Acute toxicity removal in textile finishing wastewater by Fenton's oxidation, ozone and coagulation-flocculation processes

This study evaluates the effectiveness of Fenton's oxidation (FO) process and ozone (O3) oxidation compared with a coagulation-flocculation (CF) process to remove effluent toxicity as well as colour and COD from a textile industry wastewater. Daphnia magna was used to test acute toxicity in raw and pre-treated wastewater. The operational parameters for each process were determined on the basis of complete toxicity removal. The FO process removed COD at a higher rate (59%) than O3 (33%) while colour removal was similar (89% and 91%, respectively). The CF process removed both COD and colour at rates similar to the FO process. A colour range of 150-250 platin-cobalt (Pt-Co) unit was assessed for toxicity.     

Comparison of the ozonation and Fenton process performances for the treatment of antibiotic containing manure

An integrated treatment method based on magnesium salt extraction followed by chemical oxidation was used for the treatment of a veterinary antibiotic, oxytetracycline (OTC) contaminated cow manure since animal manure can be an important source for antibiotic pollution in the environment. Pretreatment with magnesium salt enhanced the efficiencies of subsequent oxidation processes by extracting 63.9% of OTC from the manure thereby making it more favorable for oxidation with the hydroxyl radicals produced by the Fenton and ozone oxidation processes. Both the 24 h Fenton oxidation process with 434 mM H₂O₂ and 43.4 mM Fe²⁺ doses and the 1-h ozonation process with an applied ozone dose of 2.5 mg min^− 1 provided more than 90% OTC removal from the manure slurry. However, the second-order OTC removal rate constant of Fenton process (119 M^− 1s^− 1) was remarkably lower than that obtained with the ozonation process (548 M^− 1s^− 1). The oxidant dose was a significant factor for the efficiency of the Fenton treatment but not for the ozone treatment. The efficiencies of both the Fenton and ozone oxidation processes were not affected by the pH adjustment of the manure slurry.     

Treatment of olefin plant spent caustic by combination of neutralization and Fenton reaction

Spent caustic from olefin plants contains much H2S and some mercaptans, phenols and oil. A new treatment process of spent caustic by neutralization followed by oxidation with Fenton's reagent (Fe2+/H2O2) was successfully developed. Over 90% of dissolved H2S were converted to gas phase by neutralization at pH = 5 and T = 70 degrees, and the vent gas stream could be introduced to sulfur recovery plant. The neutralized liquid was oxidized with OH. free radical, which was provided by a Fenton's reagent. The residual sulfides in the neutralized spent caustic were oxidized to less than 0.1 mg/L. The total COD removal of spent caustic is over 99.5% and the final COD value of the effluent can be lower than 100 mg/L under the following oxidation conditions: reaction time = 50 min, T = 90 degrees, Fe2+ = 100 mg/L, and a stoichiometric H2O2/COD = 1.1. The value is better than the 800 mg/L value obtained by common WAO process. The optimum pH of the Fenton reaction is around 2 for this process, and the oxidation step can maintain a pH value in the range of 1.8-2.4. Moreover, the iron catalyst can be recycled without affecting process effectiveness thus preventing secondary pollution.     

Electro-oxidative abatement of low-salinity reverse osmosis membrane concentrates

The present study encompasses the application of electrolysis as novel treatment technique for the abatement of low-salinity concentrates generated from the filtrative treatment of water and wastewater. Four different materials have been tested as anode for a number of brine samples in a one-compartment electrolytic cell in galvanostatic mode. It was found that PbO(2) and SnO(2) anodes initiated electrochemical precipitation through an increase of the pH. Boron-doped diamond (BDD) and RuO(2) anodes successfully oxidised the pollutants in the brine and a linear removal of total ammonia nitrogen (TAN) and chemical oxygen demand (COD) was observed during the first phase of oxidation. Oxidation was predominantly achieved through indirect hypochlorite bulk oxidation; the higher oxidation rate and extent for the BDD anode was attributed to the higher selectivity and activity of the latter. Overall performance of the BDD electrode was higher than for RuO(2): higher rates for TAN (17.9 vs. 13.5mg/Ah) and COD (74.5 vs. 20.0mg/Ah) removal as well as higher overall current efficiencies (35.2% vs. 14.5%). Extensive colour removal was observed for both anodes (>90% decrease in absorbency at 455 nm).     

Treatment of landfill leachate using Fenton process and coagulation/flocculation

Coagulation/flocculation process, Fenton oxidation and combinations between them were studied, aiming to provide an efficient method for the treatment of partially stabilized leachates. Leachates were collected from a municipal landfill site, samples containing around 3800 mg/L COD, BOD₅/COD ratio about 0.11 and pH around 8. The sequence of stages implemented was: (a) coagulation/flocculation; (b) Fenton oxidation; (c) coagulation/flocculation followed by Fenton oxidation which resulted in a best COD removal (63.62%) and (d) Fenton oxidation followed by coagulation/flocculation.     

电解氧化处理垃圾渗滤液研究

采用电解氧化法对垃圾渗滤液进行深度处理的研究结果表明,电解氧化过程中,NH3－N优先于COD被氧化去除;SPR三元电极的处理效果优于DSA二元电极和石墨电极;酸性条件比碱性条件更有利于电解氧化作用对COD及NH3－N的去除;Cl^-浓度高时,有利于COD及NH3－N被氧化去除。试验得到的适宜电解氧化条件是：pH值为4、Cl^-浓度为5000mg/L、电流密度为10A/dm^2、SPR三元电极为阳极、电解时间为4h。当COD及NH3－N浓度分别为693mg/L和263mg/L时,COD去除率为90．6％,NH3－N的去除率为100％。     

铁炭Fenton/SBR法处理硝基苯制药废水

为探寻硝基苯废水的适宜处理工艺，开展了铁炭Fentort／SBR工艺处理硝基苯制药废水的试验研究。结果表明，铁炭内电解结合Fenton氧化的预处理工艺可有效去除废水中的硝基苯类物质，并提高了废水的可生化性。当原水的pH值为2～3、H2O2投加量为500～600mg／L时，调节预处理出水pH值至7～8并经沉淀处理后，对COD和硝基苯类物质的总去除率分别可达47％和92％。后续混合废水经SBR工艺处理后出水水质能满足国家污水排放标准。     

Ozonation kinetics of cork-processing water in a bubble column reactor

The oxidative degradation of organic pollutants present in cork-processing water at natural pH (6.45) was studied in a bubble column ozonation reactor. A steady reduction in both chemical oxygen demand (COD) and total organic carbon (TOC) was observed under the action of ozone alone and the feasibility of deep mineralisation (organic matter removal more than 90% in 120 min under the following experimental conditions: liquid volume 9L; superficial gas velocity 6.8x10(-3) m s(-1); ozone partial pressure 1.31 kPa; initial COD 328 mg L(-1); initial TOC 127 mg L(-1)) was demonstrated. The monitoring of pH, redox potential (ORP) and the mean oxidation number of carbon (MOC) was correlated with the oxidation and mineralisation of the organic species in the water. The ozonation of cork-processing water in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modelled by the two-film theory of mass transfer and chemical reaction. Under the experimental conditions used, and in contrast with the literature, it was determined that the reaction follows a fast kinetic regime at the beginning of the oxidation process, shifting to the moderate and the slow kinetic regimes at later stages of the oxidation reaction. The dynamic change of the rate coefficient estimated by the model was correlated to changes in the water composition.     

Stabilized leachates: ozone-activated carbon treatment and kinetics

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3–1.5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1×10⁻³ molL⁻¹ ozone inlet feeding concentration and 50 Lh⁻¹ gas flow-rate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 gL⁻¹. Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models.     

Fenton试剂氧化法深度处理焦化废水的研究

以实际焦化废水经A2O工艺处理后的出水为研究对象,考察了Fenton试剂氧化法深度处理焦化废水的效果和影响因素。结果表明,Fenton试剂氧化法对焦化废水具有良好的深度处理效果,在进水COD为100～340mg/L、色度为480～940倍的条件下,出水COD和色度等指标均可达到《城市污水再生利用工业用水水质》(GB/T19923—2005)的要求。在试验条件下,最佳的反应参数:初始pH值为2.5,反应温度为40～50℃,Fe2+投加量为0.4mmol/L,反应时间为2～3h,H2O2投加量为4～8mmol/L。     

废塑料造粒洗气废水处理工程实例

废塑料造粒生产过程中的废气采用水吸收作为预处理,会产生高浓度难降解有机废水。先通过气浮去除水中浮油、悬浮物,再经过Fenton氧化预处理,提高其可生化性,然后采用UASB+接触氧化工艺处理,最后用次氯酸钠去除部分氨氮,其出水水质达到所在工业园区污水厂纳管标准(COD≤350 mg/L、NH₃-N≤50 mg/L、甲苯≤0.2 mg/L)。工程调试运行结果显示,COD、NH₃-N和甲苯平均去除率分别达96.1%、89.9%、99.8%,在技术上和经济上是可行的。     

Complete treatment of olive pomace leachate by coagulation, activated-carbon adsorption and electrochemical oxidation

A battery scheme comprising sequential alum coagulation, activated-carbon adsorption and electrochemical oxidation over boron-doped diamond electrodes to mineralize a leachate from olive pomace processing is demonstrated. The effect of coagulant and adsorbent concentration on treatment efficiency was assessed in the range 0.1-50 mM Al(3+) and 2.5-50 g/L activated-carbon and optimal conditions were established. Coagulation at 7.5mM Al(3+) resulted in substantial solids and color removal (i.e. 80% and 93%, respectively). This was accompanied by only 30% chemical oxygen demand (COD) reduction (initial COD was about 3,500 mg/L). The latter increased to 80% though when coagulation was coupled with adsorption at 25 g/L activated carbon. Electrochemical oxidation of the original effluent for 360 min led to 63% and 82% COD reduction at 10 and 20A current intensity, respectively. When this process was tested as a polishing stage following coagulation and adsorption, overall COD removal reached values of 92% and 97%, respectively. The final effluent was also colorless and solids free. However, the treated effluent still exhibited ecotoxicity possibly due to the formation of ecotoxic oxidation products.     

Catalytic degradation of CH2O and C6H5CH2OH in wastewaters

The heterogeneous oxidation of benzyl alcohol and formaldehyde in aqueous medium has been investigated. The catalytic oxidation of these compounds is carried out in the presence of Ni-oxide system at ambient temperature. The results show that under studied conditions, a 90% conversion of CH2O to CO2 and a complete oxidation of C6H5CH2OH to C6H5COOH is achieved. Addition of H2SO4 to adjust pH to 2 further precipitates benzoic acid. The precipitate is filtered and the resulting filtrate is free of organic substances (COD is below 10 mg O2 dm(-3)). Based on the results obtained, a technology for purification of wastewaters containing benzyl alcohol as well as a catalytic method for degradation of CH2O in aqueous solutions have been developed.     

Oxidation of enrofloxacin with conductive-diamond electrochemical oxidation, ozonation and Fenton oxidation. A comparison

The treatment of enrofloxacin synthetic wastewaters using conductive-diamond electrochemical oxidation (CDEO), ozonation and Fenton oxidation has been studied. Results show that the three technologies can reduce the organic content of enrofloxacin synthetic wastewaters but with different performances. CDEO was the most efficient technology in terms of mineralization but not on COD removal, which was more efficiently achieved by ozonation. This indicates that ozonation is efficient in the breakage of the complex molecules but not on the removal of final carboxylic acids. The high initial efficiency in terms of oxidant-use obtained by Fenton oxidation evidences that it is very efficient in the removal of the enrofloxacin, although it rapidly leads to the formation of refractory compounds to the treatment. This indicates the significance of other oxidation mechanisms (e.g. coagulation) that enhance the results obtained by the expected hydroxyl-mediated oxidation. Ammonium ions were the primary product species in CDEO and nitrate ions in ozonation, whereas Fenton effluents contained similar amounts of both nitrogen ionic species.     

Aged raw landfill leachate: membrane fractionation, O3 only and O3/H2O2 oxidation, and molecular size distribution analysis

Large molecular refractory organic compounds (i.e., humic substances) were the major chemical oxygen demand (COD) components of aged raw landfill leachate. To investigate the behaviours of the large molecular refractory organic compounds when they were subjected to oxidation with ozone only (O3 only) and ozone combined with hydrogen peroxide (O3/H2O2), the aged raw landfill leachate first was filtered with 0.8 and 0.45 microm pore size filters in series, then was sequentially fractionated with 10,000 MWCO; 5000 MWCO; and 1000 MWCO membranes, and four samples were formed: 0.45 microm-10,000 Da; 10,000-5000 Da; 5000-1000 Da; and < 1000 Da. Mass distribution profiles of COD, 5-day biochemical oxygen demand (BOD5), colour and metals in the aged raw leachate were developed through mass balance. After membrane fractionation of the aged raw leachate, the metals were fractionated with the humic substances. Each fractionated sample as well as the aged raw leachate was oxidised with O3 only and O3/H2O2. The H2O2 enhanced the reduction of COD and colour; while, the BOD5 after O3 only was always higher than that of O3/H2O2. The addition of H2O2 improved the peak reduction of large molecules, but the effects of H2O2 on the fractions of 10,000-5000 Da and 5000-1000 Da were likely insignificant, which is in accordance with the COD results. No correlation was found between the BOD5 increase and the area of new peak formed after oxidation. However, the BOD5 of each sample after oxidation with O3 only was the logarithmic function of its total peak area.     

Mineralization of some natural refractory organic compounds by biodegradation and ozonation

The objective of this study was to explore the extent of mineralization, reduction in color and reduction of COD of gallic acid, tannin and lignin by ozonation and a combination of aerobic biodegradation and ozonation. Ozonation of pure aliquots (phase I experiments) resulted in the decline in TOC, COD, COD/TOC ratio, UV absorbance at 280 nm and color of the three model compounds investigated, with COD removals of greater than 80% and high removals (>90%) of UV absorbance at 280 nm and color observed in all cases at an ozone dose of 6 mg ozone/mg initial TOC or higher. Aerobic biodegradation of pure gallic acid, tannin and lignin aliquots resulted in COD decline of approximately 36-38%. Subsequent ozonation (phase II experiments) resulted in further decline in TOC, COD, COD/TOC ratio, and increase in UV absorbance at 280 nm and color removals. COD and TOC removals comparable to phase I experiments were obtained with 30-40% lower ozone absorption in phase II experiments. The biodegradation step was quite effective in removing specific UV absorbance at 280 nm, with up to 75% removal observed. Subsequent ozonation increased overall specific UV absorbance at 280 nm to greater than 90%.     

Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.     

Treatment of biorefractory organic compounds in wool scour effluent by hydroxyl radical oxidation

Wool scouring effluent that had been treated with chemical flocculation and aerobic biological treatment (Sirolan CFB effluent) was tertiary treated by hydroxyl radical oxidation to remove residual organic compounds. These compounds impart a high chemical oxygen demand of 500-3000 mg/L and dark colour. However, a H2O2/UV process was found to effectively treat the majority of residual compounds, with up to 75% COD, 85% total organic carbon, and 100% removal of colour (T(480 nm)) achieved. This was despite the effluent being strongly absorbing in the UV region, with a film thickness of 0.21 mm reducing T(254 nm) by 50%. Treatment was unaffected by pH over the range 3-9. H2O2/UV treatment increased the biodegradability of the effluent (5-day biochemical oxygen demand increased from < 10 to 86 mg/L), but a combined chemical and biological process did not increase maximum COD removal or overall process efficiency. The tertiary treated effluent had a final COD in the range 125-750 mg/L, equating to a total COD removal from raw wool scour effluent of approximately 97.5%. This degree of treatment is sufficient for discharge in many, but not all, circumstances.     

聚氯乙烯离心母液的处理及回用

采用接触氧化法处理悬浮法生产聚氯乙烯产生的离心母液,工程实践表明:离心母液经接触氧化工艺处理后COD去除率>85%,出水COD<50mg/L;再经过砂滤、臭氧氧化、活性炭过滤等深度处理后,出水COD、pH、浊度、电导率均达到回用要求。深度处理费用低于自来水基本水费(天津),也低于用自来水制备脱盐水的费用。     

Elimination of resin acids by advanced oxidation processes and their impact on subsequent biodegradation

Wood pulping and paper production generate a considerable amount of wastewater, containing many pollutants among them resin and fatty acids. Resin acids contribute substantially to effluent toxicity and were identified to be detrimental to microorganisms of activated sludge and in particular to bacteria in anaerobic wastewater treatment system and other forms of aquatic life. The objective of the present study was to check the applicability of the ozone and advanced oxidation processes (AOPs) to eliminate resin acids from aqueous solutions and to determine the ozone dose required. Furthermore, an investigation of the influence of the oxidation methods on subsequent biological destruction of the byproducts was performed. Aqueous solution of the resin acids: abietic, dehydroabietic and isopimaric acids with different initial composition were subjected to ozonation or AOP processes at different ozone doses. After ozonation or advanced oxidation pretreatment the model solutions were biodegraded in aerated vessels containing activated sludge. During ozonation of the resin acids aqueous solutions the resin acids were almost eliminated, however the reduction of chemical oxygen demand (COD) was rather low. The ozone dose required to obtain reduction of resin acids >90% was in the range of 0.1-0.7mgO(3)/mgCOD, depending on the composition and concentration of model solutions. The toxicity of ozonated resin acids solutions decreased with increasing applied ozone dose up to about 0.3-0.5mgO(3)/mgCOD, thereafter increased. Ozonation and other AOP processes did not increase the rate of biodegradation of resin acids model solutions in aerated activated sludge systems compared to not pretreated solutions.