Treatment of textile dyehouse wastewater by TiO2 photocatalysis

The oxidative degradation of an actual textile dyehouse wastewater was investigated by means of photocatalysis in the presence of TiO2. The UV-A-induced photocatalytic oxidation over TiO2 suspensions was capable of decolorizing the effluent completely, as well as reducing chemical oxygen demand (COD) sufficiently (COD reduction generally varied between about 40% and 90% depending on the operating conditions) after 4 h of treatment. Two crystalline forms of TiO2, viz. anatase and rutile, were tested for their photocatalytic activity and anatase was found to be more active than rutile. The extent of photocatalytic degradation was found to increase with increasing TiO2 concentration up to 0.5 g/L TiO2, above which degradation remained practically constant, reaching a plateau. Furthermore, textile effluent degradation was enhanced at acidic conditions (i.e. pH = 3) and in the presence of hydrogen peroxide. To assess catalyst activity on repeated use, experiments were performed where the catalyst was recovered and reused; after three successive uses, TiO2 had sufficiently retained its photocatalytic activity. Finally, the luminescent marine bacteria Vibrio fischeri was used to assess the acute ecotoxicity of samples prior to and after the photocatalytic treatment and it was found that ecotoxicity was fully eliminated following photocatalytic oxidation.     

Photocatalytic degradation of reactive black 5 in aqueous solutions: Effect of operating conditions and coupling with ultrasound irradiation

The degradation of reactive black 5 (RB 5), a representative diazo dye found in textile effluents, by means of ultraviolet irradiation (9W UVA) over TiO(2) suspensions, ultrasound irradiation (80kHz, 135W) and their combined application was investigated. Several commercial TiO(2) catalysts were screened and an anatase Hombicat UV 100 sample exhibited considerable activity in terms of solution decoloration, COD and ecotoxicity reduction. Photocatalytic degradation increased with increasing TiO(2) loading (in the range 0.05-1g/L) and decreasing dye concentration (in the range 120-20mg/L) and solution pH (in the range 9-2.6). At the typical conditions employed in this study (60mg/L dye, 0.25mg/L catalyst, ambient pH=5.8, oxygen sparging), complete decoloration was achieved after 60min of reaction. Addition of H(2)O(2) up to 0.01M hindered degradation, scavenging the photogenerated holes and hydroxyl radicals. Ultrasound irradiation resulted in low decoloration, e.g. less than 10% after 60min at 60mg/L dye and oxygen sparging and slightly improved under an argon atmosphere. The simultaneous application of ultraviolet and ultrasound irradiation resulted in increased decoloration compared to that achieved by photocatalysis and sonolysis operating separately; moreover, the overall sonophotocatalytic effect was greater than the additive effect of the two processes, implying possible synergy.     

Advanced oxidation of a reactive dyebath effluent: comparison of O3, H2O2/UV-C and TiO2/UV-A processes

In the present study the treatment efficiency of different AOPs (O3/OH- H2O2/UV-C and TiO2/UV-A) were compared for the oxidation of simulated reactive dyebath effluent containing a mixture of monochlorotriazine type reactive dyes and various dye auxiliary chemicals at typical concentrations encountered in exhausted reactive dyebath liquors. A525 (color), UV280 (aromaticity) and TOC removal rates were assessed to screen the most appropriate oxidative process in terms of reactive dyebath effluent treatment. Special emphasis was laid on the effect of reaction pH and applied oxidant (O3, H2O2) dose on the observed reaction kinetics. It was established that the investigated AOPs were negatively affected by the Na2CO3 content (= 867 mg/L) which is always present at high concentrations in dychouse effluents since it is applied as a pH buffer and dye fixation agent during the reactive dyeing process. The ozonation reaction exhibited almost instantaneous decolorization kinetics and a reasonable TOC reduction rate. It appeared to be stable under the investigated advanced oxidation conditions and outranked the other studied AOPs based on the above mentioned criteria. Besides, the electrical energy requirements based on the EE/O parameter (the electrical energy required per order of pollutant removal in 1 m3 wastewater) was calculated for the homogenous AOPs in terms of decolorization kinetics. In view of the electrical energy efficiency, ozonation and H2O2/UV-C oxidation at the selected treatment conditions appear to be promising candidates for full-scale dyehouse effluent decolorization.     

Kinetic characteristics of bacterial azo-dye decolorization by Pseudomonas luteola

A Pseudomonas luteola strain expressing azoreductase activity was utilized to remove the color of an azo dye (reactive red 22) from contaminated solutions. The effects of substrate concentrations, medium compositions, and operation parameters (e.g., pH, temperature, dissolved oxygen, etc.) on decolorization of the azo dye by a P. luteola strain were systematically investigated to reveal the key factors that dominate the performance of azo-dye decolorization. The metabolites resulting from bacterial decolorization were analyzed by high-performance liquid chromatography (HPLC) and mass spectrometery (MS). The results show that the dissolved oxygen and glucose concentration retarded decolorization of reactive red 22 by P. luteola. The optimal azo-dye decolorization occurred at 37 degrees C, while more rapid decolorization took place over pH 7-9. Yeast extract and tryptone strongly enhanced the decolorization. The Michaelis-Menten model can satisfactorily describe the dependence of specific decolorization rate on the concentration of substrate (reactive red 22 or yeast extract). Decolorization of the azo dye by intact cells of P. luteola was essentially independent of the growth phase, whereas the azoreductase activity of the cell-free extract decreased in the order of late-stationary phase > early-stationary phase > mid-log phase. This suggests that mass transfer of the azo dye across the cell membrane may be the rate-limiting step. The HPLC and MS analyses suggest that both partial reduction and complete cleavage of the azo bond could contribute to decolorization of reactive red 22 by P. luteola.     

Treatment of textile waste effluents by ozonation and chemical coagulation

Ozonation experiments in a multiple reactor system were conducted to investigate the efficiency of this process in reducing the color and chemical oxygen demand of the textile waste effluents. It has been observed that decolorization of those waste effluents can be achieved in less than 10 min in all tested cases. In conjunction with chemical coagulation, the chemical oxygen demand of those waste effluents can be consistently reduced by up to 70% or more. Ozonation is capable of decomposing the highly structured dye molecules into smaller ones which can be easily biodegraded in an activated sludge process. Hence combination of ozonation, chemical coagulation and the activated sludge processes can provide a very effective means for dealing with this particular type of industrial waste effluent.     

Investigation of isolation and immobilization of a microbial consortium for decoloring of azo dye 4BS

Eight high-effective decolorization strains were isolated by enrichment using Direct Fast Scarlet 4BS as sole source of carbon and energy. The optimal microbial consortium consisting of fungus 8-4(*) and bacterium 1-10 was selected by optimizing combination decolorization experiments with these eight freely suspended strains, whose decolorization activity was higher than individual strains due to synergistic reaction with each other. The optimal microbial consortium was also immobilized using polyvinyl alcohol (PVA) as the carrier. This paper optimized the immobilization and operational conditions, investigated the effect of the environmental factors (temperature, pH and dissolved oxygen (DO)) and initial dye concentration on the rate of decolorization by immobilized microbial consortium. The results showed that the optimal decolorization activity was observed in pH range (5-8), temperature range (25-40 degrees C) under shaking culture of high DO level. Decolorization with the optimal microbial consortium gave a relatively high maximum decolorization activity (ca. 81.25 mgl(-1)h(-1)), which occurred at a dye concentration of 1000 mgl(-1), suggesting the applicability of the strains in remediation of wastewater containing high azo dye concentrations. The immobilized beads could be reused for more than 30 cycles, without losing any degradation capacity. The changes of UV-visible spectra and the change curve of COD of 4BS solution before and after decolorization cultivation and the proliferation and distribution of microbial consortium in gel beads were also microscopically observed, which could be used for conferring the decolorization mechanisms of dye 4BS.     

Optimal aeration control in a nitrifying activated sludge process

An important tool to minimise energy consumption in activated sludge processes is to control the aeration system. Aeration is a costly process and the dissolved oxygen level will determine the efficiency of the operation as well as the treatment results. What aeration control should achieve is closely linked to how the effluent criteria are defined. This paper explores how the aeration process should be controlled to meet the effluent discharge limits in an energy efficient manner in countries where the effluent nitrogen criterion is defined as average values over long time frames, such as months or years. Simulations have been performed using a simplified Benchmark Simulation Model No. 1 to investigate the effect of different levels of suppressing the variations of the effluent ammonium concentration. Optimisation is performed where the manipulated variable for aeration (the oxygen transfer coefficient, K_La) is minimised with the constraint that the average daily flow-proportional ammonium concentration in the effluent should reach a desired level. The optimisation results are compared with constant dissolved oxygen concentrations and supervisory ammonium control with different controller settings. The results demonstrate and explain how and why energy consumption can be optimised by tolerating the ammonium concentration to vary around a given average value. In these simulations, the optimal oxygen peak-to-peak amplitude range between 0.7 and 1.8 mg/l depending on the influent variation and ammonium level in the effluent. These variations can be achieved with a slow ammonium feedback controller. The air flow requirements can be reduced by 1-4% compared to constant dissolved oxygen set-points. Optimal control of aeration requires up to 14% less energy than needed for fast feedback control of effluent ammonium.     

Electrochemical oxidation of table olive processing wastewater over boron-doped diamond electrodes: treatment optimization by factorial design

The electrochemical treatment of an effluent from edible olive processing over boron-doped diamond electrodes was investigated. The effect of operating conditions, such as initial organic loading (from 1340 to 5370 mg/L chemical oxygen demand (COD)), reaction time (from 30 to 120 min), current intensity (from 5 to 14 A), initial pH (from 3 to 7) and the use of 500 mg/L H2O2 as an additional oxidant, on treatment efficiency was assessed implementing a factorial experimental design. Of the five parameters tested, the first three had a considerable effect on COD and total phenols removal, while the other two were statistically insignificant. In most cases, high levels of phenols degradation and decolorization were achieved followed by moderate mineralization. The analysis was repeated at more intense conditions, i.e., initial COD up to 10,000 mg/L, reaction times up to 240 min and current up to 30 A; at this level, the effect of treatment time and applied current was far more important than the starting COD concentration. Treatment for 14 h at optimal conditions (30 A and an initial loading of about 10,000 mg/L) led to 73% COD removal with a zero-order kinetic constant of 8.5mg/(L min) and an energy consumption efficiency of 16.3 g COD/(m3 A h).     

Removal of dyes from a synthetic textile dye effluent by biosorption on apple pomace and wheat straw

This paper deals with two low-cost, locally available, renewable biosorbents; apple pomace and wheat straw for textile dye removal. Experiments at total dye concentrations of 10, 20, 30, 40, 50, 100, 150, and 200 mg/l were carried out with a synthetic effluent consisting of an equal mixture of five textile dyes. The effect of initial dye concentration, biosorbent particle size, quantity of biosorbent, effective adsorbance, dye removal and the applicability of the Langmuir and Freundlich isotherms were examined. One gram apple pomace was found to be a better biosorbent, removing 81% of dyes from the synthetic effluent at a particle size of 2 mm x 4 mm and 91% at 600 microm. Adsorption of dyes by apple pomace occurred at a faster rate in comparison to wheat straw. Both the isotherms were found to be applicable in the case of dye adsorption using apple pomace.     

Wet air oxidation of table olive processing wastewater: determination of key operating parameters by factorial design

The wet air oxidation of an effluent from edible olive processing was investigated. Semibatch experiments were conducted with 0.3L of effluent loaded into an autoclave and pure oxygen fed continuously to maintain an oxygen partial pressure of 2.5MPa. The effect of operating conditions, such as initial organic loading (from 1240 to 5150mg/L COD), reaction time (from 30 to 120min), temperature (from 140 to 180 degrees C), initial pH (from 3 to 7) and the use of 500mg/L H(2)O(2) as an additional oxidant, on treatment efficiency was assessed implementing a factorial experimental design. All five parameters had a statistically considerable effect on COD removal, alongside second order interactions of COD with reaction temperature, contact time and effluent pH. In most cases, high levels of phenols degradation (up to 100%) and decolorization (up to 90%) were achieved followed by low to moderate mineralization (up to 70%). The oxidation of phenols was affected to a considerable level by the initial COD, reaction temperature and contact time, as well as the second order interaction between COD and temperature, while all other effects were insignificant.     

IC反应器在微氧条件下的运行特性研究

采用人工合成废水对IC反应器在微氧和厌氧条件下去除COD的效果、沼气产量、出水VFA、颗粒污泥粒径分布及颗粒污泥浓度等进行对比试验研究.结果表明:在进水COD分别为1 000、2 000、2 600、3 300、4 000 mg/L时,与厌氧相比,微氧时(溶解氧控制在0.5～1.0 mg/L)对COD的去除率分别增长了4.0%、4.0%、2.6%、1.5%、0.9%,沼气产量分别增长了160.0%、137.0%、78.0%、90.5%、50.9%;两种条件下的出水VFA均在200 mg/L以下,但与厌氧相比,微氧的出水VFA值更低、波动更小、变化更平稳;微氧时颗粒污泥的MLSS减少了3.6%,而MLVSS/MLSS值增长了0.6%,表明颗粒污泥的活性增强.     

Fate of dissolved organic nitrogen in two stage trickling filter process

Dissolved organic nitrogen (DON) represents a significant portion of nitrogen in the final effluent of wastewater treatment plants (WWTPs). Biodegradable portion of DON (BDON) can support algal growth and/or consume dissolved oxygen in the receiving waters. The fate of DON and BDON has not been studied for trickling filter WWTPs. DON and BDON data were collected along the treatment train of a WWTP with a two-stage trickling filter process. DON concentrations in the influent and effluent were 27% and 14% of total dissolved nitrogen (TDN). The plant removed about 62% and 72% of the influent DON and BDON mainly by the trickling filters. The final effluent BDON values averaged 1.8 mg/L. BDON was found to be between 51% and 69% of the DON in raw wastewater and after various treatment units. The fate of DON and BDON through the two-stage trickling filter treatment plant was modeled. The BioWin v3.1 model was successfully applied to simulate ammonia, nitrite, nitrate, TDN, DON and BDON concentrations along the treatment train. The maximum growth rates for ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria, and AOB half saturation constant influenced ammonia and nitrate output results. Hydrolysis and ammonification rates influenced all of the nitrogen species in the model output, including BDON.     

Decolorization of dark brown colored coffee effluent by solar photo-Fenton reaction: effect of solar light dose on decolorization kinetics

The decolorization of dark brown colored coffee effluent by solar photo-Fenton process has been studied. Effects of accumulated solar light energy and dosage of Fenton reagents (iron and hydrogen peroxide) on the color removal have been examined. With increasing Fe dosage the rate of the decolorization increased but the enhancement was not pronounced beyond 10 mg L⁻¹. Although addition of H₂O₂ increased the decolorization rate up to around 1000 mg L⁻¹ of H₂O₂, further addition of H₂O₂ could not enhance the color removal. At excess dosages of Fenton reagents, the color removal was not improved due to their scavenging of hydroxyl radicals. It was found that the pseudo-first order decolorization kinetic constant based on the accumulated solar energy is a sole parameter unifying solar photo-Fenton decolorization processes under the different weather conditions. The kinetic constant can be readily used to calculate the amount of solar energy required to achieve a certain degree of color removal. The mineralization was rather slower as compared with the decolorization. The decolorization capability with solar irradiation was found to be comparable to UV light irradiation. The present results suggest that abundant solar energy driving decolorization of coffee effluent by photo-Fenton reaction is highly efficient.     

UV light assisted decolorization of dark brown colored coffee effluent by photo-Fenton reaction

The photochemical decolorization of coffee effluent has been examined by photo-Fenton (UV/Fe²⁺/H₂O₂) process. Effects of UV light intensity, initial coffee concentration, iron dose and H₂O₂ dose on the color removal of model coffee effluent have been investigated. The rate of decolorization increased with decreasing initial coffee effluent concentration. It was found that the Fe ion dose and UV light intensity enhanced the decolorization rate. The decolorization process of coffee effluent could be divided into three established phases. At the beginning of the photo-Fenton process, the instantaneous and significant increase in color of the solution was found (Phase-I). In the subsequent phase (Phase-II), the decolorization rate was initially fast and subsequently decreased. In Phase-III, the rate was accelerated and then the complete decolorization of model coffee effluent was achieved. In order to elucidate the mechanisms of coffee effluent color removal process, the concentration changes in Fe³⁺ and Fe²⁺ besides H₂O₂ were measured during the course of the photo-Fenton process. The rate-determining step in Phase-II was the photo-Fenton reaction or photoreduction of Fe³⁺. On the other hand, the decolorization process in Phase-III was highly affected by Fenton reaction or decomposition of H₂O₂ with Fe²⁺. About 93% mineralization of 250 mg L⁻¹ model coffee effluent was achieved after 250 min. A comparative study for TiO₂, ZnO and photo-Fenton oxidation processes has been also carried out and the photo-Fenton process was found to be the most effective for color removal of coffee effluent.     

Optimum temperature shift for Nitrobacter winogradskyi: Effect of dissolve oxygen and nitrate concentrations

The temperature that maximizes the rate at which Nitrobacter winogradskyi oxidizes nitrite-nitrogen (i.e. the optimum temperature) was shown to have a complicated dependence on ambient dissolved oxygen and nitrite concentrations. In general, the optimum temperature shifted to lower values as dissolved oxygen and nitrite concentrations fell. A steep, almost linear drop in optimum temperature with decreasing values of the logarithm of nitrite concentration was found at dissolved oxygen concentrations above 0.1 ppm (gm⁻³ and nitrite-nitrogen concentrations below 10 ppm. A sharp nonlinear drop in optimum temperature with decreasing values of the logarithm of dissolved oxygen concentration occurred at dissolved oxygen concentrations below 1–2 ppm. At higher dissolved oxygen concentrations, the optimum temperature asymptotically approached a maximum value that increased with nitrite concentration. The solubility of oxygen placed an upper bound on the optimum temperature. At the dissolved oxygen and nitrite concentrations usually found in natural waters and domestic wastewaters, the rate of NO₂⁻-N oxidation should have an optimum temperature below 15°C and as a result should be thermally inhibited at higher temperatures. The negative thermal sensitivity of the NO₂⁻-N oxidation rate above 15°C means that nitrite accumulation may be a side-effect of elevated temperatures in some nitrifying systems.     

Advanced treatment of the reverse osmosis concentrate produced during reclamation of municipal wastewater

The work investigated the treatment of the concentrate produced from the reverse osmosis treatment of an MBR effluent. Two conventional chemical processes, coagulation and activated carbon adsorption, and three advanced oxidation processes (electrochemical treatment, photocatalysis and sonolysis) were applied. Coagulation with alum gave dissolved organic carbon (DOC) removals up to 42%, while FeCl(3) achieved higher removals (52%) at lower molar doses. Adsorption with granular activated carbon showed the highest DOC removals up to 91.3% for 5 g/L. The adsorption isotherm was linear with a non-adsorbable organic fraction of around 1.2 mg/L DOC. The three oxidation methods employed, electrolytic oxidation over a boron-doped diamond electrode, UVA/TiO2 photocatalysis and sonolysis at 80 kHz, showed similar behavior: during the first few minutes of treatment there was a moderate removal of DOC followed by further oxidation at a very slow rate. Electrolytic oxidation was capable of removing up to 36% at 17.8A after 30 min of treatment, sonolysis removed up to 34% at 135W after 60 min, while photocatalysis was capable of removing up to 50% at 60 min.     

CAST工艺处理城市污水的强化脱氮研究

介绍了镇江征润州污水处理厂CAST工艺的运行情况，结合该厂实际运行状况开展了强化脱氮效果的生产性试验研究。结果表明，该工艺对COD、SS和TP的去除率均能维持在80％以上，但对氨氮的去除效果较差；在该厂运行模式下，控制进水／曝气前30min的DO〈0．5mg／L、进水／曝气后30min的DO浓度在1．0-3．0mg／L、纯曝气DO浓度在2．0-3．0mg／L，可以实现同步硝化反硝化和硝化／反硝化作用下的共同脱氮，使脱氮效率提高了57％左右；在控制进水／曝气后DO〈0．5mg／L、纯曝气DO浓度在1．0-3．0mg／L的条件下，可以实现同步硝化反硝化作用下的脱氮，但较难实现理想的脱氮效果。     

Electrochemically assisted photocatalytic degradation of Acid Orange 7 with beta-PbO2 electrodes modified by TiO2

Modification of beta-PbO(2) electrodes was carried out by TiO(2) co-deposition and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The 2.0 g TiO(2) (the amount of TiO(2) used in 200 mL electrodeposition solution) modified beta-PbO(2) electrode was more compact and more uniform in comparison with the unmodified beta-PbO(2) electrode. TiO(2) particles were tightly attached on and between beta-PbO(2) crystals on modified beta-PbO(2) electrode. It was also used in electrochemically assisted photocatalytic degradation (EAPD) of Acid Orange 7. Compared with the total efficiency by a single application of ultraviolet irradiation and electrochemical procedure, application of a 1.5 V potential in EAPD improved the apparent first-order rate constant by 44.2% for 2.0 g TiO(2) modified beta-PbO(2) electrode even if it was not freshly used. A synergetic effect was significant. Within the amount of TiO(2) investigated, the more TiO(2) used in electro-deposition solution, the higher the degradation efficiencies were. Effects of initial dye concentration, initial pH values and applied potentials across the electrodes were investigated. Acidic condition and high potentials applied across the electrodes favored color or TOC removal of the dye. Decolorization rate decreased with an increase in the dye concentration in the range of 5-50mg/L. Experiments above demonstrate that TiO(2) modified beta-PbO(2) electrode, which realized TiO(2) immobilization successfully, performed well in EAPD of Acid Orange 7.     

Meeting the phosphorus consent with biological nutrient removal under UK winter conditions

It is estimated that up to 342 wastewater treatment plants (Wwtps) in England and Wales will require a phosphorus (P) consent by 2010. Although biological P removal is considered to be the most sustainable option for P removal, it has always been problematic for plants that remove both nitrogen and P due to the inadequate concentration of organic material during wet periods. Two biological nutrient removal (BNR) configurations, the Johannesburg (JHB) process and a combined JHB and five-stage Bardenpho process, were evaluated over a period of 2 years to assess the impact of sewage strength on bio-P removal. The JHB achieved an average effluent total phosphorus (TP) of 2.4 mg/L and the combined JHB and five-stage process averaged 1.4 mg/L effluent TP. The major problems affecting the performance of both configurations were: dissolved oxygen (DO) in the recycled mixed liquor, nitrate in the return activated sludge (RAS) and low influent biological oxygen demand (BOD) concentrations. Acetate dosing proved successful as a source of volatile fatty acids (VFAs) in the anaerobic zone during periods of low-strength sewage. An acetate dosing strategy based on the influent flow rate to the plant was found to be a simple and effective technique that ensured that a consent of <1 mg TP/L could be met.     

Photocatalytic degradation of non-steroidal anti-inflammatory drugs with TiO2 and simulated solar irradiation

The aim of this work is to evaluate and compare the degradation achieved for three non-steroidal anti-inflammatory drugs (NSAIDs) by heterogeneous TiO2 photocatalytic means in aqueous solution at laboratory scale. The selected pharmaceutical compounds were diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP). These compounds were used in their sodium salt chemical form. Previous experiments (adsorption, photolysis and thermodegradation) were developed to evaluate non-catalytic degradation for each NSAID. Photocatalytic experiments were carried out in a Xe-lamp reactor in order to study the influences of different operational conditions (catalyst load, temperature and dissolved oxygen concentration). These results showed that the optimum amount of TiO2, to achieve maximum degradation, of IBP was 1g/L. In contrast, the maximum degradation for DCF or NPX was observed at a TiO2 loading of 0.1g/L. Temperature had a significant effect only for NPX degradation, achieving almost 99% phototransformation. No significant differences were observed for DCF and IBP at 20, 30 and 40 degrees C. Dissolved oxygen concentration was an important parameter to increase the degradation for NPX and IBP. However, it was observed that its rate of mineralization did not increase. Intermediate metabolites were detected in all cases. Hydroxyl metabolites were the most important residual compounds after the photocatalytic treatment of IBP. The inhibition percentage of bioluminescence from Vibro fischeri--as a toxicity parameter--increased during the irradiation time due to the residual concentration of the hydroxyl metabolites generated. However, after 120 min, in experiments with 40 mg/L of dissolved oxygen, a decrease of the % inhibition was observed. Only photocatalytic treatment of IBP drives to a satisfactory biodegradability index BOD5/COD (between 0.16 and 0.42) and, only in this case, a post-biological treatment could be suggested.