Reactive Dye Removal Using Inorganic–Organic Composite Material: Kinetics,Mechanism, and Optimization

An inorganic–organic composite material (MCPAM) consisting of magnesium chloride and polyacrylamide, was applied to remove reactive dye (Cibacron Red FN-R) from aqueous solution through coagulation–flocculation process. MCPAM with the ratio of 90% MgCl₂/10% PAM was the best ratio in removing reactive dye. Kinetics of reactive dye removal was investigated using pseudo-kinetics model and it fits pseudo-second-order reaction model. The mechanism of reactive dye removal was investigated through physicochemical properties of supernatant, flocs, and sludge. The change of conductivity and pH denotes the interactions between reactive dye and MCPAM. The chemical structure, settling, and microstructure of sludge indicate the formation of sludge during coagulation–flocculation process. The settled sludge volume and sludge volume index (SVI) that of MCPAM was lower than that of MgCl₂. The flocs formed using MCPAM was also relatively compact and larger in size compared to that of MgCl₂. The reactive dye removal was optimized through central composite design whereby color removal (%) and chemical oxygen demand (COD) reduction (%) were optimized by five operating factors, namely, concentration of dye, pH, dosage of MCPAM, agitation speed, and agitation time. The optimal values reported for color removal (%) and COD reduction (%) were of 97–98% and 60–81%, respectively.     

Olive mill wastewater treatment by a pilot-scale subsurface horizontal flow (SSF-h) constructed wetland

Performances of a pilot-scale reed bed for the olive mill wastewater (OMW) treatment were investigated, by monitoring influent and effluent pH, total suspended solids (TSS), chemical oxygen demand (COD), total Kjeldahl nitrogen (TKN), total phosphorus and polyphenols. In order to reduce the suspended matter concentration and to avoid clogging, OMW was pre-treated by adding lime putty, calcium hydroxide and hydraulic lime. The best results were obtained with 2 g/L of hydraulic lime. Pre-treated OMW was dosed in the reed bed at dilution ratios of 1/3 and 1/10 (v/v), pointing up that the latter only did not give rise to reed suffering and allowed to obtain good and durable removal efficiencies, above all for COD (74.1+/-17.6%) and polyphenols (83.4+/-17.8%). Recycling of the effluent was quite effective for the improvement of the wastewater quality, allowing a further removal of 26-70%, depending on the parameter taken into account. A post-dosage study, carried out by feeding the reed bed with the effluent of an activated sludge plant, pointed up a rapid decreasing of the outlet concentrations of the investigated parameters to values compatible with Italian regulations concerning wastewater discharge in surface water. Polyphenols were the exception, being their outlet concentration at the end of post-dosage study around 2 mg/L.     

Early-stage flocculation kinetics of polystyrene latex particles with polyelectrolytes studied in the standardized mixing: Contrast of excess and moderate polyelectrolyte dosage

Standardized mixing procedure was applied to the analysis of flocculation of polystyrene latex (PSL) particles with polyelectrolytes. After confirming the initial enhancement of flocculation rate in the very beginning followed by abrupt stop with excess dosage, attention was shifted to the system of moderate dosage. In the former, effects of ionic strength were further analyzed to find the consistency with adsorption isotherm. In the latter, flocculation started slowly in the beginning, sometime slower than salt-induced rapid coagulation, however, the rate gradually increases in the middle stage. Often, the increased rate exceeds that of salt-induced rapid coagulation. This behavior emerged more clearly in the case of lower ionic strength. This is the indication that the rate of relaxation of polymer on the colloidal surface is a function of surface coverage and ionic strength. The ultimate degree of flocculation is usually higher than that observed for excess dosage. The size distribution of flocs was also examined, however, no clear difference between different experimental conditions was confirmed for the same degree of flocculation.     

Effect of coagulation conditions on the dewatering properties of sludges produced in drinking water treatment

The coagulation and flocculation processes in conventional drinking water treatment generate aggregates which settle to form a sludge waste. This sludge can be dewatered further by thickening, centrifugation and filtration operations in order to recover water and minimise the volume of the waste stream.A range of water treatment sludges generated in the laboratory were characterised according to a phenomenological method that is valid from the dilute free-settling regime to the concentrated cake compression stages. These were compared with plant samples.Experimental results show that raw water natural organic matter (NOM), coagulant dose and coagulation pH affected both the rate and potential extent of dewatering. Similar effects were observed for both aluminium sulfate and ferric chloride. These results suggest that increasing dose or pH leads to an increase in the proportion of rapidly precipitated material in the sludge or flocs, which form looser aggregates and hence exhibit inferior dewatering properties.     

聚合氯化铝的制备及在微污染水处理中的应用

用酸溶法制备聚合氯化铝,对合成产品进行红外光谱分析,并应用于微污染原水的处理。处理微污染原水结果表明:当投加量为40.0 mg/L,pH值为6.0～9.0时,剩余浊度达到1.0NTU以下,总有机碳(Total Or-ganic Carbon,TOC)去除率达到41.2%。对比试验结果表明自制的聚合氯化铝的除浊效果优于一些常见工业聚合氯化铝。     

Fenugreek mucilage as a flocculating agent for sewage treatment

The use of fenugreek mucilage, a natural polysaccharide and a direct food additive, as a flocculating agent for removal of suspended and dissolved solids from sewage effluent has been reported. A flocculation study has been done by the standard jar test method. The percent removal of suspended solid (SS) and dissolved solid (TDS) was determined by varying the polymer dose, pH and contact time. X-ray diffraction patterns of the solid waste material of mucilage and flocs (so obtained after treatment) were used to suggest the incorporation of the crystalline waste material in the mucilage. The optimal mucilage concentration was found to be 0.16 mg/l. The suitable pH range for maximum solid removal (SS and TDS) was alkaline and the time required for treatment was 1-3 h.     

Treatment of pulp and paper mill wastewaters with poly aluminium chloride and bagasse fly ash

The present study deals with the use of poly aluminium chloride (PAC) as a coagulant and bagasse fly ash (BFA), which is generated in sugar mills, as an adsorbent for the removal of chemical oxygen demand (COD) and colour of pulp and paper mill effluents. Under optimal conditions of pH 3 and initial PAC dosage of 3 g/l, about 80% COD removal and 90% colour removal were obtained. The optimal conditions for the adsorptive removal of COD and colour with BFA were pH 4 and BFA dosage of 2 g/l. Under these conditions, COD and colour removal were, respectively, 50 and 55%. Adsorptive removal of COD by BFA followed second-order kinetics. Intra-particle diffusion was found to be rate controlling. Freundlich and Langmuir adsorption isotherms were found to fit the equilibrium adsorption data with BFA. Two-stage treatment using PAC (3 g/l) as a coagulant in the first stage and BFA (2 g/l) as an adsorbent in the second stage gave the combined COD and colour removal of nearly 87 and 95%, respectively, for different effluents without any pH adjustment. Two-stage adsorptive treatment using BFA (2 g/l) in both the stages gave a combined COD and colour removal of about 70%. The sludge obtained can be dewatered by centri-clarifiers, dried, briquetted and incinerated to recover its energy content.     

Natural organic matter removal by coagulation during drinking water treatment: A review

Natural organic matter (NOM) is found in all surface, ground and soil waters. An increase in the amount of NOM has been observed over the past 10-20 years in raw water supplies in several areas, which has a significant effect on drinking water treatment. The presence of NOM causes many problems in drinking water and drinking water treatment processes, including (i) negative effect on water quality by causing colour, taste and odor problems, (ii) increased coagulant and disinfectant doses (which in turn results in increased sludge volumes and production of harmful disinfection by-products), (iii) promoted biological growth in distribution system, and (iv) increased levels of complexed heavy metals and adsorbed organic pollutants. NOM can be removed from drinking water by several treatment options, of which the most common and economically feasible processes are considered to be coagulation and flocculation followed by sedimentation/flotation and sand filtration. Most of the NOM can be removed by coagulation, although, the hydrophobic fraction and high molar mass compounds of NOM are removed more efficiently than hydrophilic fraction and the low molar mass compounds. Thus, enhanced and/or optimized coagulation, as well as new process alternatives for the better removal of NOM by coagulation process has been suggested. In the present work, an overview of the recent research dealing with coagulation and flocculation in the removal of NOM from drinking water is presented.     

The role of polymer adsorption kinetics in flocculation

The adsorption of polymeric flocculants on the surfaces of suspended solid particles is a non-equilibrium process. It is postulated that the process is controlled by an irreversible attachment between polymer molecules and solid particles. The frequency of such collisions determines the kinetics of adsorption and the distribution of adsorbed polymer on individual particle surfaces. A simplified model is presented in which polymer–particle collision frequencies determine the distribution of adsorbed polymer, and therefore, the adhesion efficiency of the particle–particle collisions that lead to flocculation. The implications of the model with regard to the effects of process variables, such as polymer molecular weight, particle size distribution, solids concentration and mixing conditions, are discussed at length. The critical importance of initial dispersion stability on polymer dosage requirements and overall process performance is demonstrated. The model provides considerable insight into the mechanisms involved in the use of progressive polymer addition to control adsorption and enhance flocculation efficiency.     

Enhanced flocculation activity of polyacrylamide‐based flocculant for purification of industrial wastewater

The flocculation activity of commercially available anionic poly (acrylamide‐co‐acrylic acid), p (AAm‐co‐AA) has been significantly improved, without any inorganic coagulant aid. The effect of three types of surfactants, anionic sodium lauryl ether sulfate (SLES) (Palm Epimen), nonionic cocamide DEA, zwitterionic amphoteric Amphotensid B5, and one organic cation, trimethylammonium bromide (TAB) on coagulation/flocculation performance have been investigated. The performance has been analysed in terms of turbidity, total suspended solid (TSS), total iron (TI) content, and BTEX for treating two kinds of industrial wastewater, produced water (PW) and starch water. We have shown that adding a small amount of each of the studied surfactants, and especially cationic TAB, significantly increases the coagulation/flocculation performance without modifying pH levels. A combination of low dosage of flocculant (310 ppb) and TAB (310 ppb), after 5 minutes, presented 88%, 81%, and 62% reduction in turbidity, TSS, and TI content, respectively, whereas by using 5 ppm of flocculant alone (16 times more), only 76%, 75%, and 43% removal was obtained. The results reveal that TAB performs as an efficient coagulant booster. Compared with regular inorganic coagulants, it is more cost‐effective, reduces the consumption of treatment chemicals, and the pH‐dependency of contaminants removal.     

The preparation of an adsorbent from mixtures of sewage sludge and coal-tar pitch using an alkaline hydroxide activation agent

The increasing generation of sewage sludge and its subsequent treatment are very sensitive environmental problems. For the more stable and sanitary treatment of this sewage sludge, there have been many studies, including the recent attempt to prepare an adsorbent from sewage sludge via recycling. In this study, of the adsorbent preparation methods, chemical activation was utilized, and in order to find the optimum conditions, several variables were tested, such as the activation agent concentration, activation temperature and activation time. The activation agents used in this study were alkaline hydroxides: KOH and NaOH. The properties of prepared adsorbent were also measured by analyzing the iodine adsorptivity and surface area. In addition, the prepared adsorbent, the BOD, COD, SS, T-N and T-P removal efficiencies from the effluent water of a sewage treatment plant were examined via column test. From the test, the optimum conditions for KOH-activation were 1 mol/l, 800 °C and 1.5 h for the activation agent concentration, activation temperature and activation time, respectively; whereas those for NaOH-activation were 1.25 mol/l, 850 °C and 1.5 h. From the application of the prepared adsorbent to the effluent water of the sewage treatment plant, the measured BOD, COD, SS, T-N and T-P removal efficiencies, the P1-800 adsorbent had the highest efficiencies for BOD, COD and SS of 56.68, 57.76 and 81.45%, respectively.     

Electron beam pretreatment of sewage sludge before anaerobic digestion

The pretreatment of waste-activated sludge (WAS) by electron beam irradiation was studied in order to improve anaerobic sludge digestion. The irradiation dose of the electron beam was varied from 0.5 to 10 kGy. Batch and continuous-flow stirred tank reactors (CFSTRs) were operated to evaluate the effect of the electron beam pretreatment on anaerobic sludge digestion. Approximately 30–52% of the total chemical oxygen demand (COD) content of the WAS was solubilized within 24 h after electron beam irradiation. A large quantity of soluble COD, protein, and carbohydrates leached out from cell ruptures caused by the electron beam irradiation. Volatile fatty acids production from the irradiated sludge was approx 90% higher than that of the unirradiated sludge. The degradation of irradiated sewage sludge was described by two distinct first-order decay rates (k ₁ and k ₂). Most initial decay reaction accelerated within 10 d, with an average k ₁ of 0.06/d for sewage sludge irradiated at all dosages. The mean values for the long-term batch first-order decay coefficient (k ₂) were 0.025/d for irradiated sewage sludge and 0.007/d for unirradiated sludge. Volatile solids removal efficiency of the control reactor fed with unirradiated sewage sludge at a hydraulic retention time (HRT) of 20 d was almost the same as that of the CFSTRs fed with irradiated sludge at an HRT of 10 d. Therefore, disintegration of sewage sludge cells using electron beam pretreatment could reduce the reactor solid retention time by half.     

Coke wastewater treatment methods: Mini review

Coke wastewater production and its treatment is an alarming issue worldwide. Coke oven produces coke wastewater with a highly loaded and contaminated stream. Coke wastewater with high BOD (biochemical oxygen demand), COD (chemical oxygen demand), and nutrients impart serious threat if disposed of without treatment. It also contains phenol, ammonia, cyanide, thiocyanate & polycyclic aromatic hydrocarbons (PAHs). Because of composition and specificity of coke oven pollutants, appropriate selection of treatment method is a crucial step. The present literature review found that efficient treatment of coke wastewater can be done either by chemical or biological method. The chemical method is mostly performed by coagulation followed by sedimentation or flocculation, while biological method is preferably activated sludge process or nitrification/denitrification processes. An extensive review study on possible treatment methodologies of coke wastewater has been performed. This study focuses on comparison of performance of various treatment methods for coke wastewater.     

Study of flocculation with PONILIT GT-2 anionic polyelectrolyte applied into a chemical wastewater treatment

This paper discusses the applications of synthetic PONILIT GT-2 anionic polyelectrolyte in conjuction with ferric sulfate in a chemical wastewater treatment viz. wastewater from ceramics manufacturing. Synthetic wastewaters with different colloid concentrations were prepared and the coagulation-flocculation process followed by sedimentation and/or filtration was studied. Variables associated with the chemical wastewater composition, mixing time, and the coagulant and flocculant dose are considered in order to appreciate the process efficiency in terms of turbidity, chemical oxygen demand (COD), and color removal. The degrees are higher for turbidity and color (> 80 %) removal respectively, and, satisfactory for COD (< 50 %). An empirical model was elaborated by a third order rotatable design 2³ type, considering ferric sulfate dose, polyelectrolyte dose, and mixing time as independent variables, while the turbidity and color removal efficiencies were chosen as optimization criteria. The empirical model was found adequate for the chemical wastewater treatment. Also, an analysis of the model was performed to find the optimal operating conditions, in order to apply this process for an efficient chemical wastewater treatment using ferric sulfate as coagulation agent and PONILIT GT-2 anionic polyelectrolyte as flocculation agent. The optimal values correspond to a ferric ions concentration of 6.093 mg/L, a polyelectrolyte dose of 0.651 mg/L, and a mixing time of 24.024 minutes for turbidity removal (95.869 %), respectively, and, to a ferric ions concentration of 6.01 mg/L, a polyelectrolyte dose of 0.69 mg/L, and a mixing time of 26 minutes for color removal (98.741 %).      

Electrosteric stability of styrene/acrylic acid copolymer latices under emulsion polymerization reaction conditions

Acrylic acid (AA) is used in many emulsion polymerization formulations to improve the colloidal stability during and after the production of latex products. Theoretically, the improved stability originates from electrostatic repulsion complemented with steric repulsion. The objective of this work was to study the contribution of AA to the colloidal stability of polystyrene and styrene/AA copolymer latices under simulated reaction conditions. The strength of electrostatic and steric repulsion forces as a function of the electrolyte concentration, pH, and temperature was investigated via coagulation experiments with monomer‐swollen latices in stirred tank reactors. Transmission electron microscopy pictures and dynamic light scattering measurements provided an understanding of the conditions and mechanisms leading to coagulation. The experiments demonstrated that the presence of surface‐bound carboxylic groups only improved the colloidal stability if the carboxylic groups were charged, that is, at a high pH. At a low pH, the copolymer latices were even less stable than the homopolymer latex, and this indicated that the addition of AA did not improve the colloidal stability of a growing polystyrene latex. With respect to emulsion polymerization process operations, insufficient mixing and a highly concentrated electrolyte feed were found to be sources of fouling and enhanced macroscopic coagulation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 726–732, 2005     

Synthesis of a new flocculant based on poly(acrylamide-co-(N-octyl-4-vinylpyridinium bromide)) [AM5/VP5C8Br]-application for the turbidity removal from clay suspension

The interactions between poly(acrylamide-co-(N-octyl-4-vinylpyridinium bromide)) [AM5/VP5C8Br] cationic polyelectrolyte, and clay particles in dilute aqueous suspensions are studied in the aim of adsorption and flocculation. The extents of both phenomena are significantly influenced by the ionic strength of the medium. The adsorption of the clay particles on the copolymer chains occurs initially by the hydrophobic interaction. As flocculation mechanisms, the hydrophobic interaction between copolymer chains and the clay particles appears to be principal. In this work, we have prepared a copolymer which has been characterized by conductivity, viscosity, ¹H NMR, and FT-IR spectroscopies. The copolymer dosage and pH are two of the most important experimental parameters in the coagulation/flocculation operations used for study and optimization of the wastewater treatment operations. Under optimized conditions, 97% efficiency of the turbidity elimination, with a very low flocculant concentration of 3?ppm have been achieved in order to produce drinking water with standard limits around the world (< 1 NTU). The conclusion drawn on the basis of these results is that wastewater treatment using this new copolymer [AM5/VP5C8Br] has proved to be a good flocculant in overseeing of wastewater turbidity problems.     

Removal of Tannic Acid Stabilizes CuO Nanoparticles from Aqueous Media by PAFC: Effect of Process Conditions and Water Chemistry

The increased utilization of CuO nanoparticles (CuO NPs) in various fields has raised concerns about their discharge into water containing a wide range of organic ligands. Moreover, the adsorption of these ligands can stabilize the CuO NPs in drinking water treatment plants. Thus, their removal from potable water is important to mitigate the risk to humans. The present study explored the efficacy of the coagulation–sedimentation (C/S) process for the removal of tannic acid (TA)-stabilized CuO NPs using polyaluminum ferric chloride (PAFC) as a coagulant. Moreover, the influence of process conditions (stirring speed) and water chemistry (i.e., pH and ionic strength (IS)) were also investigated to determine their impact on removal. The results showed that stirring speed in the reaction phase significantly affected the removal due to increased flocculation compared with stirring speed in the mixing phase. In addition, pH and IS affect the colloidal stability and removal efficiency of CuO NPs. A relatively better removal performance (<99%) of CuO NPs was found at lower coagulant dosage in the pH range 6–8. The addition of organic ligands reversed the surface charge potential and enhanced the colloidal stability of CuO NPs, resulting in the destabilization of TA-CuO NPs, thereby reducing the optimum PAFC dosage for removal. By contrast, the IS above the critical coagulation concentration decreased the removal efficiency due to inhibition of the ionic activity of PAFC hydrolysate in the aqueous environment. Fourier transform infrared findings of TA-CuO NPs composite flocs suggest that the primary removal mechanism might be mediated via the combined effect of neutralization, complexation as well as adsorption.     

Conversion of municipal solid waste into carboxylic acids by anaerobic countercurrent fermentation: effect of using intermediate lime treatment

Municipal solid waste (MSW) and sewage sludge (SS) were combined and anaerobically converted into carboxylate salts by using a mixed culture of acid-forming microorganisms. MSW is an energy source and SS is a source of nutrients. In this study, MSW and SS were combined, so they complemented each other. Four fermentors were arranged in series for a countercurrent fermentation process. In this process, the solids and liquid were transferred in opposite directions, with the addition of fresh biomass to fermentor 1 and fresh liquid media to fermentor 4. An intermediate lime treatment of solids exiting fermentor 3 before entering fermentor 4 was applied to improve the product acid concentration from the untreated MSW/SS fermentations. All fermentations were performed under anaerobic conditions at 40 degrees C. Calcium carbonate was added to neutralize the carboxylic acids and to control the pH. Iodoform was used as a methanogen inhibitor. Carboxylic acid concentration and gas composition were determined by gas chromatography. Substrate conversion was measured by volatile solids loss, and carboxylic acid productivity was calculated as the function of the total carboxylic acids produced, the amount of liquid in all fermentors, and time. The addition of intermediate lime treatment increased product concentration and conversion by approx 30 and 15%, respectively. The highest carboxylic acid concentrations for untreated MSW/SS fermentations with and without intermediate lime treatment were 22.2 and 17.7 g of carboxylic acid/L of liquid, respectively. These results confirm that adding a treatment step between fermentor 3 and fermentor 4 will increase the digestibility and acid productivity of the fermentation.     

Conversion of municipal solid waste into carboxylic acids by anaerobic countercurrent fermentation

Municipal solid waste (MSW) and sewage sludge (SS) were combined and anaerobically converted into carboxylate salts by using a mixed culture of acid-forming microorganisms. MSW is an energy source and SS is a source of nutrients. In this study, MSW and SS were combined, so they complemented each other. Four fermentors were arranged in series for a countercurrent fermentation process. In this process, the solids and liquid were transferred in opposite directions, with the addition of fresh biomass to fermentor 1 and fresh liquid media to fermentor 4. An intermediate lime treatment of solids exiting fermentor 3 before entering fermentor 4 was applied to improve the product acid concentration from the untreated MSW/SS fermentations. All fermentations were performed under anaerobic conditions at 40°C. Calcium carbonate was added to neutralize the carboxylic acids and to control the pH. Iodoform was used as a methanogen inhibitor. Carboxylic acid concentration and gas composition were determined by gas chromatography. Substrate conversion was measured by volatile solids loss, and carboxylic acid productivity was calculated as the function of the total carboxylic acids produced, the amount of liquid in all fermentors, and time. The addition of intermediate lime treatment increased product concentration and conversion by approx 30 and 15%, respectively. The highest carboxylic acid concentrations for untreated MSW/SS fermentations with and without intermediate lime treatment were 22.2 and 17.7 g of carboxylic acid/L of liquid, respectively. These results confirm that adding a treatment step between fermentor 3 and fermentor 4 will increase the digestibility and acid productivity of the fermentation.     

Two-step upflow anaerobic sludge bed system for sewage treatment under subtropical conditions with posttreatment in waste stabilization ponds

A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions.