载锰污泥活性炭催化臭氧氧化草酸废水的研究

为研究在催化臭氧化过程中,载锰污泥活性炭对草酸废水降解的催化效果,以及为污泥的资源化探索一条新途径,本实验采用连续流臭氧氧化实验,通过单因素实验方法考察了载锰污泥活性炭催化臭氧化反应的主要影响因素及最佳反应条件,同时对催化臭氧化反应机理进行了探讨。结果表明:在臭氧浓度为5.0 mg/L,载锰污泥活性炭投加量为100 mg/L,pH值为3.5的最佳反应条件下,60 min内草酸的去除率最高达91.2%。叔丁醇对草酸降解具有抑制作用,催化臭氧化反应符合羟基自由基的反应机制。该方法的处理效果较为明显,对评价催化臭氧法的效果具有较明显的参考价值。     

活性炭去除饮用水中溴酸盐的研究进展

臭氧氧化过程中产生的溴酸盐的问题已经成为目前臭氧大规模应用于饮用水中的最大制约因素。活性炭去除法是国内外最常用的去除溴酸盐的方法,且由于活性炭常作为臭氧氧化工艺必备的联用工艺,容易实现生产应用,且不需要增加额外的投资,引起了研究者的极大关注。本文全面阐述了关于活性炭／生物活性炭对溴酸盐的去除效能、去除机理及影响因素的研究进展。针对活性炭去除饮用水中溴酸盐的研究现状,提出了今后研究的主要方向和亟需解决的问题。     

Efficient taste and odour removal by water treatment plants around the Han River water supply system.

Seven major water treatment plants in Seoul Metropolitan Area, which are under Korea Water Resources Corporation (KOWACO)'s management, take water from the Paldang Reservoir in the Han River System for drinking water supply. There are taste and odour (T&O) problems in the finished water because the conventional treatment processes do not efficiently remove the T&O compounds. This study evaluated T&O removal by ozonation, granular activated carbon (GAC) treatment, powder activated carbon (PAC) and an advanced oxidation process in a pilot-scale treatment plant and bench-scale laboratory experiments. During T&O episodes, PAC alone was not adequate, but as a pretreatment together with GAC it could be a useful option. The optimal range of ozone dose was 1 to 2 mg/L at a contact time of 10 min. However, with ozone alone it was difficult to meet the T&O target of 3 TON and 15 ng/L of MIB or geosmin. The GAC adsorption capacity for DOC in the three GAC systems (F/A, GAC and O3 + GAC) at an EBCT of 14 min is mostly exhausted after 9 months. However, substantial TON removal continued for more than 2 years (>90,000 bed volumes). GAC was found to be effective for T&O control and the main removal mechanisms were adsorption capacity and biodegradation.     

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.     

O3/TiO2/γ-Al2O3协同降解苯酚的研究

采用催化臭氧化技术对降解苯酚进行研究。考察了进气流量、苯酚初始浓度、催化剂投加量、pH值及温度等因素对苯酚降解的影响。研究结果表明:在一定范围内,随着进气流量的增加、温度的降低,苯酚的降解速率加快;溶液pH值对催化臭氧化有比较重要的影响,在pH值为8~10时,苯酚的去除率最高。     

Screening of chemical oxidation processes and other methods for decolorization of urine for its re-use as toilet-flush liquid in ecological sanitation systems.

Because of its potential use as fertilizer, urine ("yellow water") is a resource originating from sanitation. Its separate collection in no-mix toilets is a beneficial aspect of ecological (source control) sanitation. In order to avoid dilution of the fertilizing nutrients with toilet flush water, the utilization of yellow water as toilet flush liquid seems to be advantageous. To be accepted for this purpose, urine has to be decolorized (and also deodorized). In this study activated carbon adsorption, irradiation with UV light of different wavelengths, the advanced oxidation processes ultrasound, UV/H2O2, and photocatalytic oxidation have failed to decolorize urine. Biological treatment caused brown colour of the treated urine. Only ozonation was successful in colour removal, although it did not affect TOC. In spite of darkening of yellow water during biological treatment (generation of humic substances), smaller ozone doses were required for decolorizing the biologically pre-treated urine than for original urine. Photocatalytic oxidation of biologically treated urine also removed brown colour, but the original yellow colour remained. In ozonated urine, yellow colour was reconstituted unless hydrogen peroxide was added. In addition to colour removal, ozone contributed to deodorization as a consequence of ammonia stripping and probably of phenol oxidation.     

Removal of volatile organic compounds by heterogeneous ozonation on microporous synthetic alumina silicate

A hybrid process combining adsorption and ozonation was examined as an alternative treatment for odorous volatile organic compounds (VOCs). Methyl ethyl ketone (MEK) was chosen to study the influence of operating parameters. Two synthetic aluminosilicates (faujasite-Y and ZSM-5) were tested for adsorption and reactivity with ozone. The adsorption equilibrium measurement on both adsorbents showed that adsorption performance depends on temperature but is not sensitive to relative humidity, due to the hydrophobic properties of the materials. Adsorbed VOCs were oxidized at low temperature when ozonated flow was sent to the reactor. Regeneration of the fixed bed was achieved at the same time, releasing mainly CO(2) and H(2)O. Intermediates of oxidation, such as 2,3-butanedione and acetic acid, were identified, leading to incomplete mineralization. The influence of concentration and humidity are discussed. Four successive cycles were tested: after the first adsorption/ozonation cycle, the adsorption efficiency was not affected during subsequent cycles. These results show that the same sample of adsorbent can be used in the treatment process for a long time. Ozonation regeneration is a promising process for VOC removal.     

Removal of geosmin and 2-methylisoborneol by biological filtration.

The quality of drinking water is sometimes diminished by the presence of certain compounds that can impart particular tastes or odours. One of the most common and problematic types of taste and odour is the earthy/musty odour produced by geosmin (trans-1, 10-dimethyl-trans-9-decalol) and MIB (2-methylisoborneol). Taste and odour treatment processes including powdered activated carbon, and oxidation using chlorine, chloramines, potassium permanganate, and sometimes even ozone are largely ineffective for reducing these compounds to below their odour threshold concentration levels. Ozonation followed by biological filtration, however, has the potential to provide effective treatment. Ozone provides partial removal of geosmin and MIB but also creates other compounds more amenable to biodegradation and potentially undesirable biological instability. Subsequent biofiltration can remove residual geosmin and MIB in addition to removing these other biodegradable compounds. Bench scale experiments were conducted using two parallel filter columns containing fresh and exhausted granular activated carbon (GAC) media and sand. Source water consisted of dechlorinated tap water to which geosmin and MIB were added, as well as, a cocktail of easily biodegradable organic matter (i.e. typical ozonation by-products) in order to simulate water that had been subjected to ozonation prior to filtration. Using fresh GAC, total removals of geosmin ranged from 76 to 100% and total MIB removals ranged from 47% to 100%. The exhausted GAC initially removed less geosmin and MIB but removals increased over time. Overall the results of these experiments are encouraging for the use of biofiltration following ozonation as a means of geosmin and MIB removal. These results provide important information with respect to the role biofilters play during their startup phase in the reduction of these particular compounds. In addition, the results demonstrate the potential biofilters have in responding to transient geosmin and MIB episodes.     

Ozonation and combined ozone/H2O2, UV/ozone and UV/H2O2 for treatment of fuel oxygenates MTBE, ETBE, TAME, and DIPE from water--a comparison of removal efficiencies.

Methyl tert-butylether (MTBE) used as fuel oxygenate poses problems for water suppliers since it is persistent in the aquatic environment and the removal efficiency by conventional water treatment methods (aeration or activated carbon filtration) is rather low. Substitution by other ether compounds such as ethyl tert-butylether (ETBE), tert-amylmethylether (TAME) or di-isopropylether (DIPE) is discussed, however, their environmental behaviour is similar to that of MTBE. Experiments investigating the elimination efficiency of AOP were carried out in tap water and water from Lake Constance. The elimination efficiency for all treatment processes was found to follow the order: MTBE < TAME approximately equal ETBE < DIPE For all compounds under investigation, neither pure ozonation nor UV irradiation yield a considerable concentration decline. Only the formation of highly reactive OH radicals shows a potential for removing the ethers from water. Therefore the addition of H2O2 in equimolar ratio prior to ozone admixing proved to be quite efficient. The application of combined UV/H2O2 showed good results in all cases; the best concentration decline was achieved with UV/ozone. The rate of elimination of the three substitutes for MTBE (ETBE, TAME and DIPE) is higher in all processes; nevertheless, no complete removal could be achieved. Therefore, from the point of view of water suppliers, the use of other ethers as substitute for MTBE is posing the same problems as MTBE.     

组合工艺控制有机物及消毒副产物前体物的特性研究

通过XAD-8树脂将水中有机物分成疏水性、亲水性两部分,对传统常规处理工艺(混凝气浮、过滤)和深度处理工艺(臭氧氧化、生物活性炭)出水的DOC,UV254THMFP,HAAFP指标以及疏水、亲水有机物去除率进行了检测分析。结果表明,生物活性炭(BAC)单元工艺能同时去除疏水性和亲水性两种有机物,且两者去除率均为最高。其次去除效果较好的是传统的常规工艺。臭氧工艺具有将天然的疏水性有机物氧化成可生化降解的亲水性小分子有机物的特点,在预臭氧+常规以及O3-BAC组合工艺中,起到了强化去除有机物和消毒副产物前体物的效果。     

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.     

Evaluating ozone dose for AOC removal in two-step GAC filters

Upgrading an existing post-ozonation plant with two-step granular activated carbon (GAC) filtration for assimilable organic carbon (AOC) removal was studied. The effects of ozone dose on AOC formation and its removal in the subsequent two-step GAC filtration was studied using chemically pretreated 2 to 14° C humic lake water. Two parallel pilot-plant trains with different ozone doses (0 to 1.2 mgO₃/mgTOC) and a shortterm ozonation study were performed. The optimum ozone dose for maximum AOC formation was 0.4–0.5 mgO₃/mgTOC. The AOC-P17 of ozonated water was three-fold higher and AOC-NOX over ten-fold higher than in non-ozonated water, while the following biofiltration (first step) removed 51 % and 72 % of AOC-P17 and AOC-NOX, respectively. The adsorber (second step) contributed to less than 10% of the overall AOC reduction. It appeared that biofiltration is a feasible method in upgrading water treatment plants for AOC removal even when treating cold humic waters, while the subsequent adsorber seems to have less significance for AOC removal.     

Effects and mechanism of ozonation for degradation of sodium acetate in aqueous solution

The degradation efficiencies and mechanism of ozonation for the degradation of sodium acetate in aqueous solution were investigated under atmospheric pressure at room temperature (293 K). The effects of the initial pH value, reaction time, and concentrations of HCO3-, CO32-, CaCl2, and Ca(OH)2 on the removal rate of chemical oxygen demand (COD) were studied. The results indicated that ozonation obviously improved the degradation rate of sodium acetate when the pH value of the solution was not less than 8.5. A suitable long reaction time may be helpful in increasing the COD removal rate, and a removal rate of 36.36% can be obtained after a 30-minute treatment. The COD removal rate increased firstly and decreased subsequently with the increase of the HCO3- concentration (from 0 to 200 mg/L), and under the same experimental condition it reached the optimum 34.66% at the HCO3- concentration of 100 mg/L. The COD removal rate was 5.26% lower when the concentration of was 200 mg/L than when there was no HCO3-. The COD removal rate decreased by 15.68% when the CO32- concentration increased from 0 to CO32- 200 mg/L. has a more obvious scavenging effect in inhibiting the formation of hydroxyl radicals than HCO3-. CaCl2 and Ca(OH)2 could increase the degradation efficiency of sodium acetate greatly, and the COD removal rates reached 65.73% and 83.46%, respectively, after a 30-minute treatment, 29.37% and 47.10% higher, respectively, than with single ozone oxidation. It was proved that the degradation of sodium acetate in the ozonation process followed the mechanism of oxidization with hydroxyl free radicals (·OH).     

臭氧—生物活性炭处理效果的影响因素与工艺分析

桐乡市果园桥水厂深度处理工艺投入运行已逾五年。通过对二期臭氧—生物活性炭工艺长达五年的跟踪分析,阐述了臭氧接触、生物活性炭以及臭氧—生物活性炭工艺对耗氧量的去除效果,分析了水温、处理负荷、原水耗氧量、臭氧投加量等因素对耗氧量去除率的影响,并且从活性炭物理指标的下降程度说明了生物活性炭工艺的中后期以生物作用为主。总体而言,多因素综合影响着臭氧—生物活性炭工艺的处理效果。     

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.     

Pre-ozonation in the activated sludge process: fate of nitrogen species

The objective of this research was to include ozonation prior to an activated sludge treatment and investigate the effect on the nitrogen species, their fate and the consequences of this oxidation upon the biomass. Three parallel treatment systems were used: the base system, where feed went directly to the activated sludge reactor, and two others, where the influent was ozonated at two different dosages, 15 and 25 mg/L of influent, prior to the biological reactors. The results from the ozonation chamber show a high oxidation capacity of the entering ammonia and organic nitrogen, proportional to the ozone dose. The oxidation product was nitrate. No de-nitrification was expected because a high oxygen concentration (4 mg/L) was maintained in the reactors. The reactors receiving ozonated influent showed a lower assimilation of nitrogen by the biomass. The sludge nitrogen content resulted in 11, 9.3 and 7.4% dry-weight corresponding to no-ozone, low ozone and high ozone dosages, respectively. In spite of the lower ammonia available in the ozonated flows, the corresponding reactors showed a higher specific nitrification rate. The ozonated system also performed better in terms of chemical oxygen demand (COD) and biochemical oxygen demand (BOD5) removals, besides showing a higher true biomass yield coefficient.     

Catalytic ozonation for odour removal of high temperature alumina refinery condensate

Odour emissions from aluminium processing can cause an impact on local communities surrounding such facilities. Of particular concern is fugitive odours emitted from the handling and use of refinery condensate streams, particularly the digestion condensate. This study evaluated the application of using catalytic ozonation to treat alumina refinery condensate in order to remove the potential emission of odourous compounds from the industrial wastewater. The technical challenges in treating the alumina refinery condensate are the high pH and temperatures of the wastewater effluent (over 80 °C and pH above 10) due the industrial process. The odour removal efficiencies for different catalysts (FeCl(3), MnO, and MnSO(4)) under experimental conditions in terms of controlled pH, temperature and ozone dosage were determined before and after ozone treatment using dynamic olfactometry. The result demonstrated that the addition of both FeCl(3) and MnO catalysts improved odour removal efficiencies during the ozonation of alumina condensates at similar pH and temperature conditions. FeCl(3) and MnO had similar enhancement for odour removal, however MnO was determined to be more appropriate than MnSO(4) for odour removal due to the colouration of the treated condensate.     

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.     

The basics of oxidants in water treatment. Part B: ozone reactions.

The oxidation of organic and inorganic compounds during ozonation can occur via ozone or OH radicals or a combination thereof. Ozone is an electrophile with a high selectivity. The reactions of ozone with inorganic compounds are typically fast and occur by an oxygen atom transfer reaction. Organic micropollutants are oxidised with ozone selectively. Ozone reacts mainly with double bonds, activated aromatic systems and non-protonated amines. The kinetics of direct ozone reactions depend strongly on the speciation (acid-base, metal complexation). The reaction of OH radicals with the majority of inorganic and organic compounds is nearly diffusion-controlled. The degree of oxidation by ozone and OH radicals is given by the corresponding kinetics and the ratio of the concentration of the two oxidants. Product formation from the ozonation of organic micropollutants has only been established for a few compounds. Numerous organic and inorganic ozonation disinfection/oxidation byproducts have been identified. The byproduct of main concern is bromate, which is formed in bromide-containing waters. A low drinking water standard of 10 microgL(-1) has been set for bromate. In certain cases (bromide > approximately 50 microgL(-1)), it may be necessary to use control measures to lower bromate formation (lowering of pH, ammonia addition, chlorination-ammonia process).     

臭氧-活性炭-反硝化生物滤池在污水再生回用中的应用

在酒仙桥污水处理厂建立200m3/d的示范工程进行高品质再生水的生产,在二级出水强化脱氮除磷的基础上,采用臭氧(O3)-活性炭(GAC)-反硝化生物滤池(DNBF)工艺进行试验研究。经过13个月的试验证明,该工艺由于O3在脱色除臭基础上,能够强化活性炭滤池的生物多样性及活性,从而使出水CODCr能够长期稳定在30mg/L以下,NH3-N小于1mg/L。在外加碳源CH3COONa条件下,系统经DNBF后出水TN小于2mg/L。同时试验发现,为了实现经济节能及良好的污水再生效果,DNBF和O3单元在流程中的位置设置非常关键,有别于污水二级处理工艺。