.05, PASiC had superior coagulation performance and comparatively low residual Al concentrations. The Al fraction in the composite PASiC coagulant seldom remained under such conditions. Experimental data also indicated that the suspended (filterable) Al fraction was the dominant species, and organic-bound or organo-Al complex Al was considered to be the major species of dissolved Al in water treated by PASiC coagulation. Additionally, the dissolved inorganic monomeric Al species dominated the dissolved monomeric Al fraction.     

Analysis of floc morphology in a continuous-flow flocculation and sedimentation reactor

The floc morphology was investigated in a continuous-flow reactor, in order to understand the evolution of flocs in practical flocculation and sedimentation processes in water utilities. Kaolin-humic acid suspension was used as the test water, and polyaluminum chloride was chosen as the coagulant. An in-situ recognition system was applied to analyze the floc size, boundary fractal dimension, and eccentricity ratios. Particle numbers and turbidity were also determined in the sedimentation stage. At a coagulant dose of 1 mg/L as Al, the average floc size increased from 62 to 78 μm and the boundary fractal dimension was around 1.14, suggesting that flocs were compact and continuously grew during the entire flocculation process. However, with the dose increased to 5 mg/L, the average floc size decreased and stabilized at around 65 μm, with the fractal dimension of 1.20. It can be concluded that the excess coagulant doses resulted in the formation of chain-shaped, lower density, and more branched structure flocs, thereby restricting flocs' further growth in the subsequent flocculation. Floc morphology analysis suggested that charge neutralization dominated in the initial flocculation stage, then the bridge and sweep mechanisms were dominant in the subsequent flocculation. In addition, compared with the traditional inclined plate settler, a novel V-shaped plate settler introduced in this study had an advantage in small size floc(less than 5 μm) removal. The V-shaped region could promote aggregate restructuring and re-flocculation; therefore, the V-shaped plate settler provides an alternative method for sedimentation.     

On-line optical determination of floc size of Fe(Ⅲ) coagulants

This study investigated the floc aggregation, average floc size, floc size variance and floc growth velocity when ferric chloride （FeCl3） and polyferric chloride （PFC） were used to treat the simulated water samples. The factors including coagulant dose, ionic strength and solution pH, which affect the floc aggregation, were studied. Experiments were carried out in a bench-scale reactor using photometric dispersion analyzer （ PDA）. Results showed that there were great differences between the floc aggregation of PFC and FeCl3. The average floc size and fioc growth velocity of PFC were much larger than those of FeCl3. Compared with FeCl3, PFC gave a better coagulation performance in wider range of pH, dosage and ionic strength. It was also found that the coagulation efficiency of PFC did not depend on average floc size but on floc growth velocity.     

Influence of coagulation mechanisms and floc formation on filterability

Minimizing particles in water is a key goal for improving drinking water quality and safety.The media filtration process,as the last step of the solid–liquid separation process,is largely influenced by the characteristics of flocs,which are formed and controlled within the coagulation process.In a laboratory-based study,the impacts of the physical characteristics of flocs formed using aluminum sulfate on the filtration treatment of two comparative water samples were investigated using a photometric dispersion analyzer and a filterability apparatus.In general,the optimum dosage for maximizing filterability was higher than that for minimizing turbidity under neutral p H conditions.For a monomeric aluminum-based coagulant,the charge neutralization mechanism produced better floc characteristics,including floc growth speed and size,than the sweep flocculation mechanism.In addition,the charge neutralization mechanism showed better performance compared to sweep flocculation in terms of DOC removal and floc filterability improvement for both waters,and showed superiority in turbidity removal only when the raw water had high turbidity.For the different mechanisms,the ways that floc characteristics impacted on floc filterability also differed.The low variation in floc size distribution obtained under the charge neutralization mechanism resulted in the flocs being amenable to removal by filtration processes.For the sweep flocculation mechanism,increasing the floc size improved the settling ability of flocs,resulting in higher filter efficiency.     

Electrokinetic characteristic and coagulation behavior flocculant polyaluminum silicate chloride (PASiC)

The electrokinetic characteristics and coagulation behaviors of polyaluminum silicate chloride(PASiC)and polyaluminum chloride (PAC) were studied and compared by streaming current(SC) measurement and jar test method.The experimental results showed that the interaction between polysilicic acid characterized negative charge and hydrolyzed aluminum species result in a decrease of the charge-neutralizing ability of PASiC, compared to PAC.The decrease has a close relationship with the basicity(B) and Al/Si molar ratio in PASiC.The less the B value and the Al/Si molar ratio,the lower the change-neutralizing ability of PASiC is.In contrast,the preparation technique for PASiC affects the charge-neutralization of PASiC to a smaller extent.In addition, compared with PAC, PASiC may enhance aggregating efficiency and give better coagulating effects.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Optimized coagulation pretreatment alleviates ultrafiltration membrane fouling: The role of floc properties and slow-mixing speed on mechanisms of chitosan-assisted coagulation

To alleviate ultrafiltration(UF) membrane fouling, the pre-coagulation of poly-aluminum chloride(PACl) with the aid of chitosan(CTS) was conducted for synthetic humic acid–kaolin water treatment. Pre-coagulation of three molecular weights(MW) CTSs(50–190 kDa(CTSL), 190–310 kDa(CTSM) and 310–375 kDa(CTSH)) was optimized with slow-mixing speeds of 30, 60 and 90 r/min, respectively. The removal efficiency and floc properties as well as membrane fouling were analyzed, and were compared to results obtained by conventional coagulation with PACl. Results showed that variations in floc properties could be ascribed to the coagulation mechanisms of CTS_L/CTS_M/CTS_H at different slow-mixing speeds, resulting in reduced UF membrane fouling. Specifically, at the low speed of 30 r/min, all three CTS types produced flocs with similar properties, while CTSLresulted in the lowest removal efficiency and aggravated irreversible fouling. At the appropriate speed of 60 r/min, CTSMgenerated the most compact flocs with the combined effects of bridging and path mechanisms. The compact cake layer formed could alleviate irreversible fouling,which was beneficial for prolonging the operation of the UF membrane. At the high speed of90 r/min, CTSHformed fragile flocs and aggravated irreversible membrane fouling. We considered membrane fouling to be affected by floc properties and the resultant removal efficiency, which was governed by the MW of the CTS used and the slow-mixing speed applied as well.     

Al(Ⅲ) speciation distribution and transformation in high concentration PACl solutions

Effects of Al（Ⅲ） concentration and pH on the speciation of Al（Ⅲ） in polyaluminum chloride （PACl） solutions especially on the Al13 fraction were investigated. A series of PACl samples were prepared over the range of Al（Ⅲ） concentration from 0.01 to 2.0 mol/L with the B （OH/Al ratio） value from 1.0 to 2.5 by forced hydrolysis of AICl3. The samples were characterized by ferron assay, pH and 27^Al NMR. It was shown that the Al（Ⅲ） concentration had a dramatic effect on the hydrolysis processes and the species distribution of PACl was in relate to the decrease of pH. The fraction of Al species, Alb （or Al13） decreased and Al0 increased with increase of total Al（Ⅲ） concentration. Under the condition of Al（Ⅲ） 2.0 reel/L, B = 2.5, the pH value was 2.73 and no Al13 could be detected. During diluting and aging, the species distribution evoIved. The Al13 could then be detected again and the amounts increased with time. If the diluted samples were concentrated by freeze dry at -35℃ or heating at 80℃, the pH value and Al13 content would decrease with the increased concentration. It demonstrated that the key factor for formation of Al13 in concentrated PACl was pH value.     

Simultaneous nitrogen and phosphor removal in an aerobic submerged membrane bioreactor

Simultaneous nitrification and denitrification （SND） effect and phosphor removal were investigated in a one-staged aerobic submerged membrane bioreactor on pilot-scale with mixed liquor suspended solids （MLSS） 19--20 g/L. The effects of DO concentration, sludge floc size distribution on SND were studied. Test results suggested that SND was successfully performed in the membrane bioreactor （MBR） and about 70% total nitrogen removal efficiency was achieved when DO concentration was set to 0.2-- 0.3 mg/L. The main mechanisms governing SND were the suitable sludge floc size and the low DO concentration which was caused by low oxygen transfer rate with such a high MLSS concentration in the MBR. In the meantime, phosphor removal was also studied with polymer ferric sulfate （PFS） addition and 14 mg/L dosage of PFS was proper for the MBR to remove phosphor. PFS addition also benefited the MBR operation owing to its reduction of extracellular polymer substances （EPS） of mixed liquor.     

Efficacy of two chemical coagulants and three different filtration media on removal of Aspergillus flavus from surface water

Aquatic fungi are common in various aqueous environments and play potentially crucial roles in nutrient and carbon cycling as well as interacting with other organisms. Species of Aspergillus are the most common fungi that occur in water. The present study was undertaken to elucidate the efficacy of two coagulants, aluminum sulfate and ferric chloride, used at different concentrations to treat drinking water, in removing Aspergillusflavus, as well as testing three different filtration media： sand, activated carbon, and ceramic granules, for their removal of fungi from water. The results revealed that both coagulants were effective in removing fungi and decreasing the turbidity of drinking water, and turbidity decreased with increasing coagulant concentration. Also, at the highest concentration of the coagulants, A. flavus was decreased by 99.6% in the treated water. Among ceramic granules, activated carbon, and sand used as media for water filtration, the sand and activated carbon filters were more effective in removing A.flavus than ceramic granules while simultaneously decreasing the turbidity levels in the test water samples. Post-treatment total organic carbon （TOC） and total nitrogen （TN） concentrations in the experimental water did not decrease; on the contrary, TN concentrations increased with the increasing dosage of coagulants. The filtration process had no effect in reducing TOC and TN in tested water.     

Deposition behavior of residual aluminum in drinking water distribution system: Effect of aluminum speciation

Finished drinking water usually contains some residual aluminum.The deposition of residual aluminum in distribution systems and potential release back to the drinking water could significantly influence the water quality at consumer taps.A preliminary analysis of aluminum content in cast iron pipe corrosion scales and loose deposits demonstrated that aluminum deposition on distribution pipe surfaces could be excessive for water treated by aluminum coagulants including polyaluminum chloride（PACl）.In this work,the deposition features of different aluminum species in PACl were investigated by simulated coil-pipe test,batch reactor test and quartz crystal microbalance with dissipation monitoring.The deposition amount of non-polymeric aluminum species was the least,and its deposition layer was soft and hydrated,which indicated the possible formation of amorphous Al（OH）₃.Al₁₃ had the highest deposition tendency,and the deposition layer was rigid and much less hydrated,which indicated that the deposited aluminum might possess regular structure and self-aggregation of Al₁₃could be the main deposition mechanism.While for Al₃₀,its deposition was relatively slower and deposited aluminum amount was relatively less compared with Al₁₃.However,the total deposited mass of Al₃₀ was much higher than that of Al₁₃,which was attributed to the deposition of particulate aluminum matters with much higher hydration state.Compared with stationary condition,stirring could significantly enhance the deposition process,while the effect of pH on deposition was relatively weak in the near neutral range of 6.7 to 8.7.     

Optimized production of a novel bioflocculant M-C11 by Klebsiella sp. and its application in sludge dewatering

The optimized production of a novel bioflocculant M-C11 produced by Klebsiella sp. and its application in sludge dewatering were investigated. The optimal medium carbon source,nitrogen source, metal ion, initial pH and culture temperature for the bioflocculant production were glucose, NaNO3, MgSO4, and pH 7.0 and 25°C, respectively. A compositional analysis indicated that the purified M-C11 consisted of 91.2% sugar, 4.6% protein and 3.9% nucleic acids（m/m）. A Fourier transform infrared spectrum confirmed the presence of carboxyl, hydroxyl,methoxyl and amino groups. The microbial flocculant exhibited excellent pH and thermal stability in a kaolin suspension over a pH range of 4.0 to 8.0 and a temperature range of 20 to 60°C.The optimum bioflocculating activity was observed as 92.37% for 2.56 mL M-C11 and 0.37 g/L CaCl2 dosages using response surface methodology. The sludge resistance in filtration（SRF）decreased from 11.6 × 1012 to 4.7 × 1012m/kg, which indicated that the sludge dewaterability was remarkably enhanced by the bioflocculant conditioning. The sludge dewatering performance conditioned by M-C11 was more efficient than that of inorganic flocculating reagents,such as aluminum sulfate and polymeric aluminum chloride. The bioflocculant has advantages over traditional sludge conditioners due to its lower cost, benign biodegradability and negligible secondary pollution. In addition, the bioflocculant was favorably adapted to the specific sludge pH and salinity.     

Characterization of dissolved organic matter and membrane fouling in coagulation-ultrafiltration process treating micro-polluted surface water

Coagulation–ultrafiltration(C–UF) is widely used for surface water treatment. With the removal of pollutants, the characteristics of organic matter change and affect the final treatment efficiency and the development of membrane fouling. In this study, we built a dynamic C–UF set-up to carry out the treatment of micro-polluted surface water, to investigate the characteristics of dissolved organic matter from different units. The influences of poly aluminum chloride and poly dimethyldiallylammonium chloride(PDMDAAC) on removal efficiency and membrane fouling were also investigated. Results showed that the dosage of PDMDAAC evidently increased the UV254 and dissolved organic carbon removal efficiencies,and thereby alleviated membrane fouling in the C–UF process. Most hydrophobic bases(HoB)and hydrophobic neutral fractions could be removed by coagulation. Similarly, UF was good at removing HoB compared to hydrophilic substances(HiS) and hydrophobic acid(HoA)fractions. HiS and HoA fractions with low molecule weight accumulated on the surface of the membrane, causing the increase of transmembrane pressure(TMP). Membrane fouling was mainly caused by a removable cake layer, and mechanical cleaning was an efficient way to decrease the TMP.     

Kinetics and isotherms of Neutral Red adsorption on peanut husk

Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was deter...     

Electrocatalytic reduction of ortho nitrobenzaldehyde using modified aluminum electrode and its determination

A simple, cost effective and rapid electrochemical method has been developed for the determination of micro level ortho nitrobenzaldehyde（ONB） based on outstanding properties of modified aluminum electrode tin nanorods/anodic aluminum oxide/aluminum（SnNR/AAO/Al） for the first time. The SnNR/AAO/Al electrode was fabricated by a second step anodization, followed by electrodeposition and its electrochemical behavior was investigated in detail. The cyclic voltammetry results indicated that the SnNR/AAO/Al electrode exhibited efficient electrocatalytic activity toward reduction of ONB in the acidic solution. It provides an appreciable improvement of reduction peak for ONB at-0.721 V.Furthermore, various kinetic parameters such as transfer electron number, transfer proton number and standard heterogeneous rate constant were calculated from the scan rates.The electrocatalytic behavior was further exploited as a sensitive detection scheme for the ONB determination by differential pulse voltammetry. Under the optimized conditions, the concentration range and detection limit are 0.1-100 μmol/L and 0.05 μmol/L, respectively,for ONB. The analytical performance of this modified sensor has been evaluated for detection of real sample such as river water and recovery of ONB was achieved all-out up to102.3% under standard addition method.     

Cultivation of aerobic granules for simultaneous nitrification and denitrification by seeding different inoculated sludge

Cultivation of aerobic granules for simultaneous nitrification and denitrification in two sequencing batch airlift bioreactors was studied. Conventional activated floc and anaerobic granules served as main two inoculated sludge in the systems. Morphological variations of sludge in the reactors were observed. It was found that the cultivation of aerobic granules was closely associated with the kind of inoculated sludge. Round and regular aerobic granules were prevailed in both reactors, and the physical charactedstics of the aerobic granules in terms of settling ability, specitic gravity, and ratio Of water containing were distinct wnen the inoculate sludge differe. Aerobic granules formed by seeding activated floc are more excellent in simultaneous nitrification and denitrification than that by aerobic granules formed from anaerobic granules. It was concluded that inoculated sludge plays a crucial role in the cultivation of aerobic granules for simultaneous nitrification and denitrification.