Degradation of sodium dodecyl sulphate in water using solar driven Fenton-like advanced oxidation processes

Synthetic wastewater samples containing a model surfactant were treated using two different Fenton-like advanced oxidation processes promoted by solar radiation; the photo-Fenton reaction and Co/PMS/UV processes. Comparison between the different experimental conditions was performed by means of the overall surfactant degradation achieved and by obtaining the initial rate in the first 15 min of reaction (IR15). It was found that, for dark Fenton reaction, the maximum surfactant degradation achieved was 14% under low iron and oxidant concentration. Increasing Fenton reagents by one magnitude order, surfactant degradation achieved 63% in 60 min. The use of solar radiation improved the reaction rate by 17% under same conditions and an additional increase of 12.5% was obtained by adjusting initial pH to 2. IR15 values for dark and irradiated Fenton reactions were 0.143 and 0.154 mmol/min, respectively, for similar reaction conditions and this value increased to 0.189 mmol/min when initial pH was adjusted. The use of the Co/PMS system allow us to determine an increase in the degradation rate, for low reaction conditions (1 mM of transition metal; 4 mM oxidant) similar to those used in dark Fenton reaction. Surfactant degradation increased from 3%, for Fenton reaction, to 44.5% in the case of Co/PMS. When solar irradiation was included in the experiments, under same reaction conditions described earlier, surfactant degradation up to 64% was achieved. By increasing Co/PMS reagent concentration by almost 9 times under irradiated conditions, almost complete (>99%) surfactant degradation was reached in 5 min. Comparing IR15 values for Co/PMS and Co/PMS/UV, it allow us to observe that the use of solar radiation increased the degradation rate in one magnitude order when compared with dark experiments and further increase of reagent concentration increased reaction rate twice.     

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.     

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.     

A comparative study of the advanced oxidation of 2,4-dichlorophenol

Advanced oxidation processes (AOPs) using UV, UV/H2O2, Fenton and photo-Fenton treatment were investigated at laboratory scale for aqueous solutions of 2,4-dichlorophenol (DCP). The effects on degradation of different reactant concentrations, irradiation time, temperature and pH were assessed. DCP removal, TOC mineralization, dechlorination and change in oxidation state were monitored. UV photolysis was less efficient for total DCP degradation than other AOPs. In contrast, photo-Fenton reaction in acidic conditions led to a higher DCP degradation in a short time. Sixty minutes of treatment were sufficient for 100% DCP removal with 75 mg l(-1) H2O2 and 10 mg l(-1) Fe(II) initial concentrations. In these conditions, a first-order degradation constant for DCP of 0.057 min(-1) was obtained.     

Photo-Fenton process as an efficient alternative to the treatment of landfill leachates

Advanced oxidation processes (AOPs), namely photo-Fenton, Fenton-like, Fenton and UV/H(2)O(2), have been investigated in the removal of organic matter and colour from landfill leachates. The leachate was characterised by high COD, low biodegradability and intense dark colour. Evaluation of COD removal as a function of the operation variables (H(2)O(2), Fe(2+), Cu(2+), UV) led to results that ranged between 30% and 77% and it was observed that the removal efficiencies decreased in the order: photo-Fenton>Fenton-like>Fenton>UV/H(2)O(2)>UV. Thus, a detailed experimental analysis was carried out to analyse the effect of the hydrogen peroxide and iron concentrations and the number of reagent additions in the photo-Fenton process, observing that: (i) the COD removal ranged from 49% to 78% depending on the H(2)O(2) dose, (ii) the total amount of organic matter removed was increased by adding the reagent in multiple steps (86%), (iii) iron concentration corresponding to a Fe(2+)/COD mass ratio=0.33 was found to be the most favourable and, (iv) after a neutralization step, the colour and residual concentrations of iron and H(2)O(2) were practically negligible in the final leachate solution.     

Combined photo-Fenton-SBR process for antibiotic wastewater treatment

The study examined combined photo-Fenton-SBR treatment of an antibiotic wastewater containing amoxicillin and cloxacillin. Optimum H₂O₂/COD and H₂O₂/Fe²⁺ molar ratio of the photo-Fenton pretreatment were observed to be 2.5 and 20, respectively. Complete degradation of the antibiotics occurred in one min. The sequencing batch reactor (SBR) was operated at different hydraulic retention times (HRTs) with the wastewater treated under different photo-Fenton operating conditions (H₂O₂/COD and H₂O₂/Fe²⁺ molar ratio). The SBR performance was found to be very sensitive to BOD₅/COD ratio of the photo-Fenton treated wastewater. Statistical analysis of the results indicated that it was possible to reduce the Fe²⁺ dose and increase the irradiation time of the photo-Fenton pretreatment. The best operating conditions of the combined photo-Fenton-SBR treatment were observed to be H₂O₂/COD molar ratio 2, H₂O₂/Fe²⁺ molar ratio 150, irradiation time 90 min and HRT of 12 h. Under the best operating conditions, 89% removal of sCOD with complete nitrification was achieved and the SBR effluent met the discharge standards.     

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.     

Pre-treatment of penicillin formulation effluent by advanced oxidation processes

A variety of advanced oxidation processes (AOPs; O3/OH-, H2O2/UV, Fe2+/H2O2, Fe3+/H2O2, Fe2+/H2O2/UV and Fe3+/H2O2/UV) have been applied for the oxidative pre-treatment of real penicillin formulation effluent (average COD0 = 1395 mg/L; TOC0 = 920 mg/L; BOD(5,0) approximately 0 mg/L). For the ozonation process the primary involvement of free radical species such as OH* in the oxidative reaction could be demonstrated via inspection of ozone absorption rates. Alkaline ozonation and the photo-Fenton's reagents both appeared to be the most promising AOPs in terms of COD (49-66%) and TOC (42-52%) abatement rates, whereas the BOD5 of the originally non-biodegradable effluent could only be improved to a value of 100 mg/L with O3/pH = 3] treatment (BOD5/COD, f = 0.08). Evaluation on COD and TOC removal rates per applied active oxidant (AOx) and oxidant (Ox) on a molar basis revealed that alkaline ozonation and particularly the UV-light assisted Fenton processes enabling good oxidation yields (1-2 mol COD and TOC removal per AOx and Ox) by far outweighed the other studied AOPs. Separate experimental studies conducted with the penicillin active substance amoxicillin trihydrate indicated that the aqueous antibiotic substance can be completely eliminated after 40 min advanced oxidation applying photo-Fenton's reagent (pH = 3; Fe(2+):H2O2 molar ratio = 1:20) and alkaline ozonation (at pH = 11.5), respectively.     

Treatment of gasoline-contaminated waters by advanced oxidation processes

In this study, the efficiency of advanced oxidative processes (AOPs) was investigated toward the degradation of aqueous solutions containing benzene, toluene and xylenes (BTX) and gasoline-contaminated waters. The results indicated that BTX can be effectively oxidized by near UV-assisted photo-Fenton process. The treatment permits almost total degradation of BTX and removal of more than 80% of the phenolic intermediates at reaction times of about 30 min. Preliminary investigations using water contaminated by gasoline suggest a good potentiality of the process for the treatment of large volumes of aqueous samples containing these polluting species. Heterogeneous photocatalysis and H2O2/UV system show lower degradation efficiency, probably due to the heterogeneous character of the TiO2-mediated system and lost of photonic efficiency of the H2O2/UV system in the presence of highly colored intermediated.     

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.     

Photo-assisted Fenton type processes for the degradation of phenol: a kinetic study

In this study the application of advanced oxidation processes (AOPs), dark Fenton and photo-assisted Fenton type processes; Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), Fe(0)/H(2)O(2), UV/Fe(2+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) and UV/Fe(0)/H(2)O(2), for degradation of phenol as a model organic pollutant in the wastewater was investigated. A detail kinetic modeling which describes the degradation of phenol was performed. Mathematical models which predict phenol decomposition and formation of primary oxidation by-products: catechol, hydroquinone and benzoquinone, by applied processes were developed. The study also consist the modeling of mineralization kinetic of the phenol solution by applied AOPs. This part, besides well known reactions of Fenton and photo-Fenton chemistry, involves additional reactions which describe removal of iron from catalytic cycle through formation of ferric complexes and its regeneration induced by UV radiation. Phenol decomposition kinetic was monitored by HPLC analysis and total organic carbon content measurements (TOC). Complete phenol removal was obtained by all applied processes. Residual TOC by applied Fenton type processes ranged between 60.2 and 44.7%, while the efficiency of those processes was significantly enhanced in the presence of UV light, where residual TOC ranged between 15.2 and 2.4%.     

Pre-ozonation coupled with UV/H2O2 process for the decolorization and mineralization of cotton dyeing effluent and synthesized C.I. Direct Black 22 wastewater

The decolorization and mineralization of cotton dyeing effluent containing C.I. Acid Black 22 as well as synthesized C.I. Acid Black 22 wastewater by means of advanced oxidation processes (AOPs), such as UV/H2O2, O3 and pre-ozonation coupled with UV/H2O2 processes, were evaluated in this study. It was observed that the UV/H2O2 process took longer retention time than ozonation for color removal of dye bath effluent. Reversely, the total organic carbon (TOC) removal showed different phenomena that ozonation and UV/H2O2 process obtained 33 and 90% of removal efficiency for 160 min of retention time, respectively. Additionally, laboratory synthesized dye wastewater was substantially more efficient in the decolorization process than dye bath effluent. Therefore, in this work, pre-ozonation coupled with UV/H2O2 process was employed to enhance the reduction of both color and TOC in dye bath effluent at the same time. At the same time, the retention time demand was reduced to less than 115 min for 90% removal of TOC and color by this combined process.     

Color, TOC and AOX removals from pulp mill effluent by advanced oxidation processes: a comparative study

Pulp mill effluent containing toxic chemicals was treated by different advanced oxidation processes (AOPs) consisting of treatments by hydrogen peroxide, Fenton's reagent (H2O2/Fe2+), UV, UV/H2O2, photo-Fenton (UV/H2O2/Fe2+), ozonation and peroxone (ozone/H2O2) in laboratory-scale reactors for color, total organic carbon (TOC) and adsorbable organic halogens (AOX) removals from the pulp mill effluent. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC, color, AOX removals were investigated. Almost every method used resulted in some degree of color removal from the pulp mill effluent. However, the Fenton's reagent utilizing H2O2/Fe2+ resulted in the highest color, TOC and AOX removals under acidic conditions when compared with the other AOPs tested. Approximately, 88% TOC, 85% color and 89% AOX removals were obtained by the Fenton's reagent at pH 5 within 30 min. Photo-Fenton process yielded comparable TOC (85%), color (82%) and AOX (93%) removals within 5 min due to oxidations by UV light in addition to the Fenton's reagent. Fast oxidation reactions by the photo-Fenton treatment makes this approach more favorable as compared to the others used.     

Imidacloprid oxidation by photo-Fenton reaction

This paper presents experimental results on the imidacloprid removal from wastewater using homogeneous photo-Fenton reactions illuminated with black light lamps. Multivariate experimental design was used to identify the effect of initial Fe(II) and H₂O₂ concentrations on process performance. The initial iron concentration played a key role in the process kinetics, whereas hydrogen peroxide concentration directly affected the extent of the oxidation process.

Imidacloprid degradation proceeded via two distinctive kinetics regimes, an initial stage of rapid imidacloprid reduction, followed by a slower oxidation process until complete removal. Under optimal conditions, more than 50% imidacloprid degradation was observed after less than 1 min treatment, and TOC and COD removal up to 65% and 80%, respectively, were measured after all hydrogen peroxide was consumed.

Raw imidacloprid samples presented significant acute toxicity to Daphnia magna and genotoxic effects on Bacillus subtilis sp. Such toxic effects remained detectable even after significant pesticide removal had been achieved, due to the presence of toxic by-products. Both acute toxicity and genotoxicity disappeared after considerable mineralization resulting in final low molecular weight by-products. Results obtained here confirm that design and operation of photo-Fenton processes should focus on toxicity removal rather than on specific target pollutants.     

The decolorization and mineralization of acid orange 6 azo dye in aqueous solution by advanced oxidation processes: a comparative study

The comparison of different advanced oxidation processes (AOPs), i.e. ultraviolet (UV)/TiO(2), O(3), O(3)/UV, O(3)/UV/TiO(2), Fenton and electrocoagulation (EC), is of interest to determine the best removal performance for the destruction of the target compound in an Acid Orange 6 (AO6) solution, exploring the most efficient experimental conditions as well; on the other hand, the results may provide baseline information of the combination of different AOPs in treating industrial wastewater. The following conclusions can be drawn: (1) in the effects of individual and combined ozonation and photocatalytic UV irradiation, both O(3)/UV and O(3)/UV/TiO(2) processes exhibit remarkable TOC removal capability that can achieve a 65% removal efficiency at pH 7 and O(3) dose=45mg/L; (2) the optimum pH and ratio of [H(2)O(2)]/[Fe(2+)] found for the Fenton process, are pH 4 and [H(2)O(2)]/[Fe(2+)]=6.58. The optimum [H(2)O(2)] and [Fe(2+)] under the same HF value are 58.82 and 8.93mM, respectively; (3) the optimum applied voltage found in the EC experiment is 80V, and the initial pH will affect the AO6 and TOC removal rates in that acidic conditions may be favorable for a higher removal rate; (4) the AO6 decolorization rate ranking was obtained in the order of O(3)相似文献   

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.     

Degradation of DMSO by ozone-based advanced oxidation processes

The present study investigates the oxidation of dimethyl sulfoxide (DMSO) by conventional ozonation and the advanced oxidation processes (AOPs). The major degradation products identified were methanesulfinate, methanesulfonate, formaldehyde, and formic acid in ozonation process. The subsequent degradation of intermediates shows that methanesulfonate is more resistance to ozonation, which reduces the mineralization rate of DMSO. The effect of t-butanol addition and ozone gas flow dosage on the degradation rate was evaluated. The rate constant of the reaction of ozone (k(D)) with DMSO was found to be 0.4162 M(-1)S(-1). In the second part of this study, DMSO degradation and TOC mineralization were investigated using O(3)/UV, O(3)/H(2)O(2) and UV/H(2)O(2) processes. In all theses processes the degradation of target organics is more pronounced than TOC removal. The efficiencies of these processes were evaluated and discussed. The formation of sulfate ion in all AOPs have been identified and compared with other processes. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of DMSO in wastewater.     

Degradation of carbofuran by using ozone, UV radiation and advanced oxidation processes.

The degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate), a frequently used carbamate derivative pesticide that is considered a priority pollutant, is carried out in batch reactors by means of single oxidants: ozone, UV radiation and Fenton's reagent; and by the advanced oxidation processes (AOPs) constituted by combinations of ozone plus UV radiation, UV radiation plus H(2)O(2), and UV radiation plus Fenton's reagent (photo-Fenton system). For all these reactions, the apparent pseudo-first-order rate constants are evaluated in order to compare the efficiency of each process. In addition and by means of a competition kinetic model, the rate constants for the reaction of carbofuran with ozone and with hydroxyl radicals are also determined. The improvement in the decomposition levels of carbofuran reached by the combined processes in relation to the single oxidants, due to the generation of the very reactive hydroxyl radicals, is also established in every process. For the oxidant concentrations applied, the most effective process in removing carbofuran was the photo-Fenton system.     

Toxicity assessment from electro-coagulation treated-textile dye wastewaters by bioassays

In this study the pollutant removal from a textile dyeing wastewater has been investigated by using the electro-coagulation technique with iron electrodes. In order to obtain optimal values of the system state variables, a 3³ full factorial experimental design was applied. The electro-coagulation (EC) process response was evaluated on the basis of COD removal and decolourisation values. The electrolysis time and density current were statistically significant for the COD removal and decolourisation. Based on the lettuce seeds (Lactuca sativa) and brine shrimp (Artemia salina), the lowest toxicity level was achieved in 5 min of electrolysis time. Due to the remaining high toxicity level above 30 min of electrolysis time, the EC process is not adequate to be used in a single effluent treatment, suggesting that this electrochemical process of up to 5 min could be used as part of a complete effluent treatment system.     

The use of basalt powder as a natural heterogeneous catalyst in the Fenton and Photo-Fenton oxidation of cationic dyes

The use of naturally present heterogeneous catalysts has recently been an essential issue in the Fenton and photo-Fenton processes. In this study, the uses of basalt as a catalyst for the Fenton and photo-Fenton reactions for methylene Blue (MB) and Basic Red 18 (BR18) degradations were investigated. Basalt was selected because of the presence of the iron (III) oxide in the structure. Basalt was characterized by X-Ray Fluorescence (XRF) and X-Ray Diffraction (XRD) analysis to obtain the chemical composition and the crystalline phase. The surface charge and the surface area were obtained by zeta potential and Brunauer Emmett-Teller (BET) analysis. Fourier Transform Infrared Spectroscopy (FTIR) and scanning electron microscope (SEM) were utilized to explore the functional group and the surface morphology. Fenton and photo-Fenton processes were applied to explore the best degradation method. Adsorption was also tested and the adsorption process had minimum removal efficiency (12% for MB and 17% for BR18). The removal efficiencies for MB and BR18 by the Fenton process were 87% and 28%, respectively. The photo-Fenton process had maximum removal efficiency with 100% for MB and 70% for BR18. The optimum conditions were 70 mg/L dye concentration, 5 mM H₂O₂, 1.0 g/L basalt loading and pH 2. Basalt has shown reuse capability as a catalyst for three consecutive cycles.