Electrochemical treatment of anionic surfactants in synthetic wastewater with three-dimensional electrodes

The electrochemical oxidation of anionic surfactants (sodium dodecyl benzene sulfonate, DBS) contained in simulated wastewater treated by three-dimensional electrode system with combined modified kaolin served as packed bed particle electrodes and Ti/Co/SnO(2)-Sb(2)O(3) anode was studied, the chemical oxygen demand (COD) removal of pollutants in the solutions was also investigated. The results showed that the three-dimensional electrodes in combined process could effectively decompose anionic surfactants. The COD removal efficiency can reach 86%, much higher than that of Ti/Co/SnO(2)-Sb(2)O(3) electrodes used singly or modified kaolin employed singly (graphite as anode and cathode) on the same condition of pH 3 and 38.1 mA/cm(2) current density. The current efficiency and kinetic constant were calculated and energy consumption was studied. At the same time the influence of pH and current density on COD removal efficiency with combined three-dimensional electrodes was also investigated, respectively. The optimal initial pH value of degradation is 3 (acid condition), and a minor COD removal increase follows higher current density.     

Electrochemical oxidation of pulp and paper making wastewater assisted by transition metal modified kaolin

The electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes was investigated. H(2)O(2), which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destroy the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification and the results showed that the transition metals were completely supported on kaolin and formed a porous structure with big BET surface. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. From the results it can be founded that when the initial pH was at 3, current density was 30 mA cm(-2); catalyst dose was 30 g dm(-3), COD (chemical oxygen demand) removal could reach up to 96.8% in 73 min.     

Application of molybdenum and phosphate modified kaolin in electrochemical treatment of paper mill wastewater

Pulp and paper mill wastewater is characterized by very high chemical oxygen demand (COD) values that inhibit the activity of microorganisms during biological oxidations. The electrochemical degradation of pulp and paper mill wastewater catalyzed by molybdenum and phosphate (Mo-P) modified kaolin with graphite as anode and cathode was investigated. The catalyst was characterized by XRD, XPS and SEM spectra and the effects of pH, metal ion and introduction of NaCl on the efficiency of the electrochemical degradation process were also studied. It was found out that the modified kaolin loaded with Fe(3+) had higher electrochemical catalytic activity in the electrochemical degradation of paper mill wastewater at pH 4. A 96% COD removal efficiency was obtained in 40min of electrochemical treatment of the wastewater at current density 30mAcm(-2). A possible mechanism for degradation of the mill wastewater constituents was also proposed.     

Treatment of bactericide wastewater by combined process chemical coagulation, electrochemical oxidation and membrane bioreactor

Bactericide wastewater (BIW) contains isothiazolin-ones, high salinity, toxicity and non-biodegradable organic concentrations. In order to enhance biodegradable capacity, chemical coagulation and electrochemical oxidation were applied to pretreatment processes. FeSO(4).7H2O, pH 12 and 20 mmol/l were determined as optimal chemical coagulation condition; and 15 mA/cm2 of current density, 10 ml/min of flow rate and pH 7 were chosen for the most efficient electrochemical oxidation condition at combined treatment. The wastewater which consisted mainly of isothiazolin-ones and sulfide was efficiently treated by chemical coagulation and electrochemical oxidation. The optimal pretreatment processes showed 60.9% of chemical oxygen demand (COD), 99.5% of S(2-) and 96.0% of isothiazolin-ones removal efficiency. A biological treatment system using membrane bioreactor (MBR) adding powder-activated carbon (PAC) was also investigated. COD of the wastewater which was disposed using a MBR was lower than 100 mg/l.     

CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol

This paper presents an original approach to the removal of phenol in synthetic wastewater by catalytic wet peroxide oxidation with copper binding activated carbon (CuAC) catalysts. The characteristics and oxidation performance of CuAC in the wet hydrogen peroxide catalytic oxidation of phenol were studied in a batch reactor at 80 °C. Complete conversion of the oxidant, hydrogen peroxide, was observed with CuAC catalyst in 20 min oxidation, and a highly efficient phenol removal and chemical oxygen demand (COD) abatement were achieved in the first 30 min. The good oxidation performance of CuAC catalyst was contributed to the activity enhancement of copper oxide, which was binding in the carbon matrix. It can be concluded that the efficiency of oxidation dominated by the residual H₂O₂ in this study. An over 90% COD removal was achieved by using the multiple-step addition in this catalytic oxidation.     

Studies on degradation of Methyl Orange wastewater by combined electrochemical process

The combined process of electro-catalytic oxidation and de-colorization of wastewater contained Methyl Orange (MO) in a double-anode system, with iron plate and graphite plate as anodes and graphite plate as cathode assisted by Co2O3-CuO-PO4(3-) modified kaolin, was investigated systematically. The effects of pH, current density and electrolyte on de-colorization efficiency were also studied. Chemical oxygen demand (COD) was selected as another parameter to evaluate the efficiency of this combined degradation method on treatment of MO wastewater and the results revealed that when initial pH was 5.0, current density was 30 mA cm(-2), NaCl as electrolyte and its concentration was 2.5 g dm(-3), the color removal efficiency and COD removal can reach 100% and 89.7%, respectively. Meanwhile, the kinetics and the possible mechanism were also discussed.     

Electrochemical catalytic treatment of wastewater by metal ion supported on cation exchange resin

The electrochemical oxidation of phenol in synthetic wastewater and paper mill wastewater catalyzed by metal ion supported on cation exchange resin in suspended bed electrolytic reactor with graphite electrode has been investigated. The catalyst was characterized by SEM and XPS spectra and the effects of pH, the different metal ion and NaCl on the efficiency of the electrochemical oxidation phenol process were also studied. It was found that the catalyst containing Fe(3+) had the highest electrochemical catalytic activity for the electrochemical oxidation of phenol. When the initial concentration of phenol was 200 ppm, up to 90% chemical oxygen demand (COD) removal was obtained in 10 min. When the catalyst containing Fe(3+) was used to the paper mill wastewater, it still showed high efficiency. The COD removal could get to 75% in 60 min.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Electrochemical oxidation of phenol in a parallel plate reactor using ruthenium mixed metal oxide electrode

In this study, electrochemical oxidation of phenol was carried out in a parallel plate reactor using ruthenium mixed metal oxide electrode. The effects of initial pH, temperature, supporting electrolyte concentration, current density, flow rate and initial phenol concentration on the removal efficiency were investigated. Model wastewater prepared with distilled water and phenol, was recirculated to the electrochemical reactor by a peristaltic pump. Sodium sulfate was used as supporting electrolyte. The Microtox bioassay was also used to measure the toxicity of the model wastewater during the study. As a result of the study, removal efficiency of 99.7% and 88.9% were achieved for the initial phenol concentration of 200 mg/L and chemical oxygen demand (COD) of 480 mg/L, respectively. In the same study, specific energy consumption of 1.88 k Wh/g phenol removed and, mass transfer coefficient of 8.62 x 10(-6)m/s were reached at the current density of 15 mA/cm(2). Electrochemical oxygen demand (EOD), which can be defined as the amount of electrochemically formed oxygen used for the oxidation of organic pollutants, was 2.13 g O(2)/g phenol. Electrochemical oxidation of petroleum refinery wastewater was also studied at the optimum experimental conditions obtained. Phenol removal of 94.5% and COD removal of 70.1% were reached at the current density of 20 mA/cm(2) for the petroleum refinery wastewater.     

Photoelectrocatalytic decontamination of oilfield produced wastewater containing refractory organic pollutants in the presence of high concentration of chloride ions

The feasibility study of the application of the photoelectrocatalytic decontamination of high saline produced water containing refractory organic pollutants was investigated in the slurry photoelectrocatalytic reactor with nanometer TiO2 particle prepared with sol-gel method using the acetic acid as hydrolytic catalyst. The efficiency of the photoelectrocatalytic decontamination of produced water was determined with both COD removal from the tested wastewater and the decrease of mutagenic activity evaluated by Ames tests. The experimental results showed that the photoelectrocatalysis is a quite efficient process for decontaminating the produced water, although there are high concentration of salt existed in oilfield wastewater. We found that the COD removal efficiencies by photoelectrocatalytic process are much higher than that of by photocatalytic or electrochemical oxidation individually in the photoelectrocatalytic reactor. The COD removal can be substantially improved by the added H2O2 and the generation of active chlorine from high concentration chlorides in the wastewater. The effects of various operating conditions, such as initial COD concentration, applied cell voltage, catalyst amount and initial pH value of solution, on the photoelectrocatalytic efficiencies, is also investigated in detail. The results showed that when the raw produced wastewater was diluted in a 1:1 (v/v) ratio, there is a highest COD removal efficiency. And the photoelectrocatalytic degradation of organic pollutants in saline water is much favored in acidic solution than that in neutral and/or alkaline solution.     

Pretreatment of wastewater from triazine manufacturing by coagulation, electrolysis, and internal microelectrolysis

We studied the pretreatment of concentrated wastewater from triazine manufacturing by coagulation, electrolysis, and internal microelectrolysis. Results show that coagulation by polyaluminum chloride at dosage of 0.5 g/L could remove up to 17.2% chemical oxygen demand (COD) from the wastewater. Electrolysis using iron electrode achieved 33.2% COD removal at current of 2A in 180 min, which was attributed to coagulation and oxidation of the organic contaminants in the wastewater by the radicals (OH and O) and oxidants (O2, O3, and H2O2) produced in electrochemical reactions. Internal microelectrolysis using iron chips and granular activated carbon (GAC) showed that up to 60.5% COD could be removed under the conditions of iron/GAC/wastewater volumetric ratio of 3:2:490, sparge ratio (ratio of air flow rate to volume of wastewater) of 2:490 min(-1), and reaction time of 132 h. COD reduction in internal microelectrolysis was attributed to a combination of chemical and physical processes, mainly oxidation by radicals and oxidants formed in electrochemical reactions, adsorption on, co-precipitation with, and enmeshment in ferrous and ferric hydroxides resulted from Fe2+ released during anode oxidation. The results suggest that internal microelectrolysis using iron chips and GAC is a promising, low-cost alternative for pretreating concentrated wastewater from pesticide manufacturing.     

Combined advanced oxidation and biological treatment processes for the removal of pesticides from aqueous solutions

Advanced oxidation processes were combined with biological treatment processes in this study to remove both pesticides and then the COD load from aqueous solutions. It was found that O(3) and O(3)/UV oxidation systems were able to reach 90 and 100%, removal of the pesticide Deltamethrin, respectively, in a period of 210 min. The use of O(3) combined with UV radiation enhances pesticides degradation and the residual pesticide reaches zero in the case of Deltamethrin. The combined O(3)/UV system can reduce COD up to 20% if the pH of the solution is above 4. Both pesticide degradation and COD removal in the combined O(3)/UV system follow the pseudo-first-order kinetics and the parameters of this model were evaluated. The application of the biological treatment to remove the bulk COD from different types of feed solution was investigated. More than 95% COD removal was achieved when treated wastewater by the O(3)/UV system was fed to the bioreactor. The parameters of the proposed Grau model were estimated.     

Improvement of COD and color removal from UASB treated poultry manure wastewater using Fenton's oxidation

The applicability of Fenton's oxidation as an advanced treatment for chemical oxygen demand (COD) and color removal from anaerobically treated poultry manure wastewater was investigated. The raw poultry manure wastewater, having a pH of 7.30 (+/-0.2) and a total COD of 12,100 (+/-910) mg/L was first treated in a 15.7 L of pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB reactor was operated for 72 days at mesophilic conditions (32+/-2 degrees C) in a temperature-controlled environment with three different hydraulic retention times (HRT) of 15.7, 12 and 8.0 days, and with organic loading rates (OLR) between 0.650 and 1.783 kg COD/(m3day). Under 8.0 days of HRT, the UASB process showed a remarkable performance on total COD removal with a treatment efficiency of 90.7% at the day of 63. The anaerobically treated poultry manure wastewater was further treated by Fenton's oxidation process using Fe2+ and H2O2 solutions. Batch tests were conducted on the UASB effluent samples to determine the optimum operating conditions including initial pH, effects of H2O2 and Fe2+ dosages, and the ratio of H2O2/Fe2+. Preliminary tests conducted with the dosages of 100 mg Fe2+/L and 200 mg H2O2/L showed that optimal initial pH was 3.0 for both COD and color removal from the UASB effluent. On the basis of preliminary test results, effects of increasing dosages of Fe2+ and H2O2 were investigated. Under the condition of 400 mg Fe2+/L and 200 mg H2O2/L, removal efficiencies of residual COD and color were 88.7% and 80.9%, respectively. Under the subsequent condition of 100 mg Fe2+/L and 1200 mg H2O2/L, 95% of residual COD and 95.7% of residual color were removed from the UASB effluent. Results of this experimental study obviously indicated that nearly 99.3% of COD of raw poultry manure wastewater could be effectively removed by a UASB process followed by Fenton's oxidation technology used as a post-treatment unit.     

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.     

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.     

Catalytic and non-catalytic wet air oxidation of sodium dodecylbenzene sulfonate: kinetics and biodegradability enhancement

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) were investigated as suitable precursors for the biological treatment of industrial wastewater containing sodium dodecylbenzene sulfonate (DBS). Two hours WAO semi-batch experiments were conducted at 15 bar of oxygen partial pressure (P(O2)) and at 180, 200 and 220 degrees C. It was found that the highest temperature provides appreciable total organic carbon (TOC) and chemical oxygen demand (COD) abatement of about 42 and 47%, correspondingly. Based on the main identified intermediates (acetic acid and sulfobenzoic acid) a reaction pathway for DBS and a kinetic model in WAO were proposed. In the case of CWAO experiments, seventy-two hours tests were done in a fixed bed reactor in continuous trickle flow regime, using a commercial activated carbon (AC) as catalyst. The temperature and P(O2) were 140-160 degrees C and 2-9 bar, respectively. The influence of the operating conditions on the DBS oxidation, the occurrence of oxidative coupling reactions over the AC, and the catalytic activity (in terms of substrate removal) were established. The results show that the AC without any supported active metal behaves bi-functional as adsorbent and catalyst, giving TOC conversions up to 52% at 160 degrees C and 2 bar of P(O2), which were comparable to those obtained in WAO experiments. Respirometric tests were completed before and after CWAO and to the main intermediates identified through the WAO and CWAO oxidation route. Then, the readily biodegradable COD (COD(RB)) of the CWAO and WAO effluents were found. Taking into account these results it was possible to compare whether or not the CWAO or WAO effluents were suitable for a conventional activated sludge plant inoculated with non adapted culture.     

Degradation of cationic red X-GRL by electrochemical oxidation on modified PbO(2) electrode

This work investigated the degradation of an azo dye, cationic red X-GRL, by electrochemical oxidation on a novel PbO(2) anode modified by fluorine resin. The influences of treatment time, electrolyte concentration, current density, temperature and initial dye concentration on the color and COD removal were critically examined. This process showed a high current efficiency and competitive energy consumption for effective treatment of dye wastewater containing a certain salt content. In the investigated electrolyte concentrations, high salt content exhibited insignificant promotion on the color and COD removal but favored the decrease of energy consumption. During treatment, the current efficiency decreased but the energy consumption increased with treatment time; thus, this method was more suitable for the pretreatment of high-concentrated azo dye wastewater. Based on the degradation intermediates identification, a simplified degradation pathway for cationic red X-GRL was proposed.     

Electrochemical oxidation of a textile dye wastewater using a Pt/Ti electrode

Textile dye wastewater (TDW) from a reactive azo dyeing process was treated by an electrochemical oxidation method using Ti/Pt as anode and stainless steel 304 as cathode. Due to the strong oxidizing potential of the chemicals produced (chlorine, oxygen, hydroxyl radicals and other oxidants) when the wastewater was passed through the electrolytic cell the organic pollutants were oxidized to carbon dioxide and water. A number of experiments were run in a batch, laboratory-scale, pilot-plant, and the results are reported here according to residence time and initial addition of HCl in raw wastewater. When of 2 ml of HCl 36% were added and after 18 min of electrolysis at 0.89 A/cm(2), chemical oxygen demand (COD) was reduced by 86%, biochemical oxygen demand (BOD(5)) was reduced by 71%, ADMI color units were reduced by 100%, and TKN was reduced by 35%. The biodegradability of the wastewater was improved because the COD/BOD ratio decreased from 2.16 to 1.52. At the same time the efficiency of the electrode was about 170 g h(-1) A(-1) m(-2). and the mean energy consumption was 21 kW h/kg of COD. These results indicate that this electrolytic method could be used for effective TDW oxidation or as a feasible detoxification and color removal pretreatment stage for biological post treatment.     

Advanced oxidation processes applied to tannery wastewater containing Direct Black 38--elimination and degradation kinetics

The application of advanced oxidation processes (H(2)O(2)/UV, TiO(2)/H(2)O(2)/UV and TiO(2)/UV) to treat tannery wastewater was investigated. The experiments were performed in batch and continuous UV reactors, using TiO(2) as a catalyst. The effect of the hydrogen peroxide concentration on the degradation kinetics was evaluated in the concentration range 0-1800 mg L(-1). We observed that the degradation rate increased as the hydrogen peroxide increased, but excessive H(2)O(2) concentration was detrimental because it acted as a hydroxyl radical scavenger since it can compete for the active sites of the TiO(2). In the H(2)O(2)/UV treatment, the COD removal reached around 60% in 4 h of reaction, indicating that the principal pollutants were chemically degraded as demonstrated by the results for BOD, COD, nitrate, ammonium and analysis of the absorbance at 254 nm. Artemia salina toxicity testing performed in parallel showed an increase in toxicity after AOP treatment of the tannery 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.