Slaughterhouse wastewater treatment by combined anaerobic baffled reactor and UV/H2O2 processes

Combined processes of biological anaerobic baffled reactor (ABR) and UV/H₂O₂ at a laboratory scale were studied to treat a synthetic slaughterhouse wastewater. In this study, the total organic carbon (TOC) loadings of 0.2-1.1 g/(L day) were used. The results revealed that combined processes had a higher efficiency to treat the synthetic slaughterhouse wastewater. Up to 95% TOC removal was obtained for an influent concentration of 973.3 mgTOC/L at the hydraulic retention time (HRT) of 3.8 days in the ABR and 3.6 h in the UV photoreactor. Meanwhile, up to 97.7% and 96.6% removal of chemical oxygen demand (COD) and 5-day carbonaceous biochemical oxygen demand (CBOD₅) were observed in the ABR for the same influent concentration, respectively. Comparatively, for an influent concentration of 157.6 mgTOC/L, the UV/H₂O₂ process alone with the TOC loading of 0.06-1.9 g/(L h) was also studied, in which, up to 64.3%, 83.7%, and 84.3% of TOC, COD, and CBOD₅ removal were observed, respectively, at the HRT of 2.5 h with hydrogen peroxide (H₂O₂) concentration of 529 mg/L. It was found that individual ABR and UV/H₂O₂ processes enhanced the biodegradability of the treated effluent by an increased CBOD₅/COD ratio of 0.4 to 0.6. An optimum H₂O₂ dosage of 3.5 (mgH₂O₂)/(mgTOC_in h) was also found for the UV/H₂O₂ process.     

Electro-Fenton degradation of azo dye using polypyrrole/anthraquinonedisulphonate composite film modified graphite cathode in acidic aqueous solutions

Amaranth azo dye has been degraded by electro-Fenton method using an undivided cell containing the polypyrrole (PPy)/anthraquinonedisulphonate (AQDS) composite film modified graphite cathode and Pt anode. In acidic media, the PPy/AQDS composite film exhibits the characteristic of gas diffusion cathode and is highly efficient for hydrogen peroxide electrogeneration with high generation rate and current efficiency. This new electro-Fenton system can degrade amaranth azo dye efficiently in various acidic solutions. The amaranth decay and total organic carbon (TOC) removal were determined as a function of pH, cathode potential, Fe²⁺ and doping AQDS concentrations. Total dye decay and 80.3% mineralization were achieved at the optimum conditions (pH 3.0, E_cath = −0.65 V vs. SCE, 2.0 mM Fe²⁺ concentration). The electrochemical stability and electrocatalytic activity of the composite film after use in electro-Fenton process were also investigated using cyclic voltammetry (CV) and Fourier transfer infrared (FTIR) spectroscopy technologies.     

Advanced oxidation of catechol: A comparison among photocatalysis, Fenton and photo-Fenton processes

The aim of this work was to compare the behaviour of Fenton, photo-Fenton and photocatalysis processes to treat catechol solutions which are pollutants occurring in wastewaters from many industries. The effect of different process parameters, such as initial catechol concentration, H₂O₂/FeSO₄ ratio in Fenton and photo-Fenton oxidation, TiO₂ loadings in photocatalysis and irradiation times has been studied.Fenton and photo-Fenton (H₂O₂/FeSO₄ = 600/500 (w/w) and 30 min reaction time) processes allowed us to achieve a high efficiency in the mineralization of catechol (COD removals up to 83% and 96% respectively), and removal of aromaticity (UV₂₈₀) (up to 93% and 98% respectively), for an initial catechol concentration of 110 mg/l. On the opposite, photocatalysis was not effective in the removal of higher catechol concentrations (110 and 200 mg/l), whereas a significant removal of aromaticity versus time was observed for 50 mg/l. Gas chromatography-mass spectrometry analysis, performed under selected treatment conditions, showed that total removal of catechol can occur after Fenton (2000/500 w/w; 30 min), photo-Fenton (600/500 w/w; 30 min), and photocatalysis (3 g TiO₂/l; 240 min) treatments.     

Degradation of 2-chlorophenol by Fenton and photo-Fenton processes

The photodegradation of a specific organic pollutant using the Fenton and the photo-Fenton processes has been examined in aqueous solution. The applications of the Fenton process and the photo-Fenton process to the degradation of 2-chlorophenol (2-CP) were investigated. The dependence on the following experimental conditions had been evaluated: initial pH (1.0–9.0), hydrogen peroxide (0.67–2 mM), ferrous ions (0.1–2 mM), initial concentration of 2-CP (0.1–2 mM). The optimal experimental conditions were 1 mM H₂O₂, 1 mM ferrous ion and pH 3.0. Under the optimal conditions, the degradation efficiency of 2-CP in the photo-Fenton process was enhanced 4% more than that of the Fenton process. Experimental results about the degradation of 2-CP show that UV irradiation improves the degradation efficiency of the Fenton process. The major intermediate formed during the degradation of 2-CP was p-benzoquinone.     

Degradation of surfactant used in iron mining by oxidation technique: Fenton,photo-Fenton,and H2O2/UV—A comparative study

Reuse of water in mining helps reduce the volume of tailings directed to dams, avoiding overloads and ruptures, as occurred in Brumadinho, Brazil. Water reuse in mining requires treatment mainly for removing the surfactant substances used. Photo-Fenton and UV/H₂O₂ showed 96% to 98% degradation results of anionic surfactants within 5 minutes, suggesting this technique is faster than biological systems that can take days. This paper aims to study the degradation of a surfactant used in the flotation process by UV/H₂O₂, Fenton, and photo-Fenton oxidation techniques. The compound was characterized by FTIR and MALDI-TOF. In degradation experiments, the variation in reactants concentrations was evaluated with hydrogen peroxide, iron sulphate heptahydrate, and oxalic acid. We used a synthetic solution of surfactant in the reverse flotation of ore with 180 mg/L. The reaction was monitored with TOC analysis and a spectrophotometer throughout the reaction. The UV/H₂O₂ and Fenton system were studied by varying peroxide and iron concentrations, with 120 minute tests. Additionally, photo-Fenton concentrations, the pH variation (1.5-8.0), temperature (15°C, 21°C, and 60°C), and time were evaluated. The results showed the most efficient degradation was that using photo-Fenton, which achieved total TOC removal using 4500 mg/L of peroxide and 364 mg/L of iron for 330 minutes, while the UV/H₂O₂ system achieved 29% and 49% TOC removal of the Fenton. It is verified that the oxidative processes can be applied to degrade the surfactants present in the water recovered from the flotation processes.     

Photolytic treatment of organic constituents and bacterial pathogens in secondary effluent of synthetic slaughterhouse wastewater

The reduction and degradation of total organic carbon (TOC) and bacteria from a secondary effluent of synthetic slaughterhouse wastewater using vacuum-ultraviolet (VUV) and ultraviolet-C (UV-C) processes and their combination (UV-C/VUV and VUV/UV-C) were investigated. The TOC removal rates under continuous mode operation ranged from 5.5 to 6.2%. In addition, the treatment with the UV-C/H₂O₂ and VUV/H₂O₂ processes under continuous mode operation doubled the TOC removal rates 10.8 and 12.2%, respectively. The optimum molar ratio of H₂O₂/TOC was found to be 2.5 and 1.5 for the UV-C and VUV processes, respectively. It was observed that all photochemical processes were able to totally inactivate different strains of bacteria with concentrations up to 10⁵ CFU/mL within 27.6 s. Finally, a kinetic model was developed to simulate the TOC degradation from a secondary effluent of synthetic slaughterhouse wastewater.     

Photoelectro-Fenton combined with photocatalytic process for degradation of an azo dye using supported TiO2 nanoparticles and carbon nanotube cathode: Neural network modeling

In this work, treatment of an azo dye solution containing C.I. Basic Red 46 (BR46) by photoelectro-Fenton (PEF) combined with photocatalytic process was studied. Carbon nanotube-polytetrafluoroethylene (CNT-PTFE) electrode was used as cathode. The investigated photocatalyst was TiO₂ nanoparticles (Degussa P25) having 80% anatase and 20% rutile, specific surface area (BET) 50 m²/g, and particle size 21 nm immobilized on glass plates. A comparison of electro-Fenton (EF), UV/TiO₂, PEF and PEF/TiO₂ processes for decolorization of BR46 solution was performed. Results showed that color removal follows the decreasing order: PEF/TiO₂ > PEF > EF > UV/TiO₂. The influence of the basic operational parameters such as initial pH of the solution, initial dye concentration, the size of anode, applied current, kind of ultraviolet (UV) light and initial Fe³⁺ concentration on the degradation efficiency of BR46 was studied. The mineralization of the dye was investigated by total organic carbon (TOC) measurements that showed 98.8% mineralization of 20 mg/l dye at 6 h using PEF/TiO₂ process. An artificial neural network (ANN) model was developed to predict the decolorization of BR46 solution. The findings indicated that artificial neural network provided reasonable predictive performance (R² = 0.986).     

Modeling dye degradation kinetic using dark- and photo-Fenton type processes

Dark- and photo-Fenton type processes, Fe²⁺/H₂O₂, Fe³⁺/H₂O₂, Fe⁰/H₂O₂, UV/Fe²⁺/H₂O₂, UV/Fe³⁺/H₂O₂ and UV/Fe⁰/H₂O₂, were applied for the treatment of model colored wastewater containing two reactive dyes, C.I. Reactive Blue 49 and C.I. Reactive Blue 137, and degradation kinetics were compared. Dye degradation was monitored by the means of UV/VIS, adsorbable organic halides (AOX) and total organic carbon (TOC) analysis, thus determining decolorization and dechlorination of triazine structure, as well as mineralization of model colored wastewater. Both dark- and photo-Fenton type processes were proven to be very efficient for color removal; ≥98% was achieved in all cases. Significant improvements in the mineralization of studied dyes were achieved by the assistance of UV light, as it was expected. It was demonstrated that the degradation kinetic of applied dyes depended on the presence of UV light, as well as type of iron catalyst and dye structure. On bases of the obtained experimental results, the mathematical models were developed describing dye degradation kinetics in all studied systems. Since UV light was used in order to enhance the efficiency of dark-Fenton type processes, mathematical model describing dye degradation by UV photolysis providing the values of quantum yields for each of the dye was developed and incorporated in model for photo-Fenton type processes. A sensitivity analysis for the evaluation of importance of each reaction used in mathematical models was also performed.     

Mechanism and kinetic study for the degradation of lindane by photo-Fenton process

Because application of classical treatment methods cannot allow an easily Lindane (gamma 1α,2α,3β,4α,5α,6β-hexachlorocyclohexane) degradation, development of more powerful water treatment techniques, like advanced oxidation processes (AOPs), was necessary. The degradation of lindane (γ-HCH) has been studied using the photo-Fenton reaction. The degradation kinetics under irradiation was optimized in respect to H₂O₂ concentration and Fe²⁺ concentration at a constant lindane concentration. The degradation rate follows pseudo-first order kinetics with respect to lindane and organic clorine mineralization. Application of photo-Fenton system also assures total organic carbon removal with 95% efficiency at 2 h irradiation. The possible pathways of lindane photodegradation is also proposed.     

Treatment of phenol formaldehyde production wastewater by electrooxidation-electrofenton successive processes

ABSTRACT

Treatments of phenol formaldehyde producing wastewater (PFPW) by electrooxidation (EO) and electro-Fenton (EF) successive processes were carried out in a batch electrolytic reactor using graphite (Gr) and stainless steel (Ss) electrodes. After the completion of the EO process, the wastewater was further treated with EF process. The influence of operating variables such as current density, operating time, initial pH_i and H₂O₂ concentration was evaluated for removals of phenol, TOC and COD in PFPW. Gr/Gr, Gr/Ss or Ss/Ss and Ss/Gr electrode pair were used as anode and cathode. The best removal efficiency in the EO process was obtained with Gr/Gr (93%) as compared to Gr/Ss (82%), Ss/Ss (63%) and Ss/Gr (55%). The removal efficiencies for the EO process using Gr-Gr electrode pair were obtained as 93% for phenol, 61% for COD and 44% for TOC at initial pH_i 7,5 g/L of NaCl, 50 mA/cm² and 5 h. In the EF process, the removal efficiencies at pH_i 3,5 mA/cm² and 30 mM H₂O₂ and 45 min were 100% for phenol, 76% for COD and 59% for TOC. This study provided that the successive processes are an effective method for the removal of phenolic compounds from the wastewater.     

Heterogeneous photo-Fenton oxidation of reactive azo dye solutions using iron exchanged zeolite as a catalyst

The heterogeneous photo-Fenton-type oxidation of reactive azo dye solutions has been investigated in a quartz batch reactor using artificial UVA as a light source. Fe-exchanged zeolite has been used as a heterogeneous catalyst in the process. The effect of various process variables on decolorization performance of the process was evaluated by examining temperature, pH, H₂O₂ dosage, catalyst loading, initial dye concentration and light intensity. The optimal operational parameters were found as follows: 35 °C, pH as solution pH 5.2, 15 mmol H₂O₂ dosage, 1 g/L catalyst loading. Stability and reuse of the catalyst were also tested. Mineralization and comparison with homogenous photo-Fenton process were evaluated by analyzing color removal and total organic carbon (TOC) values.     

The addition of hydrogen peroxide in the electrocoagulation treatment for improving toxic organic matters removal: A comparative study

The role of hydrogen peroxide (H₂O₂) in the electrocoagulation (EC) treatment for removing toxic organic matters in wet-spun acrylic fibers (WAFs) manufacturing effluents was investigated. The addition of H₂O₂ in the EC resulted in electro-Fenton (EF) treatment, which improved the removal of organic pollutants. Biodegradability of the EF-treated effluents was significantly improved over the EF treatment and reached 0.18. In addition, evaluation of the toxicity of the treated effluents using luminous bacteria revealed that the EF treatment resulted in the greater removal of toxic compounds than the EC treatment, with 80.9% decline in the EC₅₀.     

Mineralization of an azo dye Acid Red 14 by photoelectro-Fenton process using an activated carbon fiber cathode

The mineralization of an azo dye Acid Red 14 (AR14) by the photoelectro-Fenton (PEF) process was studied in an undivided electrochemical reactor with a RuO₂/Ti anode and an activated carbon fiber (ACF) cathode able to electrochemically generate H₂O₂. Anodic oxidation and UV irradiation of AR14 were also examined as comparative experiments. Results indicate that the electro-Fenton process yielded about 60–70% mineralization of AR14, while the photoelectro-Fenton could mineralize AR14 more effectively (more than 94% total organic carbon (TOC) removal) even at low current densities assisted with UV irradiation after 6 h electrolysis. The mineralization current efficiency (MCE) of the PEF process increased with the increasing AR14 concentrations. In addition, the initial solution pH ranging from 1.49 to 6.72 had little influence on the TOC removal probably due to the formation of organic carboxylic acids which balanced the pH increase caused by the cathodic generation of hydrogen gas. The ACF cathode showed a long-term stability during multiple experimental runs for degradation of AR14, indicating its good potential for practical application in treating refractory organic pollutants in aqueous solutions.     

Effect of continuous addition of H2O2 and air injection on ferrioxalate-assisted solar photo-Fenton degradation of Orange II

An experimental study based on ferrioxalate-assisted solar photo-Fenton (SPFox) process shows how non-biodegradable azo dye Orange II (OII) solutions degradation can be enhanced or slowed down by continuous addition of hydrogen peroxide and air injection depending on operation conditions. The decoloration and mineralization of dye solution has been carried out in a solar Compound Parabolic Collector (CPC). An optimization study was done by using Multivariate Experimental Design including the following variables: flow rate of H₂O₂, air flow rate, pH and initial concentrations of Fe(II) and oxalic acid. The efficiency of photocatalytic degradation was determined from the analysis of color and Total Organic Carbon (TOC). Experimental data were fitted using neural networks (NNs) which allow the simulation of the process for any value of variables in the studied experimental range. The results reveal that the continuous addition of H₂O₂ improves the photocatalytic efficiency since the scavenger effect of peroxide is minimized. On the other hand, this system permits the use of a ferrous concentration below the discharge legal limit (2 ppm) being bubbling of air not necessary in that conditions. In addition, oxalic acid can be used to pH adjustment, reducing the operation costs of Fe removal, chemicals and electric power. Under the optimal conditions, 100% decoloration of dye solution can be reached by using both processes (SPFox with H₂O₂ addition at the beginning or along the reaction) but with different reaction rates. However, the efficiency of TOC removal was higher in the SPFox process with continuous addition of H₂O₂ (95% TOC removal in SPFox system with continuous addition of peroxide versus 80% TOC removal in SPFox system when peroxide is added at the beginning of the reaction). Molecular and/or radical reaction pathway was studied by conducting the reaction in the presence and absence of tert-butylalcohol.     

A study of the photocatalytic degradation of metamitron in ZnO water suspensions

The photocatalytic degradation of the herbicide metamitron in water using ZnO under Osram ULTRA-VITALUX® lamp light was studied. The effect of the operational parameters such as initial concentration of catalyst, initial metamitron concentration, initial salt concentration (NaCl, Na₂CO₃ and Na₂SO₄) and pH was studied. The optimal concentration of catalyst was found to be 2.0 g/l. First-order rate constants were calculated for the uncatalysed reactions. On the base of the Langmuir-Hinshelwood mechanism, a pseudo first-order kinetic model was illustrated and the adsorption equilibrium constant and the rate constant of the surface reaction were calculated (0.119 l mg^− 1 and 0.836 mg l^− 1 min^− 1, respectively). The photodegradation rate was higher in acidic than in alkaline conditions. When salt effect was studied, it was found that sodium carbonate was the most powerful inhibitor used, while sodium chloride was the weakest one. A negligible inhibition was observed when the concentration of sodium chloride was 20 mM.The rate of photodecomposition of metamitron was measured using UV spectroscopy and HPLC, while its mineralization was followed using ion chromatography (IC), as well as total organic carbon (TOC) and total nitrogen (TN) analysis.Under the employed conditions, almost complete disappearance of 9 mg/ml of herbicide, 56% TOC and 34% TN removal, occurred within 4 h. The ion chromatography results showed that the mineralization led to ammonium, nitrite and nitrate ions during the process.     

Oil-Refinery Wastewater Treatment Aiming Reuse by Advanced Oxidation Processes (AOPs) Combined with Biological Activated Carbon (BAC)

The treatment of a refinery wastewater by Advanced Oxidation Processes (AOP) coupled with Biological Activated Carbon (BAC) was investigated aiming to generate water for reuse. O₃/UV and H₂O₂/UV processes were employed to oxidize the organic matter and the BAC process to remove residual organic matter from the AOP effluent. AOP promoted oxidation of recalcitrant organic matter as observed by moderate drops on the treated wastewater absorbance (31–79%) and TOC values (10–18%). BAC filters showed to be effective, reaching average efficiencies of 65% in a sufficiently long period of operation (84 days), while GAC filters were saturated after 28 days. Effluent TOC values in the range of 4 to 8.5 mg/L were achieved by the combined treatment (H₂O₂/UV + BAC), allowing water reuse.     

Degradation of Alizarin Red by electro-Fenton process using a graphite-felt cathode

The removal of the anthraquinone dye Alizarin Red S (AR) has been investigated by electro-Fenton process using a commercial graphite-felt to electrogenerate in situ hydrogen peroxide and regenerate ferrous ions as catalyst. The effect of operating conditions such as applied current, catalyst concentration, and initial dye content on AR degradation has been studied. AR decay kinetic, the evolution of its oxidation intermediates and the mineralization of the aqueous solutions were monitored during the electrolysis by UV–Vis analysis and TOC measurements. The experimental results showed that AR was completely removed by the reaction with OH radicals generated from electrochemically assisted Fenton's reaction, and the decay kinetic always follows a pseudo-first-order reaction. Applying a current of 300 mA and with catalyst concentration of 0.2 mM Fe²⁺, 95% of the initial TOC was removed in 210 min of electrolysis, meaning the almost complete mineralization of the organic content of the treated solution.     

Decomposition of acetic acid by advanced oxidation processes

Decomposition of acetic acid, known as a non-degradable organic compound, was conducted for several advanced oxidation processes such as TiO₂-UV-H₂O₂, Fe²⁺-H₂O₂-UV, UV-H₂O₂ and TiO₂-UV system. Acetic acid was efficiency decomposed within 120 minutes of UV radiation under the initial concentration of 500 ppm. The initial chemical oxygen demands (COD _cr ) tended to increase as H₂O₂ was added in most reactions. However, the initial COD _cr was not increased as H₂O₂ was consumed for the oxidation of iron salt in the photo-Fenton oxidation process. COD _cr and concentration of acetic acid rapidly decreased as the mole ratio of hydrogen peroxide increased owing to rapid decomposition of the reactant at the beginning of reaction. All reactions show first order pseudo reaction rate. The COD _cr removal rate and the decomposition efficiency of acetic acid were fastest in the UV-H₂O₂ process.     

Comparative study of chemical and electrochemical Fenton treatment of organic pollutants in wastewater

The technological and economic aspects of using the Fenton process to treat industrial wastewater containing morpholyne and diethylethanolamine, as well as sodium salts of naphthalene sulfonic acid and of ethylenediaminetetraacetic acid based on data obtained in pilot tests are discussed. Chemical Fenton technology was tested using commercial 30–35% solutions of H₂O₂ and iron (II) salts, which was followed by the additional electrochemical destruction of organic pollutants in an undivided reactor with catalytic stable anodes (CSA) and 1 g L⁻¹ NaCl as a supporting electrolyte and a source of active chlorine. An alternative electrochemical method involving the electrogeneration of hydrogen peroxide in polluted water at the gas -diffusion cathode was studied both with the addition of ferrous salt to the electrolyte prior to electrolysis (in-cell electro-Fenton) as well as with the post-electrolysis addition of Fe²⁺ in another reactor (ex-cell electro-Fenton). The accumulation of hydrogen peroxide in concentrations sufficient for the mineralization of organic pollutants was achieved in both cases with near 100% current efficiency. In comparison with wastewater treatment processes which use a purchased hydrogen peroxide reagent, the Fenton-like processes achieved an economic savings of as much as 64.5% in running costs due to the on-site electrochemical generation of H₂O₂. Preparative electrolysis in the membrane reactor showed higher current efficiencies and lower specific energy consumptions for H₂O₂ electrogeneration in comparison with the results of tests carried out in an undivided cell.     

Ozonation of Phenol-Containing Wastewater Using O3/Ca(OH)2 System in a Micro Bubble Gas-Liquid Reactor

The degradation of phenol in aqueous solution was investigated in an integrated process consisting of O₃/Ca(OH)₂ system and a newly developed micro bubble gas-liquid reactor. The effects of operating parameters such as Ca(OH)₂ dosage, reactor pressure, liquid phase temperature, initial phenol concentration and inlet ozone concentration on degradation and mineralization (TOC removal) were studied in order to know the ozonation performance of this new integrated process. It is demonstrated that the degradation and TOC removal efficiency increased with increasing inlet ozone concentration and increasing Ca(OH)₂ dosage before 2 g/L, as well as decreasing initial phenol concentration. The optimum Ca(OH)₂ dosage should exceed Ca(OH)₂ solubility in liquid phase. The reactor pressure and liquid phase temperature have little effects on the removal and TOC removal efficiency. When Ca(OH)₂ dosage exceeded 3 g/L, the degradation and TOC removal of phenol almost reached 100% at 30 and 55 min, respectively. The intensification mechanism of Ca(OH)₂ assisted ozonation was explored through analysis of the precipitated substances. The mechanism for Ca(OH)₂ intensified mineralization of phenol solution is the simultaneous removal of CO₃^2- ions, as hydroxyl radical scavengers, due to the presence of Ca²⁺ ions. Results indicated that the proposed new integrated process is a highly efficient ozonation process for persistent organic wastewater treatment.