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.     

Ruthenium catalysts supported on high-surface-area zirconia for the catalytic wet oxidation of N,N-dimethyl formamide

Three weight percent ruthenium catalysts were prepared by incipient-wet impregnation of two different zirconium oxides, and characterized by BET, XRD and TPR. Their activity was evaluated in the catalytic wet oxidation (CWO) of N,N-dimethyl formamide (DMF) in an autoclave reactor. Due to a better dispersion, Ru catalyst supported on a high-surface-area zirconia (Ru/ZrO(2)-A) possessed higher catalytic properties. Due to over-oxidation of Ru particles, the catalytic activity of the both catalysts decreased during successive tests. The effect of oxygen partial pressure and reaction temperature on the DMF reactivity in the CWO on Ru/ZrO(2)-A was also investigated. 98.6% of DMF conversion was obtained through hydrothermal decomposition within 300 min at conditions of 200 degrees C and 2.0 MPa of nitrogen pressure. At 240 degrees C and 2.0 MPa of oxygen pressure 98.3% of DMF conversion was obtained within 150 min.     

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.     

Catalytic wet air oxidation of phenol over CeO2-TiO2 catalyst in the batch reactor and the packed-bed reactor

CeO2-TiO2 catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO2-TiO2 mixed oxides show the higher activity than pure CeO2 and TiO2, and CeO2-TiO2 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO2-TiO2 1/1 catalyst at reaction temperature of 150 degrees C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO2-TiO2 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 degrees C, the air total pressure of 3.5 MPa, the phenol concentration of 1000 mg/L for 100 h continue reaction. Leaching of metal ions of CeO2-TiO2 1/1 particle catalyst is very low during the continuous reaction. CeO2-TiO2 1/1 catalyst exhibits the excellent activity and stability in the CWAO of phenol.     

Effect of hydraulic retention time on the biodegradation of complex phenolic mixture from simulated coal wastewater in hybrid UASB reactors

This study describes the feasibility of anaerobic treatment of complex phenolics mixture from a simulated synthetic coal wastewater using four identical 13.5L (effective volume) bench scale hybrid up-flow anaerobic sludge blanket (HUASB) (combining UASB+anaerobic filter) reactors at four different hydraulic retention times (HRT) under mesophilic (27+/-5 degrees C) conditions. Synthetic coal wastewater with an average chemical oxygen demand (COD) of 2240 mg/L and phenolics concentration of 752 mg/L was used as substrate. The phenolics contained phenol (490 mg/L); m-, o-, p-cresols (123.0, 58.6, 42 mg/L); 2,4-, 2,5-, 3,4- and 3,5-dimethyl phenols (6.3, 6.3, 4.4 and 21.3 mg/L) as major phenolic compounds. The study demonstrated that at optimum HRT, 24h, and phenolic loading rate of 0.75 g COD/(m(3)-d), the phenolics and COD removal efficiency of the reactors were 96% and 86%, respectively. Bio-kinetic models were applied to data obtained from experimental studies in hybrid UASB reactor. Grau second-order multi-component substrate removal model was best fitted to the hybrid UASB reactor. The second-order substrate removal rate constant (k(2(s))) was found as 1.72 h(-1) for the hybrid reactor treating complex phenolic mixture. Morphological examination of the sludge revealed rod-type Methanothrix-like, cells to be dominant on the surface.     

Combined Fenton oxidation and aerobic biological processes for treating a surfactant wastewater containing abundant sulfate

The present study is to investigate the treatment of a surfactant wastewater containing abundant sulfate by Fenton oxidation and aerobic biological processes. The operating conditions have been optimized. Working at an initial pH value of 8, a Fe2+ dosage of 600mgL(-1) and a H2O2 dosage of 120mgL(-1), the chemical oxidation demand (COD) and linear alkylbenzene sulfonate (LAS) were decreased from 1500 and 490mgL(-1) to 230 and 23mgL(-1) after 40min of Fenton oxidation, respectively. Advanced oxidation pretreatment using Fenton reagent was very effective at enhancing the biodegradability of this kind of wastewater. The wastewater was further treated by a bio-chemical treatment process based on an immobilized biomass reactor with a hydraulic detention time (HRT) of 20h after Fenton oxidation pretreatment under the optimal operating conditions. It was found that the COD and LAS of the final effluent were less than 100 and 5mgL(-1), corresponding to a removal efficiencies of over 94% and 99%, respectively.     

Magnetic and catalytic properties of Cu0.5Zn0.5Fe2O4 nanocrystallite powders

Cu0.5Zn0.5Fe2O4 nanocrystallite powders (average size 13 nm) were synthesized from Cu-Zn spent catalyst (fertilizers) industries and ferrous sulfate wastes formed during iron and steel making. Cu-Zn catalyst (22.4% Cu and 26.4% Zn) was chemically treated with sulfuric acid at temperature 80 degrees C for 1 hr for the complete dissolving of copper and zinc into sulfate solution, then the produced solution was mixed with stoichiometric ratio of ferrous sulfate and the mixture was chemically precipitated as hydroxides followed by hydrothermal processing. The parameters affecting the magnetic properties and crystallite size of the produced ferrites powder e.g., temperature, time, and pH were systemically studied. X-ray diffraction analysis was used in order to determine the average crystallite size and phase identifications of the produced powder. The magnetic properties were studied by vibrating sample magnetometry. The results showed that the average crystallite size of the powder decreased for the ferrites powder formed at 150 degrees C and then increased by increasing the temperature to 200 degrees C. Interestingly, the saturation magnetization (Bs), remanent magnetization (Br) and coercive force (Hc) were 25.03 emu/g, 0.71 emu/g, and 4.83 Oe, respectively at hydrothermal temperature 150 degrees C for 24 hr and changed to 16.38 emu/g, 0.3864 emu/g, and 5.2 Oe at 150 degrees C and 72 hr. The produced nanoferrite powders are used for studying the catalytic activity of CO conversion to CO2 at different temperatures, pH and times. The maximum conversion (82%) is obtained at temperature 150 degrees C for 24 hrs and pH 12.     

Decolourization and mineralization of commercial reactive dyes by using homogeneous and heterogeneous Fenton and UV/Fenton processes

The oxidative decolourization and mineralization of three reactive dyes in separately prepared aqueous solutions C.I. Reactive Yellow 3 (RY3), C.I. Reactive Blue 2 (RB2) and C.I. Reactive Violet 2 (RV2) by using homogeneous and heterogeneous Fenton and UV/Fenton processes have been investigated. The effects of H(2)O(2), Fe(2+) and Fe(0) concentrations, Fe(2+)/H(2)O(2) and Fe(0)/H(2)O(2) molar ratios at pH 3 and T=23+/-1 degrees C have been studied. Optimal operational conditions for the efficient degradation of all three dye solutions (100 mg L(-1)) were found to be Fe(2+)/H(2)O(2)=0.5mM/20mM and Fe(0)/H(2)O(2)=2mM/1mM. The experimental results showed that the homogeneous Fenton process employing UV irradiation was the most effective. By using this process, the high levels of mineralization (78-84%) and decolourization (95-100%) were achieved. Pseudo-first-order degradation rate constants were obtained from the batch experimental data.     

Optimization of Fenton process for the treatment of landfill leachate

The treatment of landfill leachate by Fenton process was carried out in a batch reactor. The effect of operating conditions such as reaction time, pH, H2O2 to Fe(II) molar ratio, Fenton's reagent dosage, initial COD strength, feeding mode, the type of polymer, and temperature on the efficacy of Fenton process was investigated. It is demonstrated that Fenton's reagent can effectively degrade leachate organics. Fenton process was so fast that it was complete in 30 min. The oxidation of organic materials in the leachate was pH dependent and the optimal pH was 2.5. The favorable H2O2 to Fe(II) molar ratio was 1.5, and organic removal increased as dosage increased at the favorable H2O2 to Fe(II) molar ratio. The efficacy of Fenton process was improved by adding Fenton's reagent in multiple steps than that in a single step. Furthermore, the stepwise addition of both hydrogen peroxide and ferrous iron was more effective than that of hydrogen peroxide only. Sludge settling characteristics were much improved with the addition of the proper polymer. Temperature gave a positive effect on organic removal.     

Catalytic wet peroxide oxidation of phenol solutions over CuO/CeO2 systems

Three 5% CuO/CeO(2) catalysts were synthesized by sol-gel, precipitation and combustion methods, followed by incipient wetness impregnation with copper nitrate. The samples were characterized by XRD, TPR, BET and tested for the catalytic wet peroxide oxidation of a phenol solution (5 g/L). The reaction took place in a batch reactor at atmospheric pressure, in a temperature range of 60-80°C, during 4h. Phenol conversion, H(2)O(2) consumption, pH and chemical oxygen demand were determined. The reaction temperature and the catalyst loading did improve the phenol and the H(2)O(2) conversions. The effect on the selectivity towards complete mineralization was less marked, with levels among 60-70%. Stepwise addition of H(2)O(2) was also tested.     

Anaerobic treatment of olive mill wastewater and piggery effluents fermented with Candida tropicalis

Olive mill wastewater (OMW) contains high concentrations of phenolic compounds that are inhibitory to many microorganisms making it difficult to treat biologically prior to discharge in waterways. The total mono-cyclic phenol reduction in OMW in this study was carried out by aerobic pre-treatment using the yeast Candida tropicalis in a 18 L batch reactor at 30 degrees C for 12 days followed by anaerobic co-digestion. A COD removal of 62% and a reduction in the total mono-cyclic phenol content by 51% of the mixture was achieved in the aerobic pre-treatment. Pig slurry was added as co-substrate to supplement the low nitrogen levels in the olive mill wastewater. Subsequent anaerobic treatment was carried out in a 20L fixed-bed reactor at 37 degrees C and HRT between 11 and 45 days. After a long start-up period, the OLR was increased from 1.25 to 5 kg COD m(-3)day(-1) during the last 30 days, resulting in subsequent increase in overall COD removal and biogas production, up to maximum values of 85% and 29 L(biogas)L(reactor)(-1)day(-1), respectively. Methane content of the biogas produced from the anaerobic digestion ranged between 65% and 74%.     

Decomposition of benzene in air streams by UV/TiO(2) process

Photocatalytic decomposition of gaseous benzene at room temperature was studied with a fixed-bed annular reactor using titania as the photocatalyst. The effects of humidity, UV light intensity and benzene concentration on the conversion and mineralization of benzene were presented. Experimental results can be adequately described by using the Langmuir-Hinshelwood (L-H) kinetic model. The concentration distribution of benzene in the annular reactors of various dimensions can be described by combining the reactor design equation with L-H kinetics. Deactivation of catalyst was observed and attributed to the adsorption of reaction intermediates on TiO2 surface. The deactivated TiO2 catalyst could be photochemically regenerated by ozone-purging in the presence of humidity.     

Decolorization of KN-R catalyzed by Fe-containing Y and ZSM-5 zeolites

Decolorization of an anthraquinone dye, Reactive Brilliant Blue KN-R by hydrogen peroxide was examined using Fe-containing Y and ZSM-5 zeolites as heterogeneous catalysts. Catalysts were prepared by ion-exchange and coprecipitation methods, and calcined at different temperatures. The surface morphologies, crystalline phases, and chemical-state of the catalysts were characterized by scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Influences of reaction conditions, such as dye concentration, catalyst dosage and solution pH, were evaluated and the relations between catalytic capacity and surface microstructures were discussed. The results showed that Fe-containing Y and ZSM-5 zeolites generally exhibited similar or better catalytic efficiency compared with homogeneous Fenton reagent, with Fe-containing ZSM-5 being more efficient. Synthesis method and calcination temperature affected catalytic efficiency and the stability of catalysts. Fe-containing ZSM-5, which was prepared by coprecipitation and calcined at 450 degrees C, displayed the greatest decolorization capacity. Under the conditions of initial pH 2.5, 30.0 mmol/L H(2)O(2) and 4.0 g/L catalyst, 250 mg/L KN-R could be decolorized over 90% within 20 min.     

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).     

Degradation and detoxification of formaline wastewater by advanced oxidation processes

In this study, advanced oxidation processes (AOPs) utilizing the combinations of UV/H(2)O(2), Fenton, photo-Fenton and the combination of Fenton/photo-Fenton reactions were investigated in lab-scale experiments for the degradation of formaline wastewater. The studied toxic chemicals were formaldehyde and methanol in mixture solution, so-called formalin, which is the embalming agent in mortuaries. The experimental results showed that the photo-Fenton process was the most effective treatment process among the studied AOPs. Pseudo-first-order degradation rate constants of formaldehyde and methanol were obtained from batch experimental data. In the combination of Fenton/photo-Fenton reactions, the results show that applying UV light at an early stage of the reaction might not be necessary for a speedy oxidation reaction of the Fenton process. With Fenton and photo-Fenton processes, mineralization of formaline wastewater can be achieved, as no residual TOC is detected in the effluent after the reaction period. It is suggested that Fenton and photo-Fenton processes are viable techniques for the formaline wastewater treatment as they were able to provide high degradation of formaldehyde and methanol with relatively low toxicity of the by-products in the effluent.     

Treatment of industrial oily wastewaters by wet oxidation

In the present work, the homogeneous wet oxidation (WO) of an oily wastewater (COD approximately 11,000 mg l(-1)), composed mainly of alcohols and phenolic compounds, was studied in a high-pressure agitated autoclave reactor in the temperature range of 180-260 degrees C and oxygen pressure 1 MPa. Temperature was found to have a significant impact on the oxidation of the contaminants in the wastewater. Among the compounds contained in the wastewater, ethylene glycol showed great resistance to wet oxidation. Temperatures above 240 degrees C were required for its effective degradation. Organic acids, mainly acetic acid, were the intermediate products of the wet oxidation process and their conversion to carbon dioxide was very slow. A generalised model based on a parallel reaction scheme was used to interpret the experimental data obtained. The activation energies obtained were in the range of 90-130 kJ mol(-1).     

Treatment of petroleum refinery sourwater by advanced oxidation processes

The performance of several oxidation processes to remove organic pollutants from sourwater was investigated. Sourwater is a specific stream of petroleum refineries, which contains slowly biodegradable compounds and toxic substances that impair the industrial biological wastewater treatment system. Preliminary experiments were conducted, using the following processes: H2O2, H2O2/UV, UV, photocatalysis, ozonation, Fenton and photo-Fenton. All processes, except Fenton and photo-Fenton, did not lead to satisfactory results, reducing at most 35% of the sourwater dissolved organic carbon (DOC). Thus, further experiments were performed with these two techniques to evaluate process conditions and organic matter removal kinetics. Batch experiments revealed that the Fenton reaction is very fast and reaches, in a few minutes, an ultimate DOC removal of 13-27%, due to the formation of iron complexes. Radiation for an additional period of 60 min can increase DOC removal up to 87%. Experiments were also conducted in a continuous mode, operating one 0.4L Fenton stirred reactor and one 1.6L photo-Fenton reactor in series. DOC removals above 75% were reached, when the reaction system was operated with hydraulic retention times (HRT) higher than 85 min. An empirical mathematical model was proposed to represent the DOC removal kinetics, allowing predicting process performance quite satisfactorily.     

Anaerobic biogranulation in a hybrid reactor treating phenolic waste

Granulation was examined in four similar anaerobic hybrid reactors 15.5L volume (with an effective volume of 13.5L) during the treatment of synthetic coal wastewater at the mesophilic temperature of 27+/-5 degrees C. The hybrid reactors are a combination of UASB unit at the lower part and an anaerobic filter at the upper end. Synthetic wastewater with an average chemical oxygen demand (COD) of 2,240 mg/L, phenolics concentration of 752 mg/L and a mixture of volatile fatty acids was fed to three hybrid reactors. The fourth reactor, control system, was fed with a wastewater containing sodium acetate and mineral nutrients. Coal waste water contained phenol (490 mg/L); m-, o-, p-cresols (123.0, 58.6, 42 mg/L); 2,4-, 2,5-, 3,4- and 3,5-dimethyl phenols (6.3, 6.3, 4.4 and 21.3mg/L) as major phenolic compounds. A mixture of anaerobic digester sludge and partially granulated sludge (3:1) were used as seed materials for the start up of the reactors. Granules were observed after 45 days of operation of the systems. The granules ranged from 0.4 to 1.2 mm in diameter with good settling characteristics with an SVI of 12 mL/gSS. After granulation, the hybrid reactor performed steadily with phenolics and COD removal efficiencies of 93% and 88%, respectively at volumetric loading rate of 2.24 g COD/Ld and hydraulic retention time of 24 h. The removal efficiencies for phenol and m/p-cresols reached 92% and 93% (corresponding to 450.8 and 153 mg/L), while o-cresol was degraded to 88% (corresponding to 51.04 mg/L). Dimethyl phenols could be removed completely at all the organic loadings and did not contribute much to the residual organics. Biodegradation of o-cresol was obtained in the hybrid-UASB reactors.     

Removal of organic carbon from wastepaper pulp effluent by lab-scale solar photo-Fenton process

The bleaching wastewater effluent from a pulp and paper mill (located in Tianjin, China) was treated with solar photo-Fenton process in a lab-scale reactor (22 cm x 15 cm thermostatic dish). The mill used wastepaper as raw material and the effluent contained 332 mgL(-1) of total organic carbon (TOC) and 1286 mg L(-1) of COD. The treatment involved a constant intensity of irradiation (0.2 kW/m(2)) with a solar simulator of 250 W xenon lamp and various conditions of pH, temperature, and initial concentrations of H(2)O(2) and Fe(II). The better treatment conditions were searched for in the ranges of initial Fe(II) concentration from 31 to 310 mgL(-1) (initial pH 3.0, 30 degrees C), initial H(2)O(2) concentration from 0.5 to 3 Dth (1 Dth=1883 mg L(-1) for TOC mineralization) (initial pH 3.0, 30 degrees C), initial pH from 2.0 to 6.0 (1 and 2 Dth, 10:1 of H(2)O(2)/Fe(II), 30 degrees C), and temperature from 30 to 50 degrees C (1 Dth, 10:1 of H(2)O(2)/Fe(II), initial pH 2.8). TOC removal generally showed the initial fast increase stage within the first sampling time of 15 min, followed by the gradual increase stage in the remaining sampling time of 180 min experimental time course. The highest percentage of TOC removal in the first stage was about 60% when the initial pH was either 2.8 (H(2)O(2)=1 Dth, ratio=10:1, temperature=30-50 degrees C) or 3.5 (H(2)O(2)=2 Dth, ratio=10:1, temperature=30 degrees C). Also under the latter condition, the value reached 82% at 120 min and was projected to reach 94% at 180 min. According to the positive effect of temperature increase on TOC removal observed in this experiment, further increase above these maximum values is possible if the temperature of the above condition were increased from 30 to 40 degrees C or 50 degrees C. Furthermore, under most of the treatment conditions, the TOC removal reached or was projected to reach over 60% toward the end of the experiments. The result indicated that the solar photo-Fenton process has a potential to effectively remove TOC from the wastepaper pulp effluent on a large scale.     

Photochemical treatment of 2-chlorophenol aqueous solutions using ultraviolet radiation, hydrogen peroxide and photo-Fenton reaction

In the present work, the photochemical oxidation of 2-chlorophenol aqueous solutions in a batch recycle photochemical reactor using ultraviolet irradiation and hydrogen peroxide was studied. Specifically, the effect of hydrogen peroxide initial concentration (0-10316 mg L(-1)) and 2-chlorophenol initial concentration (150-3000 mg L(-1)) was examined. The process was attended via total organic carbon (TOC), 2-chlorophenol, chloride ion, acetic acid, formic acid and pH measurements. The conversion of 2-chlorophenol observed was always much higher than the corresponding total organic carbon removal, whereas the increase in hydrogen peroxide amount in the solution led to higher values of 2-chlorophenol conversion and total organic carbon removal. Finally, the photo-Fenton reaction was applied to the oxidation of 2-chlorophenol, leading to a higher degree of mineralization of the parent compound.