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.     

An overview of the integration of ozone systems in biological treatment steps.

Despite the well-known potential and performance of combined biological and ozonation processes for wastewater treatment, only few full-scale applications are published. Beside the synergistic effects of such process combination, which lead to oxidation of recalcitrant and inhibitory compounds or intermediates by enhancement of their biodegradability, the key for raising applicability is the improvement of the ozonation efficiency. An overview about the history and progress of full-scale applications, which deals with combined ozonation and biological treatment is given. Recently more than 40 applications exist, but many of them are not published. Therefore, a couple of selected not yet published applications have been mentioned in this paper. Landfill leachate and industrial wastewater treatment were mostly applicated, while treatment of municial wastewater treatment plant (WWTP) effluents are of increasing interest due to several advantages such as disinfection, decolourisation and removal of persistent dissolved organic carbon (DOC) for water re-use and groundwater recharge.     

Ozone catalysed with solids as an advanced oxidation process for landfill leachate treatment.

Heterogeneous catalytic ozonation (HCO) of wastewater is gaining both research and industrial interests. It is proved to be an advanced oxidation process since it involves hydroxyl radicals as oxidation species. Few studies have been carried out to test HCO in the treatment of landfill leachates. This work has been carried out to test three types of catalysts: activated carbon (AC), expanded perlite (EP) and titanium dioxide (TiO2) combined with ozone at 80 g/m3 gas concentration for the treatment of a leachate generated by Jebel Chakir landfill site near Tunis-capital of Tunisia. The work has shown a reduction in COD of about 45% and an increase in biodegradability (BOD5/COD) from 0.1 to 0.34. A catalyst concentration of 0.7 g/L was found optimal for the treatment of the leachate.     

Recalcitrant COD degradation by an integrated system of ozonation and membrane bioreactor.

In order to treat wastewater to a low residual COD-concentration such as 125 mg/L, classical biological treatment is not sufficient for many types of industry. This research focused on the integrated treatment of the wastewater of the paper industry, with a membrane bioreactor (MBR) and an oxidation step. The optimal configuration was examined. Screening tests with different types of oxidation showed that ozonation after biological treatment could reduce the COD with 40% with an ozone dose of 0.4-0.8g O3/g COD. BOD/COD ratio could be increased up to 0.19. Neither combination of ozone with UV and/or hydrogen peroxide nor the process H2O2/UV or (photo-)Fenton reagents gave any improvement in COD reduction or BOD increase, unless the doses were very high. Based on these results, an integrated system MBR-ozonation was designed, with recirculation of MBR effluent over ozonation. This test showed that reduction of COD up to 125 mg/L immediately behind the MBR required a lot of ozone. A technically feasible solution was to discharge the water after an extra ozonation step, which resulted in a high total ozone dosage. The alternative, the consecutive treatment activated sludge-ozonation-activated sludge, did not give a better COD-removal with the same ozone dose as the integrated concept. The economic evaluation proves that the integrated chemical and biological treatment is expensive for the paper industry if a low discharge limit of COD has to be complied with.     

臭氧-活性炭深度处理滦河水的试验研究

对滦河水进行O3-GAC工艺深度处理中试研究表明O3-GAC能在较长时间内保持对水中有机物的去除,CODMn的平均去除率为60.19%;TOC的平均去除率为64%;UV254的平均去除率为70.41%;NH3-N的平均去除率为53.83%;对水中的浊度和色度都有明显的去除效果,尤其臭氧化对改善难生物降解有机物的可生化性有十分显著的作用;O3-GAC能有效地去除饮用水中的有害、有毒物质,提高饮用水的安全性.     

酸析—微电解—Fenton氧化预处理亚麻脱胶废水的研究

高浓度亚麻脱胶废水CODCr、色度都很高,不宜直接进行生物处理.试验采用酸析-微电解-Fenton氧化的预处理工艺,并对反应的影响因素进行了研究,试验结果表明,在pH=3,微电解90 min,H2O2投量1 500 mg/L,Fenton氧化120 min的条件下,CODCr去除率可以达到71.4%,色度去除率超过90%.同时该方法提高了废水的可生化性,有利于后续的生化处理.     

Effect of ozone, chlorine and hydrogen peroxide on the elimination of colour in treated textile wastewater by MBR.

In treating textile wastewater, the application of membrane bioreactor (MBR) technology showed high efficiency in COD and BOD5 removal. However, insufficient colour removal was achieved for possible reuse. The aim of the work presented in this paper was to test the performance of chemical advanced oxidation on the elimination of the colour downstream of an MBR. To improve the quality of the membrane bioreactor effluent three different oxidation treatments were tested at lab-scale: ozonation, chlorination and hydrogen peroxide oxidation. Colour, COD and BOD5 were controlled in order to assess the effectiveness of each process. For chlorination, even with 250 mg/L (active chlorine) only 80% colour removal (SACin = 14; SACout = 2.8) was achieved which is considered unsatisfactory. For hydrogen peroxide, the colour removal was even poorer; it was just 10% at a concentration of 250 mg/L. In contrast, good results were obtained by ozonation. By using only 38 mg/L within 20 minutes, it was possible to achieve the reuse recommendation with a satisfactory colour removal of 93% (SACin = 14; SACout = 0.98). The results showed that ozonation was the most promising method.     

Using ozone to reduce recalcitrant compounds and to enhance biodegradability of pulp and paper effluents.

The effect of ozone based oxidation on removing recalcitrant organic matter (ROM) and enhancing the biodegradability of alkaline bleach plant effluent was investigated. A bubble column ozonation tower was used in the study. The experiments were carried out at different temperatures (20 degrees C and 60 degrees C) and pH (9 and 11), with a number of biological and chemical parameters being monitored including BOD5, COD, TC, pH, color, and molecular weight distribution of organics (nominal cut off of 1,000 Da). Biodegradability of the effluent was determined based on BOD5/COD of the wastewater throughout the process. For all the experiments, ozonation enhanced the biodegradability of the effluent by 30-40%, which was associated with noticeable removal of ROM including high molecular weight (HMW) and color-causing organics by about 30% and 60%, respectively. While the biodegradability of HMW fraction increased by about 50%, there was no biodegradability improvement for low molecular weight (LMW) portion, which was originally readily biodegradable (with BOD5/COD of about 0.5). Statistical analysis of variance (ANOVA) revealed neither pH nor temperature played significant role on the ozonation process at 95% confidence level.     

Performance evaluation of physicochemical processes for biologically pre-treated livestock wastewater.

The use of a combination of biological and physicochemical methods is a promising technique to reduce highly concentrated pollutants in livestock wastewater: firstly, biodegradable organic matters, nitrogen and a part of phosphorus should be removed in a biological treatment process and then residual non-biodegradable organic matters, color and phosphorus be eliminated by physicochemical methods. In this study, therefore, the integrations of chemical coagulation, activated carbon adsorption, Fenton oxidation and ozonation were evaluated to provide an appropriate post-treatment process for biologically pre-treated livestock wastewater. With applying a single method such as coagulation and Fenton oxidation, a yellowish brown color and COD still remained. According to the experimental result, the quality of treated wastewater including color was enough to be discharged after chemical coagulation followed by ozonation or Fenton oxidation process. Among these, ozonation was the most effective technology for decolorization. Neither simple biological nor physicochemical process provides an adequate treatability for the sufficient depletion of organics and decolorization when treating livestock wastewater. Considering only the removal efficiency, the integration of Fenton oxidation and ozonation would be an efficient alternative as a post-treatment.     

臭氧技术在污水处理中的应用

臭氧作为一种强氧化剂,主要用于污水的深度处理。本文介绍了臭氧氧化的机理,探讨了臭氧及臭氧高级氧化在污水深度处理以及降解痕量有机物方面的应用,并在此基础上对今后的研究方向进行了展望,提出如何避免副产物的产生将是今后的研究重点。     

臭氧—曝气生物滤池处理难生物降解废水的试验研究进展

臭氧与曝气生物滤池组合工艺,可提高难生物降解废水的处理效率。文章综述了该组合工艺在不同行业难生物降解废水处理中色度、COD去除率等方面的研究进展,表明组合工艺对不同原水的处理效果明显。指出臭氧与曝气生物滤池组合工艺作为一种深度处理工艺是非常适合我国国情的水处理技术,尤其对我国今后中水回用、企业污水闭路循环以及＂零排放＂...     

Catalytic oxidation with Al-Ce-Fe-PILC as a post-treatment system for coffee wet processing wastewater

The effluent from the anaerobic biological treatment of coffee wet processing wastewater (CWPW) contains a non-biodegradable compound that must be treated before it is discharged into a water source. In this paper, the wet hydrogen peroxide catalytic oxidation (WHPCO) process using Al-Ce-Fe-PILC catalysts was researched as a post-treatment system for CWPW and tested in a semi-batch reactor at atmospheric pressure and 25 °C. The Al-Ce-Fe-PILC achieved a high conversion rate of total phenolic compounds (70%) and mineralization to CO(2) (50%) after 5 h reaction time. The chemical oxygen demand (COD) of coffee processing wastewater after wet hydrogen peroxide catalytic oxidation was reduced in 66%. The combination of the two treatment methods, biological (developed by Cenicafé) and catalytic oxidation with Al-Ce-Fe-PILC, achieved a 97% reduction of COD in CWPW. Therefore, the WHPCO using Al-Ce-Fe-PILC catalysts is a viable alternative for the post-treatment of coffee processing wastewater.     

Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment.

Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested batch wise, while catalytic wet air oxidation and H2O2-promoted catalytic wet air oxidation processes were studied in a trickle bed reactor, the last two using over activated carbon as catalyst. Effluent characterisation was made by means of substrate conversion (using high liquid performance chromatography), chemical oxygen demand and total organic carbon. Biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) were obtained from respirometric tests using activated sludge from an urban biological wastewater treatment plant (WWTP). The main goal was to find the proper conditions in terms of biodegradability enhancement, so that these phenolic effluents could be successfully treated in an urban biological WWTP. Results show promising research ways for the development of efficient coupled processes for the treatment of wastewater containing toxic or biologically non-degradable compounds.     

Treatment of linear alkylbenzene sulfonate (LAS) wastewater by internal electrolysis--biological contact oxidation process

Surfactant wastewater is usually difficult to treat due to its toxicity and poor biodegradability. A separate physico-chemical or biochemical treatment method achieves a satisfactory effect with difficulty. In this study, treatment of the wastewater collected from a daily chemical plant by the combination processes of Fe/C internal electrolysis and biological contact oxidation was investigated. For the internal electrolysis process, the optimal conditions were: pH = 4-5, Fe/C = (10-15):1, air-water ratio = (10-20):1 and hydraulic retention time (HRT)= 2 h. For the biological contact oxidation process, the optimal conditions were: HRT = 12 h, DO = 4.0-5.0 mg/L. Treated by the above combined processes, the effluent could meet the I-grade criteria specified in Integrated Wastewater Discharge Standard of China (GB 8978-1996). The results provide valuable information for full-scale linear alkylbenzene sulfonate wastewater treatment.     

Ozone-based reclamation of an STP effluent

The system ozone and hydrogen peroxide was used to reclaim wastewater from the secondary clarifier from a Sewage Treatment Plant (STP) of Alcalá de Henares (Madrid-Spain). The assays were performed by bubbling a gas mixture of oxygen and ozone, with approximately 24 g Nm(-3) of ozone concentration, through a volume of wastewater samples for 20 minutes at 25 degrees C. The removal of dissolved micropollutants such as Pharmaceutical and Personal Care Products (PPCPs) and Organic Carbon (TOC) was enhanced by adding periodic pulses of hydrogen peroxide while keeping pH above 8.0 throughout the runs. Removal efficiency ratios in the range of 7-26 mg O3/mg TOC and 0.24 mg O3/ng micropollutants at 5 minutes of ozonation were assessed as reference data to reclaim wastewater from STP. The relation between the extent of TOC removed and ozone doses used was related by a second-order kinetic model in which the time-integrated ozone-hydrogen peroxide concentration was included.     

Biological treatability of raw and ozonated synthetic penicillin formulation effluent.

Chemical pre-treatment of synthetic Procaine Penicillin G (PPG) effluent with ozone (applied dose = 1440 mg/h; treatment duration = 60 min) at pH = 7 was investigated. Successive biological treatability studies were performed with raw, ozonated penicillin formulation effluent and synthetic readily biodegradable substrate as simulated domestic wastewater. The PPG effluent additions were adjusted to constitute approximately 30% of the total COD in the reactor. Ozonation of PPG effluent resulted in practically complete removal of the parent pollutant accompanied by 40% COD abatement. Speaking for the raw PPG effluent, prolonged acclimation periods were necessary to obtain significant COD removal efficiencies. Batch activated sludge treatment experiments and respirometric studies have demonstrated that the selection of true retention time is extremely crucial for having high amount of slowly hydrolysable substrate or complex wastewater, like pharmaceutical effluent. The effect of ozonation time on biological treatability performance of PPG has been evaluated in the study. Pre-ozonation of PPG effluent did not improve its ultimate biodegradability.     

Integration of chemical and biological oxidation in a SBBR for tannery wastewater treatment.

This paper reports the results of an investigation aimed at evaluating the laboratory-scale performance of an innovative process for treating tannery wastewater. In this process, biological degradation, carried out in a sequencing batch biofilm reactor (SBBR), is combined with chemical oxidation by ozone. Tannery wastewater treatment was carried out, at laboratory scale, on a real primary effluent coming from a centralised plant treating wastewater produced by a large tannery district in Northern Italy. SBBR performance both without and with ozonation, was assessed with very satisfactory results. In particular, in the latter instance the recorded COD, TKN and TSS average removals, (96%), (92%) and (98%) respectively, allowed the maximum allowable concentration values fixed by the Italian regulation in force to be achieved without any additional polishing step. During the investigation biofilm properties (biofilm concentration and biofilm density) and flow dynamics aspects (head loss, shear stress, bed porosity) were also studied. A major feature of the process is that, with or without ozonation, it was characterised by very low specific sludge production (0.05 kgVSS/kgCODremoved) and high biofilm density (i.e. 87-122 gVSS/Lsludge) both contributing to a rather high biofilm concentration (i.e. 31-44 gTSS/Lfilter).     

Advanced oxidation process-biological system for wastewater containing a recalcitrant pollutant.

Two advanced oxidation processes (AOPs), ozonation and photo-Fenton, combined with a pilot aerobic biological reactor at field scale were employed for the treatment of industrial non-biodegradable saline wastewater (TOC around 200 mgL(-1)) containing a biorecalcitrant compound, alpha-methylphenylglycine (MPG), at a concentration of 500 mgL(-1). Ozonation experiments were performed in a 50-L reactor with constant inlet ozone of 21.9 g m(-3). Solar photo-Fenton tests were carried out in a 75-L pilot plant made up of four compound parabolic collector (CPC) units. The catalyst concentration employed in this system was 20 mgL(-1) of Fe2+ and the H2O2 concentration was kept in the range of 200-500mgL(-1). Complete degradation of MPG was attained after 1,020 min of ozone treatment, while only 195 min were required for photo-Fenton. Samples from different stages of both AOPs were taken for Zahn-Wellens biocompatibility tests. Biodegradability enhancement of the industrial saline wastewater was confirmed (>70% biodegradability). Biodegradable compounds generated during the preliminary oxidative processes were biologically mineralised in a 170-L aerobic immobilised biomass reactor (IBR). The global efficiency of both AOP/biological combined systems was 90% removal of an initial TOC of over 500 mgL(-1).     

Are we about to upgrade wastewater treatment for removing organic micropollutants?

Activated sludge treatment allows only for a partial removal of micropollutants, mainly via sorption and biological degradation. Ozonation and activated carbon filtration are processes bearing the potential to drastically reduce the micropollutant load discharged to the environment after (centralized) biological treatment. The estimated total costs between 0.05 and 0.20 euro per m3 treated water (depending on plant size and effluent DOC content) represent only a small fraction of the total costs for urban wastewater management and are therefore considered feasible. Full scale testing is currently planned or under way with the aim to a) confirm this cost estimation and b) to demonstrate the benefit by quantification of the effect of removal and by documenting the impact on the ecology of receiving waters. Ozonation would have the additional advantage of achieving partial disinfection. Another issue currently being intensively studied is the byproducts formed during ozonation and their toxicity. Evidence is needed that the formed ozonation byproducts are either harmless or easily degradable. Since a 5% to 20% loss of sewage is occurring due to sewer leakage and combined sewer overflow an improved reduction of micropollutant input to the aquatic environment requires that advanced centralized treatment is complemented with measures taken before discharge into the sewer. Options hereto may be waste design, labeling of compounds according to environmental friendliness or separate treatment of quantitatively significant point sources (e.g. hospital wastewater, nursery homes, industrial wastewater).     

Removal efficiency of 66 pharmaceuticals during wastewater treatment process in Japan.

Both biological treatment processes including conventional activated sludge (CAS) and biological nutrient removal (BNR) processes, and physico-chemical treatment processes including ozonation process and Title 22 process consisting of coagulation, sedimentation and filtration followed by UV or chlorination disinfection after the above biological processes, were compared from the viewpoint of removal efficiency. 66 pharmaceuticals including antibiotics, analgesics, psychoneurotic agents were measured with SPE-LC/MS/MS. 26 compounds out of 66 were detected in the influent ranging ng/L to microg/L order. Particularly, disopyramide, sulpiride, and dipyridamole that have been rarely detected before in the WWTP, occurred at concentration levels of more than 100 ng/L. The total concentration of the individual pharmaceuticals in the influent was efficiently removed by 80% during the biological treatment. But removal efficiencies of carbamazepine and crotamiton were less than 30%. The total concentration of the individual pharmaceuticals in the effluent from CAS process was 1.5 times higher than that from BNR process. Further, the total concentration of the individual pharmaceuticals in the discharge from WWTPs applying ozonation following activated sludge process was reduced to less than 20%. Physico-chemical treatment train called Title 22 treatment after CAS could not efficiently remove the pharmaceuticals. However, ozonation process followed by biological activated carbon process could efficiently reduce all the residual pharmaceuticals below their quantification limits.