Application of Fenton oxidation to cosmetic wastewaters treatment

The removal of organic matter (TOC and COD) from a cosmetic wastewater by Fenton oxidation treatment has been evaluated. The operating conditions (temperature as well as ferrous ion and hydrogen peroxide dosage) have been optimized. Working at an initial pH equal to 3.0, a Fe(2+) concentration of 200 mg/L and a H(2)O(2) concentration to COD initial weight ratio corresponding to the theoretical stoichiometric value (2.12), a TOC conversion higher than 45% at 25 degrees C and 60% at 50 degrees C was achieved. Application of the Fenton oxidation process allows to reach the COD regional limit for industrial wastewaters discharges to the municipal sewer system. A simple kinetic analysis based on TOC was carried out. A second-order equation describes well the overall kinetics of the process within a wide TOC conversion range covering up to the 80-90% of the maximum achievable conversion.     

Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater

The applicability of Fenton's oxidation to improve the biodegradability of a pharmaceutical wastewater to be treated biologically was investigated. The wastewater was originated from a factory producing a variety of pharmaceutical chemicals. Treatability studies were conducted under laboratory conditions with all chemicals (having COD varying from 900 to 7000 mg/L) produced in the factory in order to determine the operational conditions to utilize in the full-scale treatment plant. Optimum pH was determined as 3.5 and 7.0 for the first (oxidation) and second stage (coagulation) of the Fenton process, respectively. For all chemicals, COD removal efficiency was highest when the molar ratio of H(2)O(2)/Fe(2+) was 150-250. At H(2)O(2)/Fe(2+) ratio of 155, 0.3M H(2)O(2) and 0.002 M Fe(2+), provided 45-65% COD removal. The wastewater treatment plant that employs Fenton oxidation followed by aerobic degradation in sequencing batch reactors (SBR), built after these treatability studies provided an overall COD removal efficiency of 98%, and compliance with the discharge limits. The efficiency of the Fenton's oxidation was around 45-50% and the efficiency in the SBR system which has two reactors each having a volume of 8m(3) and operated with a total cycle time of 1 day, was around 98%, regarding the COD removal.     

Physical and oxidative removal of organics during Fenton treatment of mature municipal landfill leachate

Municipal landfill leachate, especially mature leachate, may disrupt the performance of moderately-sized municipal activated sludge wastewater treatment plants, and likewise tend to be recalcitrant to biological pretreatment. Recently, Fenton methods have been investigated for chemical treatment or pre-treatment of mature leachate. In this paper, the results of laboratory tests to determine the roles of oxidation and coagulation in reducing the organic content of mature leachate during Fenton treatment are presented. The efficiencies of chemical oxygen demand (COD) oxidation and coagulation were tested, and the ratio of COD removal by oxidation to that by coagulation was assessed, under various operating conditions. Low initial pH, appropriate relative and absolute Fenton reagent dosages, aeration, and stepwise addition of reagents increased COD removal by oxidation and the importance of oxidation relative to coagulation. Simultaneous aeration and stepwise reagent addition allowed comparable treatment without initial acidification pH, due to the generation of acidic organic intermediates and the continuous input of CO2. On the other hand, high COD oxidation efficiency and low ferrous dosage inhibited COD removal by coagulation. At significantly high oxidation efficiency, overall COD reduction decrease slightly due to low coagulation efficiency. Under the most favorable conditions (initial pH 3, molar ratio [H(2)O(2)]/[Fe2+]=3, [H2O2]=240 mM, and six dosing steps), 61% of the initial COD was removed, and the ratio of COD removal oxidation to coagulation was 0.75. Results highlighted the synergistic roles of oxidation and coagulation in Fenton treatment of mature leachate, and the role of oxidation in controlling the efficiency of removal of COD by coagulation.     

Use of Fenton reaction for the treatment of leachate from composting of different wastes

The oxidation of leachate coming from the composting of two organic wastes (wastewater sludge and organic fraction of municipal solid wastes) using the Fenton's reagent was studied using different ratios [Fe(2+)]/[COD](0) and maintaining a ratio [H(2)O(2)]/[COD](0) equal to 1. The optimal conditions for Fenton reaction were found at a ratio [Fe(2+)]/[COD](0) equal to 0.1. Both leachates were significantly oxidized under these conditions in terms of COD removal (77 and 75% for leachate from wastewater sludge composting and leachate from organic fraction of municipal solid wastes, respectively) and BOD(5) removal (90 and 98% for leachate from wastewater sludge composting and leachate from organic fraction of municipal solid wastes, respectively). Fenton's reagent was found to oxidize preferably biodegradable organic matter of leachate. In consequence, a decrease in the biodegradability of leachates was observed after Fenton treatment for both leachates. Nevertheless, Fenton reaction proved to be a feasible technique for the oxidation of the leachate under study, and it can be considered a suitable treatment for this type of wastewaters.     

Combined electrocoagulation and TiO(2) photoassisted treatment applied to wastewater effluents from pharmaceutical and cosmetic industries

The treated wastewater consists of refractory materials and high organic content of hydrolyzed peptone residues from pharmaceutical factory. The combination of electrocoagulation (EC) followed by heterogeneous photocatalysis (TiO(2)) conditions was maximized. The EC: iron cathode/anode (12.50 cmx2.50 cmx0.10 cm), current density 763Am(-2), 90min and initial pH 6.0. As EC consequence, the majority of the dissolved organic and suspended material was removed (about 91% and 86% of the turbidity and chemical oxygen demand (COD), respectively). After EC, refractory residues still remained in the effluent. The subsequent photocatalysis: UV/TiO(2)/H(2)O(2) (mercury lamps), pH 3.0, 4h irradiation, 0.25gL(-1) TiO(2) and 10mmolL(-1) H(2)O(2) shows high levels of inorganic and organic compounds eliminations. The obtained COD values: 1753mgL(-1) for the sample from the factory, 160mgL(-1) after EC and 50mgL(-1) after EC/photocatalyzed effluents pointed out that the combined treatment stresses this water purification.     

Decolorization of an azo dye Orange G in aqueous solution by Fenton oxidation process: effect of system parameters and kinetic study

To establish cost-efficient operating conditions for potential application of Fenton oxidation process to treat wastewater containing an azo dye Orange G (OG), some important operating parameters such as pH value of solutions, dosages of H(2)O(2) and Fe(2+), temperature, presence/absence of chloride ion and concentration of the dye, which effect on the decolorization of OG in aqueous solution by Fenton oxidation have been investigated systematically. In addition, the decolorization kinetics of OG was also elucidated based on the experimental data. The results showed that a suitable decolorization condition was selected as initial pH 4.0, H(2)O(2) dosage 1.0 x 10(-2)M and molar ratio of [H(2)O(2)]/[Fe(2+)] 286:1. The decolorization of OG enhanced with the increasing of reaction temperature but decreased as a presence of chloride ion. On the given conditions, for 2.21 x 10(-5) to 1.11 x 10(-4)M of OG, the decolorization efficiencies within 60 min were more than 94.6%. The decolorization kinetics of OG by Fenton oxidation process followed the second-order reaction kinetics, and the apparent activation energy E, was detected to be 34.84 kJ mol(-1). The results can provide fundamental knowledge for the treatment of wastewater containing OG and/or other azo dyes by Fenton oxidation process.     

Aluminium sulfate as coagulant for highly polluted cork processing wastewater: Evaluation of settleability parameters and design of a clarifier-thickener unit

This is the second part of a master project on the chemistry of aluminium as coagulant in the treatment of highly polluted cork-process-wastewater. The main aim of this second part was to determine the influence of the operating conditions on the system's settleability parameters. It is well known that it is just as important to achieve good settleability parameters in the physico-chemical treatment of wastewaters as it is to attain a high level of decontamination. These parameters will determine the dimensions of the required equipment, and hence the costs of the installation. This part of the study therefore analyzes the influence of the different operating variables on the following settleability parameters: sediment volumetric percentage, settling velocity, sludge volume index and total suspended solids just after mixture with the coagulant. The ranges used for the experimental variables were: coagulant dose (83-166 mgL(-1) of Al(3+)), coagulation mixing time (5-30 min), stirring rate (60-300 rpm), contamination level of the wastewater (Wastewater II COD approximately 2000 mg O(2) L(-1), Wastewater III COD approximately 3000 mg O(2) L(-1)), and pH (5-11). The optimal conditions found for the settling process were not the same as those that had been determined for the organic matter removal. In this case the optimal conditions were: coagulation mixing time (30 min), stirring rate (60 rpm), coagulant dose (83 mgL(-1) of Al(3+)) and pH (7-9). Finally, the Talmadge-Fitch method is used to apply the results to the design of a clarifier-thickener unit to treat 2m(3)h(-1) of wastewater. The required minimum area of the unit would be 4.11 m(2).     

Integrated treatment scheme for rubber thread wastewater: sulfide precipitation and biological processes

In this study, acidic latex wastewater containing high average zinc and acetic contents of 816mgL(-1) and 20,862mgCODL(-1), respectively, was treated successfully by a series of chemical and biological processes without any addition of acid or base for pH adjustment. Total dissolved solids of the treated effluent increased by only 1.1-fold on average for sulfide precipitation as compared to 2.8-fold for the hydroxide strategy. The oxidation-reduction potential (ORP) value of 0mV was used successfully as an indicator for optimum sulfide addition which consistently provided an appreciable reduction in effluent concentrations to less than 1 and 2mgL(-1) for zinc and residual sulfide, respectively. The anaerobic filter was very stable in handling the chemically treated wastewater up to the organic loading rate of 11.8gCODL(-1)day(-1) with an average efficiency of 92%. Methane production and biomass yield were 0.32L(gCOD(removed))(-1) and 0.014gVSS (gCOD(removed))(-1), respectively. For the activated sludge process, the optimum sludge age and hydraulic retention time were 30 and 0.8 days, respectively, which are equivalent to the organic loading rates of 2.50gCODL(-1)day(-1) or 2.13gBODL(-1)day(-1). Under these optimum conditions, average removal efficiencies for COD and BOD were 96.6 and 99.4%. Average soluble COD, BOD and suspended solids in the effluent were 71, 11 and 38mgL(-1), respectively. This integrated treatment scheme was proven to be an effective approach for highly polluted and toxic rubber thread wastewater.     

Alkydic resin wastewaters treatment by fenton and photo-Fenton processes

Advanced oxidation processes are an emerging option to treatment of the painting industry effluents. The aim of this study was to compare the effectiveness of the Fenton and photo-Fenton processes in chemical oxygen demand (COD), total organic carbon (TOC) and phenolic compounds removal from wastewaters generated during alkydic resins manufacture. The optimized treatment conditions are the following: pH 3.0, 15.15x10(-3)molL(-1) FeSO(4) and 0.30molL(-1) H(2)O(2) for a reaction time of 6h. photo-Fenton experiments were carried out in the presence of sunlight or artificial radiation and complementary additions of H(2)O(2) were made for all experiments. The best results were obtained with photo-Fenton process assisted with solar radiation, with reductions of 99.5 and 99.1% of COD and TOC levels, respectively. Fenton and photo-Fenton (with artificial irradiation) processes presented lower but not insignificant removals, within 60-80% reduction for both COD and TOC. In addition, an excellent removal (95%) of total phenols was obtained using photo-Fenton process assisted with artificial irradiation. This study demonstrated that the use of photo-Fenton process on alkydic resins wastewater treatment is very promising especially when solar light is used.     

Aluminium sulfate as coagulant for highly polluted cork processing wastewaters: removal of organic matter

This is the first part of a work on the chemistry of aluminium as coagulant in the treatment of highly polluted cork processing wastewater. The main aim of this first part was to determine the removal of organic matter - measured by reductions in chemical oxygen demand (COD), polyphenols (TP), and aromatic compounds (A) - that can be obtained using this physicochemical process. To this end, jar-test experiments were carried out to determine the optimal conditions for the process, in particular, the effective aluminium dosage, contamination level of wastewater, coagulant mixing time, stirring speed, and pH. The ranges of tested parameters for the coagulation process were: coagulant dose (33-166 mgL(-1) of Al(3+)), contamination of the wastewater (COD between 1060 and 3050 mgO(2)L(-1)), mixing time (5-30 min), stirring speed (60-300 rpm) and pH (4-11). The resulting removal capacities were in the ranges of 20-55% for COD, 28-89% for polyphenols, and 29-90% for aromatic compounds. The best results were obtained with a coagulant mixing time of 5 min and a stirring speed of 300 rpm. The optimal choices of pH and coagulant dose fundamentally depended on the contamination level of wastewater.     

Physicochemical treatments of anionic surfactants wastewater: Effect on aerobic biodegradability

The effect of different physicochemical treatments on the aerobic biodegradability of an industrial wastewater resulting from a cosmetic industry has been investigated. This industrial wastewater contains 11423 and 3148mgL(-1) of chemical oxygen demand (COD) and anionic surfactants, respectively. The concentration of COD and anionic surfactants were followed throughout the diverse physicochemical treatments and biodegradation experiments. Different pretreatments of this industrial wastewater using chemical flocculation process with lime and aluminium sulphate (alum), and also advanced oxidation process (electro-coagulation (Fe and Al) and electro-Fenton) led to important COD and anionic surfactants removals. The best results were obtained using electro-Fenton process, exceeding 98 and 80% of anionic surfactants and COD removals, respectively. The biological treatment by an isolated strain Citrobacter braakii of the surfactant wastewater, as well as the pretreated wastewater by the various physicochemical processes used in this study showed that the best results were obtained with electro-Fenton pretreated wastewater. The characterization of the treated surfactant wastewater by the integrated process (electro-coagulation or electro-Fenton)-biological showed that it respects Tunisian discharge standards.     

Treatment of pesticide wastewater by moving-bed biofilm reactor combined with Fenton-coagulation pretreatment

In order to treat pesticide wastewater having high chemical oxygen demand (COD) value and poor biodegradability, Fenton-coagulation process was first used to reduce COD and improve biodegradability and then was followed by biological treatment. Optimal experimental conditions for the Fenton process were determined to be Fe(2+) concentration of 40 mmol/L and H(2)O(2) dose of 97 mmol/L at initial pH 3. The interaction mechanism of organophosphorous pesticide and hydroxyl radicals was suggested to be the breakage of the P=S double bond and formation of sulfate ions and various organic intermediates, followed by formation of phosphate and consequent oxidation of intermediates. For the subsequent biological treatment, 3.2g/L Ca(OH)(2) was added to adjust the pH and further coagulate the pollutants. The COD value could be evidently decreased from 33,700 to 9300 mg/L and the ratio of biological oxygen demand (BOD(5)) to COD of the wastewater was enhanced to over 0.47 by Fenton oxidation and coagulation. The pre-treated wastewater was then subjected to biological oxidation by using moving-bed biofilm reactor (MBBR) inside which tube chip type bio-carriers were fluidized upon air bubbling. Higher than 85% of COD removal efficiency could be achieved when the bio-carrier volume fraction was kept more than 20% by feeding the pretreated wastewater containing 3000 mg/L of inlet COD at one day of hydraulic retention time (HRT), but a noticeable decrease in the COD removal efficiency when the carrier volume was decreased down to 10%, only 72% was observed. With the improvement of biodegradability by using Fenton pretreatment, also due to the high concentration of biomass and high biofilm activity using the fluidizing bio-carriers, high removal efficiency and stable operation could be achieved in the biological process even at a high COD loading of 37.5 gCOD/(m(2)carrierday).     

Treatment of water-based printing ink wastewater by Fenton process combined with coagulation

Attempts were made in this study to examine the efficiency of Fenton process combined with coagulation for treatment of water-based printing ink wastewater. Parameters affecting the Fenton process, such as pH, dosages of Fenton reagents and the settling time, were determined by using jar test experiments. 86.4% of color and 92.4% of chemical oxygen demand (COD) could be removed at pH 4, 50mg/l H(2)O(2), 25mg/l FeSO(4) and 30min settling time. The coagulation using polyaluminium chloride (PAC) and ferrous sulfate (FeSO(4)) was beneficial to improve the Fenton process treated effluent in reducing the flocs settling time, enhancing color and COD removal. The overall color, COD and suspended solids (SS) removal reached 100%, 93.4% and 87.2% under selected conditions, respectively. Thus this study might offer an effective way for wastewater treatment of water-based ink manufacturer and printing corporation.     

Treatment of landfill leachate by Fenton's reagent in a continuous stirred tank reactor

The treatment of landfill leachate by Fenton process was carried out in a continuous stirred tank reactor (CSTR). The effect of operating conditions such as reaction time, hydraulic retention time, pH, H(2)O(2) to Fe(II) molar ratio, Fenton's reagent dosage, initial COD strength, and temperature on the efficacy of Fenton process was investigated. It is demonstrated that Fenton's reagent can effectively degrade leachate organics. Fenton process reached the steady state after three times of hydraulic retention. The oxidation of organic materials in the leachate was pH dependent and the optimal pH was 2.5. The favorable H(2)O(2) to Fe(II) molar ratio was 3, and organic removal increased as dosage increased at the favorable H(2)O(2) to Fe(II) molar ratio. Temperature gave a positive effect on organic removal.     

Combined physical,chemical and biological treatments of wastewater containing organics from a semiconductor plant

Wastewater containing organics from a semiconductor plant was experimentally investigated in this study. The wastewater is characterized by strong color, high chemical oxygen demand (COD), a large amount of refractory volatile organic compounds and low biodegradability. Because of these characteristics, treatment of this wastewater by traditional activated sludge method is essentially impossible. In the present work, combined physical, chemical and biological methods were synergistically utilized to tackle the wastewater. The combined treatment consisted of air stripping, modified Fenton oxidation and sequencing batch reactor (SBR) method. Air stripping was employed to remove the majority of volatile organic components (notably isopropyl alcohol) from the wastewater, while the Fenton treatment decomposed the remaining refractory organics leading to simultaneous reductions of wastewater COD and color. After proper dilution with other low-strength, organics-containing wastewater stream, the wastewater effluent was finally treated by the SBR method. Experimental tests were conducted to determine the effectiveness and the optimum operating conditions of each treatment process. Test results clearly demonstrated the advantages of the combined treatments. The treatment train was found capable of lowering the wastewater COD concentration from as high as 80,000 mg/l to below 100mg/l and completely eliminating the wastewater color. The overall water quality of the final effluent exceeded the direct discharge standard and the effluent can even be considered for reuse.     

Optimization of coagulation-flocculation process for pulp and paper mill effluent by response surface methodological analysis

Coagulation-flocculation is a proven technique for the treatment of high suspended solids wastewater. In this study, the central composite face-centered design (CCFD) and response surface methodology (RSM) have been applied to optimize two most important operating variables: coagulant dosage and pH, in the coagulation-flocculation process of pulp and paper mill wastewater treatment. The treated wastewater with high total suspended solids (TSS) removal, low SVI (sludge volume index) and high water recovery are the main objectives to be achieved through the coagulation-flocculation process. The effect of interactions between coagulant dosage and pH on the TSS removal and SVI are significant, whereas there is no interaction between coagulant dosage and water recovery. Quadratic models have been developed for the response variables, i.e. TSS removal, SVI and water recovery based on the high coefficient of determination (R(2)) value of >0.99 obtained from the analysis of variances (ANOVA). The optimum conditions for coagulant dosage and pH are 1045mgL(-1) and 6.75, respectively, where 99% of TSS removal, SVI of 37mLg(-1) and 82% of water recovery can be obtained.     

A comparative study of ultrasonic cavitation and Fenton's reagent for bisphenol A degradation in deionised and natural waters

Bisphenol A (BPA), a xenobiotic that exhibits endocrine disrupting action can be found in surface water. Its complete elimination can be obtained by advanced oxidation processes, notably upon the application of ultrasonic waves. In order to evaluate the feature of ultrasound relevance and the involvement of the hydroxyl radical in the BPA sonochemical degradation, ultrasound action was compared to Fenton's reaction in the cases of deionised acidic water (pH 3) and natural water (pH 7.6, main ions concentration: Ca(2+)=486mgL(-1), Na(+)=9.1mgL(-1), Cl(-)=10mg L(-1), SO(4)(2-)=1187mgL(-1), HCO(3)(-)=402mgL(-1)). Ultrasound was performed at 300kHz and 80W. Fenton's process was operated using ferrous sulphate (100micromolL(-1)) and continuous H(2)O(2) addition at the rate as it is produced when sonication is applied in water in absence of substrate. Experiments carried out in deionised water show that both processes exhibit identical BPA elimination rate and identical primary intermediates. Main chemical pathways involve reactions with OH radical. Chemical oxygen demand (COD) and total organic carbon (TOC) analyses show that the Fenton's process is slightly more efficient than ultrasonic treatment for the removal of BPA by-products in the case of deionised water. Experiments conducted in natural water evidenced the inhibition of the Fenton process while the ultrasound action was not hampered.     

Treatment of jean-wash wastewater by combined coagulation, hydrolysis/acidification and Fenton oxidation

Performance of a full-scale combined treatment plant for jean-wash wastewater (JWW) was investigated. The combined process consisted of chemical coagulation, hydrolysis/acidification and Fenton oxidation. Chemical coagulation treatment with polymeric ferric sulfate (PFS)/lime alone proved to be effective in removing the COD (>70%) and part of the color (>50%) from the JWW. Fenton oxidation combined with hydrolysis/acidification as pretreatment offered a noticeable BOD removal efficiency. The average removal efficiencies for COD, BOD, SS, color and aromatic compounds of the combined process were about 95%, 94%, 97%, 95% and 90%, respectively, with the average effluent quality of COD 58 mg/L, BOD 19 mg/L, SS 4 mg/L and color 15(multiple), consistent with the national discharge limits for textile wastewater. The result indicated that the combined procedure could offer an attractive solution for JWW treatment with considerable synergistic advantages.     

Fenton's peroxidation and coagulation processes for the treatment of combined industrial and domestic wastewater

As a consequence of the population growth, major efforts have been made by the Egyptian government to construct new industrial areas. Tenth of Ramadan City is one of the most important industrial cities in Egypt. The wastewater generated from various industrial activities was highly contaminated with organic matters as indicated by COD (1750-3323 mg/L), TSS (900-3000 mg/L) and oil and grease (13.2-95.5 mg/L). All overall appraisals of the analytical data from the industrial wastewater indicate that pretreatment is required for all industrial sectors to achieve compliance with the Egyptian Environmental law which requires effective pretreatment of industrial wastewater prior to its discharge into public sewers. Treatability studies via conventional and Fenton processes have been investigated. The efficiency of conventional treatment methods led to 63% COD and 44% color removal by using FeCl(3) as coagulant. Various coagulant aids and powdered activated carbon (PAC) were added to 400mg/L FeCl(3) in order to enhance the removal of color. It was found that polyacrylamide polymer, bentonite and PAC increased the efficiency of the treatments where the color removal increased to 79%, by cationic polymer, 73% by anionic polymer, 84.5% by bentonite and 95% for 0.4 g/L PAC. Fenton process was investigated which under the operating conditions (pH 3.0+/-0.2, Fe(2+) dose=400 mg/L and H(2)O(2)=550 mg/L), color removal up to 100% and more than 90% of COD removal were achieved.     

A comparative study among different photochemical oxidation processes to enhance the biodegradability of paper mill wastewater

Advanced oxidation processes including UV, UV/H(2)O(2), Fenton reaction (Fe(II)/H(2)O(2)) and photo-Fenton process (Fe(II)/H(2)O(2)/UV) for the treatment of paper mill wastewater will be investigated. A comparison among these techniques is undertaken with respect to the decrease of chemical oxygen demand (COD) and total suspended solids (TSS) and the evolution of chloride ions. Optimum operating conditions for each process under study revealed the effect of the initial amounts of Fe(II) and hydrogen peroxide. Of the tested processes, photo-Fenton process was found to be the fastest one with respect to COD and TSS reduction of the wastewater within 45 min reaction time under low amounts of Fe(II) and hydrogen peroxide of 0.5 and 1.5mg/L, respectively, and amounted to 79.6% and 96.6% COD and TSS removal. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD(5)/COD, was low 0.21. When the effluent was submitted to the different types of AOPs used in this study, the biodegradability increases significantly. Within 45 min of reaction time, the photo-Fenton process appears as the most efficient process in the enhancement of the biodegradability of the organic matter in the effluent and the BOD(5)/COD ratio increased from 0.21 to 0.7.