Stabilization and dewatering of wastewater treatment plant sludge using combined bio/Fenton-like oxidation process

Wastewater sludge usually contains large amounts of water and organic materials; therefore, its stabilization and dewatering are of particular importance. The present study aimed to investigate the possibility of sludge stabilization and dewatering from wastewater sludge by bioleaching (Thiobacillus ferrooxidans), Fenton/bioleaching, and bioleaching/Fenton-like processes. To evaluate sludge stabilization and dewatering, specific resistance to filtration (SRF), volatile suspended solids (VSS), total suspended solids (TSS), and soluble chemical oxygen demand (SCOD) were measured. In biological treatment with T. ferrooxidans with Fe²⁺ (2?g?L^?1), 99.75, 33, 37, and 72% reduction were observed in SRF, VSS, TSS, SCOD, respectively, after 2 days. In the combined treatment of Fenton before bioleaching (including Fe²⁺ 2?g?L^?1 and H₂O₂ 1?g?L^?1 with Fenton oxidation for 30?min followed by biological treatment with T. ferrooxidans for 2 days), the reduction rates in TSS, VSS, SCOD, and SRF were 40.18, 40.88, 60.95, and 75.43%, respectively. In treatment with the combined method of bioleaching before Fenton-like oxidation, the removal rates of the aforementioned parameters were 52.5, 54.4, 88, and 99.82%, respectively. In comparison to Fenton oxidation and bioleaching alone, combined biological method of bioleaching/Fenton-like oxidation using a lower dose of H₂O₂ and Fe²⁺ significantly improved sludge dewatering and stabilization.     

Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water

Abstract

Some advanced oxidation processes (AOP's) such as Fenton H₂O₂/Fe²⁺, photo assisted Fenton UV/H₂O₂/Fe²⁺, UV photolysis, and photo assisted Fenton—like UV/O₂/Fe²⁺ have been tested for the degradation of Gemfibrozil in aqueous solution in a batch system and then in a membrane reactor. A nanofiltration/reverse osmosis type cross‐linked polyamide, UTC‐60 (Toray) membrane (19 cm²) was used. In the batch degradation tests, the gemfibrozil, used at 5 mg/L, was degraded by employing the four AOP's but numerous peaks of intermediates were observed at the HPLC. Indeed DOC analyses showed poor mineralization in the case of photolysis (3.1%) and UV/O₂/Fe (10%), while it was 62% using the photo assisted Fenton and 24% using the Fenton. Thus in the membrane reactor only the Fenton and the photo assisted Fenton were tested. Obtained results showed a drug degradation higher than 92%, a mineralization higher than 55%, and a membrane retention of the catalyst in solution higher than 95%.     

The sonochemical decolorisation of textile azo dye CI Reactive Orange 127

In the present study, Fenton and sono‐Fenton processes were applied to the oxidative decolorisation of synthetic textile wastewater including CI Reactive Orange 127 and polyvinyl alcohol. Process optimisation [pH, ferrous ion (Fe²⁺) and hydrogen peroxide (H₂O₂)], kinetic studies and their comparison were carried out for both of the processes. The sono‐Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35‐kHz frequency and 80 W power. The optimum conditions were determined as [Fe²⁺] = 20 mg l^?1, [H₂O₂] = 15 mg l^?1 and pH = 3 for the Fenton process and [Fe²⁺] = 25 mg l^?1, [H₂O₂] = 5 mg l^?1 and pH = 3 for the sono‐Fenton process. The colour removals were 89.9% and 91.8% by the Fenton and sono‐Fenton processes, respectively. The highest decolorisation was achieved by the sono‐Fenton process because of the production of some oxidising agents as a result of sonication. Consequently, ultrasonic irradiation in the sono‐Fenton process slightly increased the colour removal to 91.8%, while decreasing the hydrogen peroxide dosage to one‐third of that of the Fenton process.     

Fenton‐ and Fenton‐Like AOPs for Wastewater Treatment: From Laboratory‐To‐Plant‐Scale Application

Abstract

Fenton‐and Fenton‐like AOPs systems have been utilized for the oxidative degradation of some chlorinated pollutants such as chloral hydrate or 1,1,1‐trichloroethane, and for the treatment of real industrial wastewaters. Both ferrous sulfate (FeSO₄ · 7 H₂O) and Mohr's salt (NH₄)₂Fe(SO₄)₂. 6 H₂O have been used as Fe²⁺ ion sources. With Mohr's salt (MS) the Fenton‐and Fenton‐like reaction has been successfully carried out under acidic (pH 3) and neutral (pH 7) reaction conditions. The new Fenton‐like system utilizes zero‐valent iron (Fe^o) instead of ferrous sulfate has been applied for the 1,1,1‐trichloroethane and chloral hydrate degradation. Similarly, the application of catechol‐ and hydroquinone‐driven Fenton reaction for the degradation of chloral hydrate under acidic and neutral pH is a new Fenton‐like AOPs approach. The photo‐Fenton‐like reactions such as Fe³⁺/hν, Fe²⁺/H₂O₂/hν, and ferrioxalate system have been also studied for the degradation of chloral hydrate. As an irradiation source a daily light or sun light have been used. In comparison with photoreactor experiments the best system was observed to be Fe³⁺/hν. In some experiments the influence of standing time prolongation after Fenton reaction on the final degradation efficiency due to hydrolysis of intermediates such as phosgene (CCl₂?O) has also been studied. The Fenton reaction was successfully utilized for the treatment of real industrial wastewaters, in two cases even in plant‐scale applications.     

Comparison of a new immobilized Fe3+ catalyst with homogeneous Fe3+–H2O2 system for degradation of 2,4‐dinitrophenol

BACKGROUND: Heterogeneous Fenton catalysts have been used to treat various organic pollutants in an aqueous environment. The present study has investigated the degradation of 2,4‐dinitrophenol (2,4‐DNP), a priority pollutant generated by such industries as pharmaceuticals, pesticides, pigments and dyes. Degradation of 2,4‐DNP (100 mg L^?1) was studied using Fe³⁺ loaded on Al₂O₃ as a heterogeneous catalyst in the presence of H₂O₂, and the efficiency compared with the homogeneous Fe³⁺/H₂O₂ based Fenton‐like process. The effect of different parameters for both processes, such as catalyst loading, H₂O₂ concentration, initial solution pH, initial substrate concentration and temperature were investigated and the optimum operating conditions determined. RESULTS: Under optimal operating conditions of the homogeneous system ([Fe³⁺] 125 mg L^?1; [H₂O₂] 250 mg L^?1; pH 3; room temperature), 92.5% degradation was achieved in 35 min for an initial 2,4‐DNP concentration of 100 mg L^?1. In the case of immobilized Fe (Fe³⁺–Al₂O₃ catalyst), degradation improved to 98.7% under the condition 10 wt% [Fe³⁺–Al₂O₃] 1 g L^?1 catalyst loading; [H₂O₂] 250 mg L^?1; pH 3; at room temperature for the same duration. CONCLUSIONS: This study demonstrated the stability and reusability of the prepared heterogeneous catalyst. This process is a viable technique for treatment of aqueous solutions containing contaminants. Copyright © 2012 Society of Chemical Industry     

Removal of organic contaminants in paper pulp effluents by AOPs: an economic study

The degradation of the organic content of a bleaching Kraft mill effluent was carried out using Advanced Oxidation Processes (AOPs). The study was focused on the identification of the AOP, or combination of AOPs, that showed the highest efficiency together with the lowest cost. Direct UV photolysis (UV), TiO₂ assisted‐photocatalysis (TiO₂/UV), Fenton, Fenton‐like, and photo‐Fenton reactions (Fe(II)/H₂O/UV), UV‐assisted ozonation (O₃/UV) and addition of Fe²⁺ and/or H₂O₂ to the TiO₂/UV and the O₃/UV systems, were used for the degradation of a conventional cellulose bleaching effluent. The effluent was characterized by the general parameters TOC, COD and color, and analyzed for chlorinated low molecular weight compounds using GC–MS. The costs of the systems per unit of TOC reduction were compared. Fenton, Fenton‐like and photo‐Fenton reactions achieved better levels of TOC degradation than photocatalysis and with lower cost's than photocatalytic treatments. Ozonation is an effective but rather expensive process. The use of UVA light, however, increased the effectiveness of ozonation with a significant decrease (>25%) in the operational cost. © 2002 Society of Chemical Industry     

Ultrasonic pre‐treatment of biological sludge: consequences for disintegration,anaerobic biodegradability,and filterability

BACKGROUND: Disintegration was developed as a pretreatment process for sludge to accelerate the digestion processes. Ultrasonic treatment may be a good alternative for sludge disintegration. In this study, different specific energy inputs ranged between 0 and 15 880 kJ kg^?1 and very low ultrasonic densities ranged between 0.04 and 0.1 W mL^?1 were applied to biological sludge for disintegration purposes. The potential for improving anaerobic digestion through ultrasonic pre‐treatment and the effect of ultrasonic pre‐treatment on the filterability characteristics of sludge were also investigated. RESULTS: 9690 kJ kg^?1 TS of supplied energy and very low power density of 0.09 Wm L^?1 are efficient for floc disintegration. For 9690 kJ kg^?1 TS, 44% higher methane production was achieved than with raw sludge as a result of biochemical methane potential assay. The supernatant characteristics of the sludge were also affected by the ultrasonic pre‐treatment. For 9690 kJ kg^?1 TS, the soluble chemical oxygen demand (SCOD), dissolved organic carbon (DOC), total nitrogen (TN), and total phosphorus (TP) in the sludge supernatant increased by 340%, 860%, 716%, and 207.5%, respectively. CONCLUSION: Ultrasonic pre‐treatment is an effective method for biological sludge disintegration even at very low ultrasonic density levels. It leads to increased anaerobic biodegradability but deteriorates the filterability characteristics of biological sludge. Copyright © 2009 Society of Chemical Industry     

Mineralisation of the antibiotic amoxicillin in pure and surface waters by artificial UVA‐ and sunlight‐induced Fenton oxidation

BACKGROUND: The degradation and mineralisation of the antibiotic amoxicillin by photo‐Fenton reactions, mediated by artificial UVA or solar irradiation, were investigated. Experiments were conducted with 30 mg L^?1 amoxicillin solutions prepared with deionised or surface water at Fe²⁺ and H₂O₂ concentrations in the range 0.0179–0.0895 and 1–10 mmol L^?1, respectively. Black‐light irradiation at 365 nm was provided by a 13 W m^?2 lamp, while samples were exposed to sunlight at 20 W m^?2 for solar experiments. RESULTS: In all cases, quantitative amoxicillin degradation occurred within 5 min and this was accompanied by lower mineralisation rates. Mineralisation followed first‐order kinetics with respect to organic carbon content and it was not affected by the water matrix with either type of illumination. Solar‐induced reactions were only marginally faster than artificial irradiation. Increasing the H₂O₂ to Fe²⁺ concentration ratio increases the extent of mineralisation up to a point beyond which degradation is impeded due to radical scavenging associated with the high concentrations of the Fenton reagents. CONCLUSION: Amoxicillin is readily degradable by homogeneous photocatalysis, being converted to more stable intermediates as indicated by lower mineralisation rates. The process can be driven by solar irradiation, thus providing a sustainable treatment technology. Copyright © 2009 Society of Chemical Industry     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 2: Photo‐assisted Fenton oxidation

Oxidation of p‐hydroxybenzoic acid in aqueous solution by the photo‐assisted Fenton reaction (Fe²⁺ + H₂O₂ + UV) has been studied. The effects of ferrous ion concentration (0.05, 0.14 and 0.29 mmol dm^?3), temperature (10, 20, 30 and 40 °C), and initial hydrogen peroxide concentration (0.7, 1.4, 2.2 and 2.9 mmol dm^?3) on the p‐hydroxybenzoic acid conversion were established. Experimental results indicate that the kinetics of this oxidation process fits pseudo‐first‐order kinetics well. The overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ferrous ion concentration, temperature and initial hydrogen peroxide concentration was evaluated. A semi‐empirical expression is proposed for the overall reaction rate which takes into account both oxidation pathways and is a function of operating variables. © 2001 Society of Chemical Industry     

FENTON AND FENTON-LIKE AOPs FOR ALUM SLUDGE CONDITIONING: EFFECTIVENESS COMPARISON WITH DIFFERENT Fe2+ AND Fe3+ SALTS

Currently, organic polymers are adopted in alum sludge (aluminum-coagulated drinking water treatment sludge) conditioning. However, there are important concerns regarding the use of these polymers because of the unknown and long-term effects of the potential release of excess polymer to the surrounding environment when the sludge is landfilled. Therefore, as an initial action, this study aimed at investigating alternative chemical conditioning methods and focused mainly on exploiting Fenton (Fe²⁺/H₂O₂) and Fenton-like (Fe³⁺/H₂O₂) reagents as the conditioner. Experiments have been conducted to test the effectiveness of Fenton's reagent (containing the ferrous salts of chloride, sulfate, or oxalate), Fenton-like reagent (containing ferric salts of chloride and sulfate), and the coagulation method using FeCl₃ for alum sludge conditioning at constant hydrogen peroxide and iron salt concentrations of 125 and 20 mg/g DS (dry solids), respectively. The effectiveness on dewaterability of the alum sludge demonstrated that the maximum reduction (%) of SRF (specific resistance to filtration) and CST (capillary suction time) of 74% and 47%, respectively, can be obtained when Fenton's reagent was adopted for sludge conditioning. Such reduction of 64% for SRF and 38% for CST can be achieved when Fenton-like reagents were applied.     

Performance and Economic Assessment of the Treatment of Phenol with TiO2 Photocatalysis,Photo‐Fenton,Biological Aerated Filter,and Wetland Reactors

The performance and economic cost of the removal of phenol with TiO₂ photocatalysis, photo‐Fenton reactions, biological aerated filter (BAF), and constructed wetland (CW) reactors has been studied. The BAF achieved complete removal with a maximum phenol concentration of 200 mg·L^?1. The BAF‐CW combination provided a phenol‐free effluent with a maximum phenol concentration of 650 mg·L^?1. In both cases, a complete detoxification of the treated water was achieved at the concentrations studied. The efficiency of TiO₂ photocatalysis was limited to concentrations below 50 mg L^?1 to minimize removal reduction and toxicity of the intermediates. Photo‐Fenton was more efficient, but also more expensive because of the high cost of H₂O₂. The photo‐Fenton‐BAF combination is proposed to be the most suitable one.     

Control of the Fenton process for textile wastewater treatment using artificial neural networks

BACKGROUND: The Fenton process is a popular advanced oxidation process (AOP) for treating textile wastewater. However, high consumption of chemical reagents and high production of sludge are typical problems when using this process and in addition, textile wastewater has wide‐ranging characteristics. Therefore, dynamically regulating the Fenton process is critical to reducing operation costs and enhancing process performance. The artificial neural network (ANN) model has been adopted extensively to optimize wastewater treatment. This study presents a novel Fenton process control strategy using ANN models and oxygen reduction potential (ORP) monitoring to treat two synthetic textile wastewaters containing two common dyes. RESULTS: Experimental results indicated that the ANN models can predict precisely the colour and chemical oxygen demand (COD) removal efficiencies for synthetic textile wastewaters with correlation coefficients (R²) of 0.91–0.99. The proposed control strategy based on these ANN models effectively controls the Fenton process for various effluent colour targets. For treating the RB49 synthetic wastewater to meet the effluent colour targets of 550 and 1500 ADMI units, the required Fe⁺² doses were 13.0–84.3 and 5.5–34.6 mg L^?1 (Fe⁺²/H₂O₂ = 3.0), resulting in average effluent colour values of 520 and 1494 units. On the other hand, an effluent colour target of 550 ADMI units was achieved for RBB synthetic wastewater. The required Fe⁺² doses were 14.6–128.0 mg L^?1; the average effluent colour values were 520 units. CONCLUSION: The Fenton process for textile wastewater treatment was effectively controlled using a control strategy applying the ANN models and ORP monitoring, giving the benefit of chemical cost savings. Copyright © 2009 Society of Chemical Industry     

Advanced Oxidative Removal of Nitric Oxide from Flue Gas by Homogeneous Photo‐Fenton in a Photochemical Reactor

In this work, advanced oxidation removal of nitric oxide (NO) from flue gas by homogeneous Photo‐Fenton was investigated in a photochemical reactor and the effects of several influencing factors on NO removal were evaluated. The gas‐liquid reaction products were determined. The reaction pathways of NO removal are also preliminarily discussed. It was found that with the increase of Fe²⁺ concentration, NO removal efficiency first increased and then decreased. Increasing H₂O₂ concentration and UV radiation intensity greatly increased NO removal efficiency, but the growth rates gradually became smaller. NO removal efficiency greatly reduced with the increase of gas flow and NO concentration, and only slightly decreased with the increase of solution temperature, but significantly increased with the increase of initial solution pH value. The main anion product in the liquid phase was NO₃^–. With respect to removal of NO using homogeneous Photo‐Fenton, ·OH oxidation was the main reaction pathway, and H₂O₂ oxidation was the secondary reaction pathway.     

The effect of Fe2+ state in electrical property variations of Sn‐doped hematite powders

The structural, electrical, and chemical properties of Sn‐doped Fe₂O₃ powders were investigated. Various quantities of Sn‐doped Fe₂O₃ powders were synthesized using solid‐state reactions. Rietveld analysis for the powders that were doped below 2% revealed a phase‐pure Sn‐doped Fe₂O₃ structure (i.e., identical to Fe₂O₃ structure). Alternatively, the analysis for the powders that were doped more than 3% exhibited secondary phase. The unit cell volume and electrical conductivity of the phase‐pure samples increased with an increase in the doping concentration. X‐ray photoelectron spectroscopy measurements showed an increased Fe²⁺ state with the increase in Sn doping concentration. Therefore, the improved electrical conductivity and unit cell volume with the increase in doping concentration of the phase‐pure powders might be related to the increased Fe²⁺ state.     

Removal of metsulfuron methyl by Fenton reagent

The removal of metsulfuron methyl (MeS)—a sulfonyl urea herbicide from contaminated water was investigated by advanced oxidation process (AOP) using Fenton method. The optimum dose of Fenton reagent (Fe²⁺/H₂O₂) was 10 mg/L Fe²⁺ and 60 mg/L H₂O₂ for an initial MeS concentration ([MeS]₀) range of 0–80 mg/L. The Fenton process was effective under pH 3. The degradation efficiency of MeS decreased by more than 70% at pH > 3 (pH 4.5 and 7). The initial Fe²⁺ concentration ([Fe²⁺]₀) in the Fenton reagent affected the degradation efficiency, rate and kinetics. The degradation of MeS at optimum dose of Fenton reagent was more than 95% for [MeS] ₀ of 0–40 mg/L and the degradation time was less than 30 min. The determination of residual MeS concentration after Fenton oxidation by UV spectrophotometry was affected by the interferences from Fenton reagent. The estimation of residual MeS concentration after Fenton oxidation by high pressure/performance liquid chromatograph (HPLC) was interference free and represented the actual concentration of MeS and does not include the by-products of Fenton oxidation. The degradation kinetics of MeS was modelled by second order reactions involving 8 rate constants. The two reaction constants directly involving MeS were fitted using the experimental data and the remaining constants were selected from previously reported values. The model fit for MeS and the subsequent prediction of H₂O₂ were found to be within experimental error tolerances.     

Phase Transformation of Iron Oxide Nanoparticles by Varying the Molar Ratio of Fe2+:Fe3+

Co‐precipitation from a solution of ferrous/ferric mixed salt with the ratio of Fe²⁺:Fe³⁺ = 1:2 in air atmosphere is not a reliable method to synthesize magnetite (Fe₃O₄) nanoparticles because of the fact that Fe²⁺ oxidizes to Fe³⁺ and the molar ratio of Fe²⁺:Fe³⁺ changes. Therefore, the phase composition changes from magnetite to maghemite (γ‐Fe₂O₃). The influence of the initial molar ratio of Fe²⁺:Fe³⁺ on the phase composition of nanoparticles, their crystallinity and magnetic properties was studied. Experimental data from XRD, FTIR, SEM, and VSM reveal that the appropriate method to synthesize magnetite nanoparticles is reverse precipitation from only ferrous salt. It is found that by decreasing the synthesis temperature and by increasing the concentration of alkaline solution and the ratio of Fe²⁺:Fe³⁺ the crystallinity and the specific saturation magnetization (σ_s) are increased.     

Tetrachloroethylene and hexachloroethane degradation in Fe(III) and Fe(III)–citrate catalyzed Fenton systems

BACKGROUND: Tetrachloroethylene (PCE) and hexachloroethane (HCA) degradation, individually and in mixture, is investigated by Fe(III) or Fe(III)‐citrate initiated Fenton reaction under a range of hydrogen peroxide (H₂O₂) concentrations to illustrate the applicability and constraints of Fenton chemistry in degrading contaminants in polluted groundwater. RESULTS: In individual solutions Fe(III) rapidly degraded PCE for all H₂O₂ concentrations, but HCA at ≥ 0.2 mol L^?1 H₂O₂; the apparent PCE degradation rate initially increased but then decreased with increasing H₂O₂, while the HCA degradation rate was either unaffected or increased. With Fe(III)‐citrate PCE degradation was lower and no HCA degradation occurred. PCE degradation was lower in PCE‐HCA mixture, but the trend with H₂O₂ concentration was similar to the individual chemical; for HCA the residual was smaller for higher H₂O₂ concentration, but the apparent degradation rate constant was unaffected. CONCLUSION: Fe(III) catalyzed reactions can potentially degrade chemicals through reductive as well as oxidative transformations. Degradation of chemicals in mixtures occurs at a slower rate due to competition for radical moieties. The Fe(III)‐citrate complex further slowed chemical transformation. This study expands on the use of different forms of iron to catalyze the Fenton reaction to degrade chemicals. Copyright © 2012 Society of Chemical Industry     

Effects of butyric acid stress on anaerobic sludge for hydrogen production from kitchen wastes

BACKGROUND: Anaerobic digestion is an alternative technology to achieve the dual benefits of hydrogen production and waste stabilization from kitchen wastes. In this work, the butyric acid stress on anaerobic sludge was investigated in order to improve the tolerance of sludge against organic acids, and to enhance hydrogen accumulation. RESULTS: The tolerance of butyric acid in anaerobic sludge increased with the stress concentration, however, it decreased at concentrations greater than of 4.0 g L^?1. The maximum hydrogen yield reached 63.72 mL g^?1 VS at 4.0 g L^?1 stress, representing an increase of 114% compared with the control group. The concentration of volatile solids (VS) of the sludge and SCOD increased steadily with time up to 20 h. At 4.0 g L^?1 butyric acid stress, the maximum activity of β‐glucosidase, BAA‐hydrolysing protease and dehydrogenase enzyme were 14912.1 µmol PNP g^?1 TS h^?1, 134.14 µmol NH₄‐N g^?1 TS h^?1 and 7316.42 µg TF g^?1 TS h^?1, which were 2.78, 1.90 and 2.01 times that of the control, respectively. CONCLUSIONS: The feasibility of butyric acid stress on anaerobic sludge to increase hydrogen production from kitchen wastes was demonstrated. Remarkably, 4.0 g L^?1 butyric acid stress was found to be favorable for improving the tolerance of butyric acid in sludge as well as hydrogen yield in the experiment. Copyright © 2010 Society of Chemical Industry     

亚甲基蓝光度法研究基于CaO2的Fenton反应条件

CaO₂作为原位Fenton 氧化修复中H₂O₂持续供源的作用逐渐受到关注。利用亚甲基蓝分光光度法评价了基于CaO₂的Fenton反应中催化剂种类、初始pH值、CaO₂用量、催化剂和CaO₂比例、磷酸缓冲溶液浓度对羟基自由基（HO·）产率的影响。结果表明,采用Fe²⁺作为催化剂,在pH值为4、CaO₂相似文献