Optimization of Fenton process for decoloration and COD removal in tobacco wastewater and toxicological evaluation of the effluent

Decoloration and chemical oxygen demand (COD) removal in tobacco wastewater by Fenton process has been optimized under 25 +/- 2 degrees C. The results showed that the optimal range of conditions were pH 4.13-4.66, Fe(2+) 0.29-0.34 g/L and H2O2 > or = 2.73 g/L. Within this range, up to 95% of colour and 90% of COD was removed. In an enlarged system, setting the optimal conditions as pH 4.50, Fe(2+) 0.34 g/L and H2O2 4.00 g/L, the colour removal rate was 96.03 +/- 2.57%, with COD removal rate of 93.30 +/- 2.92%. The residual COD of 73.67 +/- 19.70 mg/L in effluent had hit the State's first-class standard for the industrial discharge in China (< 100 mg/L COD, GB8978-1996). The ecological safety of Fenton process has also been evaluated. When reaction completed, the content of hydroxyl free radical (OH) was 3.26 +/- 0.44 mg/L. There was no inhibition of Fenton effluent in growth of Escherichia coli, Pseudomonas putida, Pseudomonas sp. HF-1, Acinetobacter sp. TW and Sphingomonas sp. TY. No oxidative stress was induced on strain HF-1 by Fenton effluent. Thus, Fenton process was one of high-efficiency and ecologically safe strategy for tobacco wastewater advanced treatment.     

Comparison of electrocoagulation, coagulation and the fenton process for the treatment of reactive dyebath effluent.

In this paper, experimental studies were performed on a simulated reactive dyebath effluent to compare coagulation-flocculation and Fenton's oxidation with electrocoagulation using stainless steel (SS 304) and aluminium electrodes in terms of colour and COD removals as well as AOX formation potential and improvement of biological treatability. Results have indicated that FeCl3 and alum coagulation had little effect on colour removal whereas comparable colour removal efficiencies with those of electrocoagulation with steel electrodes and Fenton's oxidation were attained by FeSO4 coagulation. Almost complete colour removals accompanied with 77% COD abatement were obtained by both electrocoagulation with steel electrodes and Fenton's oxidation under optimised reaction conditions. Although electrocoagulation with aluminium electrodes yielded very limited colour removal and produced a high amount of sludge upon extended reaction time, this application brought about a marked improvement in biodegradability.     

Physico-chemical treatment for the depuration of wine distillery wastewaters (vinasses).

In the present work, an integrated Fenton-coagulation/flocculation process was applied for the depuration of wine distillery wastewaters, commonly known as "vinasses". This study evaluates the Fenton process (H2O2/Fe2+), involving oxidation--in a first stage and coagulation/flocculation (using Ca(OH)2 as base-precipitant)--in a second stage for the removal of chemical oxygen demand (COD). The experimental variables studied were the dosages of hydrogen peroxide and iron salts, the molar ratio [H2O2]o: [Fe2+]o, the effluent dilution and the manner in which the reagents were added (splitting the reagent dose of hydrogen peroxide and ferrous salt into different fractions). The optimal operating conditions of the integrated process were: [H2O2]o = 0.5 mol/L using an optimal concentration ratio [H2O2]o: [Fe2+]o= 15 mol/mol. Under these conditions, the COD removal was 74%.     

Advanced oxidation of bleached eucalypt kraft pulp mill effluent.

In this study a poorly biodegradable (BOD/COD = 0.3) industrial alkaline ECF bleaching filtrate was treated using different advanced oxidation processes to evaluate their use in combined chemical-biological treatment aimed at increasing recalcitrant COD removal and improving final effluent quality. Oxidative treatments included ozonation combined with hydrogen peroxide (2, 5, 10, 20 mmol L(-1) O3/0.7, 2, 5, 10 mmol L(-1) H2O2) and photocatalysis with hydrogen peroxide (UV/2, 4 and 8 mmolL(-1) H2O2) and with TiO2 (UV/TiO2/0.7 and 4 mmol L(-1) H2O2). The O3/H2O2 process increased effluent biodegradability by up to 68% as a result of increasing BOD and decreasing COD. Increasing the O3 dose had a greater effect on biodegradability improvement and lignin and colour removal efficiencies than increasing the H2O2 dose. A combined oxidant dose of 5 mmol L(-1) O3 and 2 mmol L(-1) H2O2 resulted in 75% lignin removal, 40% colour removal and 6% carbohydrate loss without mineralizing the organic carbon. The photocatalytic processes led to a decrease in effluent biodegradability through combined decrease in BOD and increase in COD and did not result in efficient lignin or colour removal. Photocatalytic oxidation was apparently inhibited by the high chloride and COD levels in the alkaline filtrate, and may be more efficient in recalcitrant COD removal if performed after biological.     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

Effect of photochemical pre-treatment on COD fractionation of a non-ionic textile surfactant.

The work presented in this paper is focused on the effect of photochemical (H2O2/UV-C) pretreatment on COD fractionation and degradation kinetics of a non-ionic textile surfactant. In the first part of the study, the COD of non-ionic surfactant was adjusted to 1000 mg/L in order to simulate real effluent originating from the textile preparation stage featuring desizing, scouring, washing and rinsing operations. The surfactant was subjected to H2O2/UV-C pretreatment for up to 120 min at a dose of 30 mM (980 mg/L) H2O2. The biodegradability studies for untreated and photochemically treated samples were evaluated on the basis of modeling of oxygen uptake rate (OUR) profiles. Modelling of OUR profiles conducted for untreated sample showed that single complex substrate was subjected to enzymatic breakdown and disintegrated into one readily and two types of slowly biodegradable substrates. After modelling the biodegradation of photochemically pretreated sample, the readily biodegradable COD fraction was reduced, on the other hand, more slowly biodegradable organics were generated. A higher disintegration rate was obtained for chemically pretreated samples. However, other kinetic constants of growth and hydrolysis processes were not affected considerably.     

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.     

Application of statistical experimental design to the treatment of bleaching kraft mill effluent using a mediated free radical system.

The aim of this work was to evaluate the effect of chelator mediated-Fenton reaction (CMFR) on the chemical oxygen demand (COD) removal from bleaching kraft mill effluent. Effluent treatments were carried out to study the effect of the chelator 3, 4-dihydroxyphenylacetic acid (DOPAC), Fe3+ and H2O2 concentrations on COD removal. For optimization of COD removal, the methodology of statistical experimental design was employed. The estimated second-order polynomial multiple regression model predicts a maximum COD removal of 75.5% (COD/COD0 = 0.245) at the confidence level of 95%. Analysis of variance (ANOVA) showed a good coefficient of determination (R2) value of 0.90, thus ensuring a satisfactory adjustment of the second-order regression model with the experimental data. Indeed, CMFR proved to be a potential process to treat industrial effluents characterized by its high COD.     

Treatability of cefazolin antibiotic formulation effluent with O3 and O3/H2O2 processes.

The effect of applying ozonation and perozonation to antibiotic cefazolin-Na formulation effluents were investigated in this study. Twenty minutes of ozonation at a rate of 1,500 mg/L-h was observed to remove COD by 38%, whereas a COD removal efficiency of 40% was achieved via H2O2 enhanced ozonation (same conditions + 31.25 mM H2O2). Both of the pretreatment alternatives were monitored to elevate the BOD5/COD ratio from 0.01 to 0.08. The initially inert COD was reduced by 38% using ozonation and by 60% employing H2O2 enhanced ozonation. In terms of the lowest achievable effluent COD levels after bio-treatment, ozonation was observed to yield a residual COD of 205 mgL(-1), while a residual COD of 135 mgL(-1) was involved for perozonation. According to the results of acute toxicity on Phaedactylum tricornutum, ozonated and perozonated samples exhibited more toxicity than the untreated effluent after 4 days. The activated sludge inhibition test demonstrated that both of the pretreatment alternatives efficiently eliminated the inhibition of investigated formulation effluent.     

Treatment of oilfield wastewater by Fenton's process.

A combination of coagulation and Fenton's process was used for the removal of total oxygen carbon (TOC) from oilfield wastewater. Compared with aluminium sulfate, ferric coagulant had better TOC removal efficiency at the same mass dosage. In Fenton's process, the effect of H2O2 and Fe2+ dose on the removal of TOC was studied. The optimum conditions required for TOC removal were an Fe3+ concentration of 40-50 mg/L, an H2O2 dose of 50 mmol/L and an Fe2+ concentration of 1.0 mmol/L. GC-MS chromatographic analysis indicated that most of the alkyl hydrocarbons of carbon numbers < 21 were removed in the first minute of Fenton's process mainly through adsorption. Alkyl hydrocarbons and phenols were oxidized almost completely following 120 min of treatment. The pathway of newly formed intermediates in Fenton's process was proposed on the basis of the GC/MS chromatogram.     

Effects of oxidant concentration and temperature on decolorization of azo dye: comparisons of UV/Fenton and UV/Fenton-like systems

This study applies photo-Fenton and photo-Fenton-like systems to decolorize C.I. Reactive Red 2 (RR2). The oxidants were H(2)O(2) and Na(2)S(2)O(8); Fe(2+), Fe(3+), and Co(2+) were used to activate these two oxidants. The effects of oxidant concentration (0.3-2 mmol/L) and temperature (25-55 °C) on decolorization efficiency of the photo-Fenton and photo-Fenton-like systems were determined. The decolorization rate constants (k) of RR2 in the tested systems are consistent with pseudo-first-order kinetics. The rate constant increased as oxidant concentration and temperature increased. Activation energies of RR2 decolorization in the UV/H(2)O(2)/Fe(2+), UV/H(2)O(2)/Fe(3+), UV/Na(2)S(2)O(8)/Fe(2+) and UV/Na(2)S(2)O(8)/Fe(3+) systems were 32.20, 39.54, 35.54, and 51.75 kJ/mol, respectively.     

Integrated biological (anaerobic-aerobic) and physico-chemical treatment of baker's yeast wastewater.

The UASB reactor (35 degrees C) was quite efficient for removal of bulk COD (52-74%) from simulated (on the basis of cultivation medium from the first separation process) general effluent of baker's yeast production (the average organic loading rates varied from 8.1 to 16 g COD/l/d). The aerobic-anoxic biofilter (19-23 degrees C) can be used for removal of remaining BOD and ammonia from anaerobic effluents; however, it suffered from COD-deficiency to fulfil denitrification requirements. To balance COD/N ratio, some bypass (approximately 10%) of anaerobically untreated general effluent should be added to the biofilter feed. The application of iron (III)-, aluminium- or calcium-induced coagulation for post-treatment of aerobic-anoxic effluents can fulfil the limits for discharge to sewerage (even for colour mainly exerted by hardly biodegradable melanoidins), however, the required amounts of coagulants were relatively high.     

Integrated chemical, physical and biological processes modelling of anaerobic digestion of sewage sludge.

The biological kinetic processes for anaerobic digestion (AD) are integrated into a two phase subset of a three phase mixed weak acid/base chemistry kinetic model. The approach of characterising sewage sludge into carbohydrates, lipids and proteins, as is done in the International Water Association (IWA) AD model No 1 (ADM1), requires measurements that are not routinely available on sewage sludges. Instead, the sewage sludge is characterised with the COD, carbon, hydrogen, oxygen and nitrogen (CHON) composition and is formulated in mole units, based on conservation of C, N, O, H and COD. The model is calibrated and validated with data from laboratory mesophilic anaerobic digesters operating from 7 to 20 d sludge age and fed a sewage primary and humus sludge mixture. These digesters yielded COD mass balances between 107-109% and N mass balances between 91-99%, and hence the experimental data is accepted as reasonable. The sewage sludge COD is found to be 32-36% unbiodegradable (depending on the kinetic formulation selected for the hydrolysis process) and to have a C3.5H7O2N0.196 composition. For the selected hydrolysis kinetics of surface mediated reaction (Contois), with a single set of kinetic and stoichiometric constants, for all retention times good correlation is obtained between predicted and measured results for: (i) COD; (ii) free and saline ammonia (FSA); (iii) short chain fatty acids (SCFA); (iv) H2CO3 * alkalinity; (v) pH of the effluent stream; (vi) CO2; and (vii) CH4 gases in the gas stream. The measured composition of primary sludge from two local wastewater treatment plants ranged between C3.38H7O1.91 N0.21 and C3.91H7O2.04N0.16. The predicted composition based on mass balances is therefore within 5% of the average measured composition providing persuasive validation of the model.     

Electro-Fenton as a feasible advanced treatment process to produce reclaimed water.

The feasibility of the electro-Fenton process to generate simultaneously both of the Fenton's reagent species (Fe2+/H2O2), was assessed as a potentially more economical alternative to the classical Fenton's reaction to produce reclaimed water. An air-saturated combined wastewater (mixture of municipal and laboratory effluents) was treated in discontinuous and continuous reactors at pH = 3.5. The discontinuous reactor was a 2 L electrochemical laboratory cell fitted with concentric graphite and iron electrodes. The continuous reactor tests used a pilot treatment system comprising the aforementioned electrochemical cell, two clarifiers and one sand filter. Several tests were carried out at different conditions of reaction time (0-60 min) and electrical current values (0.2-1.0 A) in the discontinuous reactor. The best operating conditions were 60 min and 1 A without filtration of effluents. At these conditions, in discontinuous and continuous reactors with filtration, the COD, turbidity and color removal were 65-74.8%, 77-92.3% and 80-100%, respectively. Fecal and total coliforms, Escherichia coli, Shigella and Salmonella sp. were not detected at the end of the pilot treatment system. Electrogeneration of the Fenton's reagent is also economical; its cost is one-fifth the cost reported for Advanced Primary Treatment.     

Effect of support and second metal in catalytic in-situ generation of hydrogen peroxide by Pd-supported catalysts: application in the removal of organic pollutants by means of the Fenton process

A catalytic system for the generation of H2O2 from formic acid and oxygen at ambient conditions has been developed. Pd-supported catalysts (Pd/C, Pd/TiO2 and Pd/Al2O3) have been tested, showing that for bulk purposes Pd/Al2O3 is more favourable while for in-situ applications Pd/TiO2 seems to be preferable. However, when these catalysts were tested in the in-situ H2O2 generation for the oxidation of phenol by means of the Fenton process (in the presence of ferrous ion), Pd/TiO2 did not demonstrate the expected results, whereas Pd/Al2O3 showed to be an efficient catalyst. Therefore, Pd/Al2O3 is offered as a good catalyst for Fenton's reactions with in-situ generated H2O2. In order to optimize the operating cost of the process, different initial concentrations of formic acid have been tested with Pd/Al2O3, and it has been seen that lowering the initial amount of formic acid favours the efficiency of the process. The effect of the addition of a second metallic (Pt, Au, Fe, Cu) active phase was studied. Concerning H2O2 generation, best results were obtained with a Pd-Au catalyst for bulk production (long time) while for in-situ application Pd-Fe showed interesting results. The Pd-Fe catalyst also performed similarly to the semi-heterogeneous Fenton system involving Pd/Al2O3 and ferrous ion in the degradation of phenol. Therefore, Pd-Fe catalyst offered an interesting prospect for making a full heterogeneous catalyst for Fenton reaction involving in-situ generation of H2O2.     

Anaerobic treatment of Hong Kong leachate followed by chemical oxidation.

Landfill leachate of Hong Kong was first treated by the upflow anaerobic sludge blanket (UASB) process. At 37 degrees C, pH 7.1-8.5 and a HRT of 5.1-6.6 days, the process removed 66-90% of COD in the leachate for loading rates of 1-2.4 g-COD/l day depending on the strength of landfill leachate. The final effluent contained 1440-1910 mg-COD/l and 70-91 mg-BOD/l. About 92.5% of the total COD removed was converted to methane and the rest was converted to biomass with an average net growth yield of 0.053 g-VSS/g-COD-removed. The granules developed in the UASB reactor were 0.5-1.5 mm in size and exhibited good settleability. The UASB effluent was then further polished by two oxidation processes. The UASB-ozonation process removed 93.0% of the 12900 mg/l of COD from the raw leachate. The UASB-Fenton-ozonation process improved the COD removal efficiency to 99.3%. The final effluent had only 85 mg/l of COD and 10 mg/l of BOD5. Ozonation was most effectively conducted at pH 7-8 with the addition of 300 mg/l of H2O2 and for the duration of 30 min. Ozonation also significantly improved the biodegradability of the organic residues. Nearly 50% of these residues could be used as carbon source in denitrification.     

Treatment of low and medium strength sewage in a lab-scale gradual concentric chambers (GCC) reactor.

One of the major challenges of anaerobic technology is its applicability for low strength wastewaters, such as sewage. The lab-scale design and performance of a novel Gradual Concentric Chambers (GCC) reactor treating low (165+/-24 mg COD/L) and medium strength (550 mg COD/L) domestic wastewaters were studied. Experimental data were collected to evaluate the influence of chemical oxygen demand (COD) concentrations in the influent and the hydraulic retention time (HRT) on the performance of the GCC reactor. Two reactors (R1 and R2), integrating anaerobic and aerobic processes, were studied at ambient (26 degrees C) and mesophilic (35 degrees C) temperature, respectively. The highest COD removal efficiency (94%) was obtained when treating medium strength wastewater at an organic loading rate (OLR) of 1.9 g COD/L.d (HRT = 4 h). The COD levels in the final effluent were around 36 mg/L. For the low strength domestic wastewater, a highest removal efficiency of 85% was observed, producing a final effluent with 22 mg COD/L. Changes in the nutrient concentration levels were followed for both reactors.     

Low-temperature post-treatment of anaerobically treated-sewage in anaerobic filter with cationic-polymer addition.

The post-treatment of domestic sewage pretreated in a 6 m3 UASB was investigated in two high-rate anaerobic filter (AF) reactors operated in parallel. The difference between the two AF reactors was only the addition of cationic polymer to the second reactor (AF + P). The reactors were operated at low temperatures, ranged between 13 and 20 degrees C. The media in each AF reactor consisted of vertical sheets of reticulated-polyurethane foam (RPF) with knobs. The results demonstrated that the AF + P reactor (HRT = 3 h) with cationic polymer addition (2 mg/L) was an efficient system for post-treatment. The removal efficiencies for total, suspended, colloidal and dissolved COD were, respectively, 41, 86 and 76 and 12% in the AF + P reactor and they were, respectively, 80, 97, 77 and 66% in the UASB + (AF + P) system. The removal of total, suspended and colloidal COD in the UASB + (AF + P) system were significantly higher than those achieved in the UASB + AF system. As hardly any nutrient was removed in the UASB + (AF + P) system, the effluent after pathogen removal is a valuable product for irrigation and fertilisation to close the water and nutrients cycle.     

Enhanced degradation of paracetamol by UV-C supported photo-Fenton process over Fenton oxidation

For the treatment of paracetamol in water, the UV-C Fenton oxidation process and classic Fenton oxidation have been found to be the most effective. Paracetamol reduction and chemical oxygen demand (COD) removal are measured as the objective functions to be maximized. The experimental conditions of the degradation of paracetamol are optimized by the Fenton process. Influent pH 3, initial H(2)O(2) dosage 60 mg/L, [H(2)O(2)]/[Fe(2+)] ratio 60 : 1 are the optimum conditions observed for 20 mg/L initial paracetamol concentration. At the optimum conditions, for 20 mg/L of initial paracetamol concentration, 82% paracetamol reduction and 68% COD removal by Fenton oxidation, and 91% paracetamol reduction and 82% COD removal by UV-C Fenton process are observed in a 120 min reaction time. By HPLC analysis, 100% removal of paracetamol is observed at the above optimum conditions for the Fenton process in 240 min and for the UV-C photo-Fenton process in 120 min. The methods are effective and they may be used in the paracetamol industry.     

Ozonation of synthetic versus natural textile tannins: recalcitrance and toxicity towards Phaeodactylum tricornutum.

A sound in-plant pollution control strategy can only be defined by paying due attention to bio-recalcitrance and toxicity. In this context the levels of toxicity and inert COD introduced to textile dyebath discharges by two alternative auxiliary chemicals, namely natural tannin (NT) and synthetic tannin (ST), were investigated. The effect of 40 minutes ozonation at 1,000 mg h(-1) at pH 3.5 on the segregated effluent streams containing the above-mentioned tannin formulations was evaluated in terms of changes in toxicity and recalcitrance. The effect of ozonation on the COD distribution of raw and ozonated NT and ST samples according to their molecular weight cut-offs was also assessed. Both untreated tannin formulations exerted high acute toxicity towards marine microalgae Phaeodactylum tricornutum. Moderate decrease in the toxicity levels of both tannins was observed upon ozonation. The raw NT formulation with a COD content more than twice that of its alternative raw ST had an initially inert soluble COD content of only 25 mg/L, while the initially inert COD was 135 mg/L for ST. As the initially inert soluble COD content of NT was considerably lower, this textile auxiliary did not need chemical pretreatment to improve its biodegradability. On the other hand, the initially inert soluble COD content of ST was reduced by 70% by ozone pretreatment. In terms of residual COD contents achievable after passing through a biological treatment system, raw NT and pretreated ST formulations yielded 100 and 95 mg/L COD, respectively. The highest proportion of COD (46% for NT and 88% for ST) was found in the <1 kDa range. The same fraction increased to 93% for NT after ozonation, while for ST no significant change was observed in the COD distribution of the molecular weight cut-offs after ozonation.