Enhanced ozonation of simulated dyestuff wastewater by microbubbles

The ozonation of synthetic wastewater containing azo dye, CI Reactive Black 5, was investigated using a microbubble generator and a conventional bubble contactor. The microbubble generator produced a milky and high intensity microbubble solution in which the bubbles had a mean diameter of less than 58 microm and a numerical density of more than 2.9 x 10(4) counts ml(-1) at a gas flow rate of less than 0.5 l min(-1). Compared with the bubble contactor, the total mass transfer coefficient was 1.8 times higher and the pseudo-first order rate constant was 3.2-3.6 times higher at the same initial dye concentration of 100 mg l(-1), 230 mg l(-1) and 530 mg l(-1) in the proposed microbubble system. The amount of total organic carbon removed per g of ozone consumed was about 1.3 times higher in the microbubble system than in the bubble contactor. The test using terephthalic acid as the chemical probe implied that more hydroxyl radicals were produced in the microbubble system, which contributed to the degradation of the dye molecules. The results suggested that in addition to the enhancement of mass transfer, microbubbles, which had higher inner pressure, could accelerate the formation of hydroxyl radicals and hence improve the oxidation of dye molecules.     

原位臭氧氧化对活性污泥系统硝化和反硝化作用的影响研究

将厌氧序批式间歇反应器(ASBR)和序批式间歇反应器(SBR)串联组成污泥减量新工艺,着重探讨了对SBR段进行原位臭氧投加时,臭氧氧化作用对系统硝化和反硝化能力的影响,并以不投加作为对照。结果表明,将臭氧原位投加到ASBR—SBR组合工艺的SBR段,臭氧投加量为0.027g(以每克MLSS计),每隔3个周期再次投加、连续运行40d,试验组SBR段臭氧投加当期出水COD去除率为86%,比对照组下降了9百分点,但臭氧氧化细胞内大量有机物进入混合液中,为反硝化作用提供了外加碳源,对污泥反硝化能力的提高起到了一定的促进作用;试验组部分硝化细菌由于臭氧的强氧化作用而失去活性,但是随着剩余污泥量的减少,系统的污泥龄延长,有利于硝化细菌的生长,使得系统的硝化能力基本未受影响;试验组臭氧投加当期SBR段出水NO2--N平均浓度比对照组的高18.9%,但经过3个周期的运行后,其SBR段出水NO2--N平均质量浓度降低至7.57mg/L,基本与对照组持平;试验组臭氧投加当期SBR段出水NO3--N的平均浓度高于对照组,但经过3个周期的运行后,试验组出水NO3--N平均浓度低于对照组;试验组臭氧投加当期SBR段出水TN和对照组的出水TN平均去除率分别为65%和75%,但试验组再经过3个周期的运行后,出水TN平均去除率可以达到72%。可见,原位投加臭氧并未对SBR段的硝化和反硝化能力产生明显的影响。     

Changes in biomass activity and characteristics of activated sludge exposed to low ozone dose

In this paper, the response mechanism of activated sludge exposed to low-dose ozone at less than 20 mg O₃ g⁻¹ total suspended solids (TSS) was studied by analyzing the changes in sludge activity and the evolution of C, N, P and metals from sludge following ozonation. The intracellular ATP concentration was not affected at less than 5 mg O₃ g⁻¹ TSS and thereafter decreased rapidly to around 60% when the ozone dose increased to 20 mg O₃ g⁻¹ TSS. Similarly, the efficiency of sludge solubilization initially changed a little and then increased rapidly to around 30% at an ozone dose of 20 mg O₃ g⁻¹ TSS. However, the activities of superoxide dismutase and protease decreased immediately upon exposure to ozone. These findings indicate that ozone firstly destroys the floc, leading to the disruption of the compact aggregates, which does not affect cells viability but induces a decrease in enzyme activities. Ozone then attacks the bacterial cells of the sludge, causing a decrease in cells viability. During ozonation, the content of carbon, nitrogen and phosphorus in the sludge matrix decreased, while the content of these elements in the micro-solids and supernatant gradually increased. Most of the released metals from the sludge matrix were found in the micro-solids.     

污泥减量过程中臭氧氧化对硝化和反硝化影响的试验研究

采用AO工艺,考察了在污泥减量过程中臭氧(O3)氧化对生物系统硝化和反硝化能力的影响.结果表明,在每克SS中O3投量为0.05 g时,氧化后污泥中的CODcr由37.5 mg/L增至700mg/L,TN由4.86 mg/L增至36.6 mg/L,NH4 -N由0.353mg/L增至7.49 mg/L,NO3--N由2.19 mg/L增至5.15 mg/L.虽然氧化系统出水NH4 -N浓度略高于对照系统,但氧化系统NH4 -N的去除率大于98%,硝化能力基本没有受到O3氧化的影响.O3氧化污泥后增加的有机物作为附加的碳源循环至缺氧段,提高了反硝化的效果,当污泥氧化比例分别为10%、20%、30%时,进入缺氧段的CODCr/TN分别平均增至11.21、11.56、11.88,氧化系统的反硝化效果也随之分别提高5%、25%、37%.     

Ozonation of o-cresol in aqueous solutions using a rotating packed-bed reactor.

Experimental results indicated that ozone transfer in the rotating packed contactor was noticeably greater than in a traditional packed-bed contactor under similar operational conditions. Ozonation in the rotating packed contactor has been shown to be feasible for achieving nearly complete decomposition of o-cresol within 1 hour. The decomposition of o-cresol by ozonation in the rotating packed contactor increased with increasing rotor speed and decreasing the gas-liquid flowrate ratio. However, the reduction of total organic carbon during the ozonation of o-cresol was not influenced by variation of rotor speed and gas-liquid flowrate ratio. The species distribution of o-cresol under various solution conditions plays a significant role in determining the decomposition behavior. In most experiments conducted in this study, the decomposition of o-cresol by ozonation was more favorable under alkaline conditions.     

臭氧处理剩余污泥的减量化实验研究

采用质子交换聚合物膜电解法（PEM）产生臭氧,单独对剩余污泥进行氧化破解实验,结果表明,随着臭氧化反应时间的增加,污泥微生物细胞裂解,胞内物质进入到污泥溶液中,污泥固体物质减少,使得TS和VTS均显著下降,处理40 min后,其去除率分别达到57.33%和72.76%;SCOD前30 min呈线性增长,通入臭氧60 min后,由处理前的3 501.24mg/L上升到6 298.32 mg/L,增长率达79.88%;SV30及滤饼含水率均呈下降趋势,表明剩余污泥的沉淀性能及脱水性能得到明显改善。实验结果表明,直接利用臭氧对剩余污泥进行处理,可获得良好的减量化效果。     

臭氧水中传质模型的研究

在传统鼓泡塔中对臭氧在水中的传质过程进行实验研究。利用实验改变进水流量、臭氧进气流量以及臭氧进气浓度等，得到臭氧传质系数、臭氧传质效率和臭氧消耗等有关参数。建立一个臭氧传质模型，可以预测不同操作条件下臭氧传质效率，从而优化控制臭氧化反应动力学。     

Performance change during long-term ozonation aimed at augmenting denitrification and decreasing waste activated sludge

Partial ozonation of return activated sludge for waste sludge minimization and soluble COD production was examined. Two nitrifying sequencing batch reactors, one control and one ozonated, were operated under alternating anoxic/aerobic conditions. During the first steady-state period of 95-136 d of ozonation, the amount of wasted solids decreased with the ozone dose up to 25%, generating soluble COD by cell lysis. However, during a subsequent period of 190-232 d of continuous ozonation, the effect of solids destruction and COD production decreased by 50%. The investigations of extracellular polymers content and floc shape analyses showed that, after prolonged daily ozone treatment, sludge floc structure becomes stronger, denser, and more ozone-resistant. The findings suggest that, for prolonged operation of partial sludge ozonation, an increase in ozone doses may be required to continuously maintain the expected solids destruction level. This in turn will increase the operational costs of the treatment.     

臭氧对活性污泥特性影响研究

探讨了臭氧对于污水生物处理中活性污泥特性的影响。结果显示 ,随着臭氧化的进行 ,促进了活性污泥生物量的减少 ,并有一定量的生物污泥被无机化 ,并且污泥的活性和存活性降低了。其中臭氧投加量低于 0 .1gO3 /gSS时污泥活性即大幅下降 ,而后污泥浓度才随着臭氧量的增加而显著降低。     

Inactivation of fungi associated with barley grain by gaseous ozone

The use of gaseous ozone as a fungicide to preserve stored barley was studied. The effects of the following operating parameters on the fungicidal efficacy of ozone were examined: 1) the applied ozone dose, 2) ozonation time, 3) water activity of barley, and 4) temperature of barley. The effect of ozonation on germination of barley was also investigated. The experimental results showed that ozone was very effective in inactivation of fungi associated with the barley regardless of whether the fungi were in the forms of spores or mycelia. However, the mycelia were less resistant to ozone. With 5 minutes of ozonation, 96% of inactivation were achieved for spores as well as for mixtures of spores and small amount of mycelia by applying 0.16 and 0.10 mg of ozone/(g barley) x min, respectively. In addition, for sealed storage silos, inactivation of fungi continued when the ozone-containing gas was held inside the silos following a continuous ozone supply. The experimental results also revealed that increases in water activity and temperature of barley enhanced the fungicidal efficacy of ozone. Results of this study also indicated that the inactivation processes could be controlled by simply monitoring the exit ozone from the reactor instead of performing the time-consuming microbial examination. This finding would make the application of ozone in the preservation of cereal grains easier, simpler, and more practically applicable. The experimental results demonstrated that although ozonation above certain strength may reduce barley germination, inactivation of fungi was achieved with ozonation strengths far below the critical point.     

畜禽养殖废水生物处理剩余污泥臭氧减量过程中的重金属释放简

采用臭氧氧化污泥减量法对畜禽养殖废水SBR中的剩余污泥进行处理。当臭氧反应时间控制在30 min时，污泥的溶解比例在30%左右（以 MLSS计）。上清液中一定量的SCOD溶出可为生物处理单元提供充足的碳源，同时在上清液中，TN、TP及水相重金属浓度增加有限，臭氧氧化后的污泥液回流污水处理系统后造成的N、P处理负荷较小，重金属对污泥微生物的活性抑制风险较低。若继续延长臭氧的反应时间，上清液SCOD、TN、TP以及重金属Cu、Pb的释放速率明显增加，同时上清液的C/N降低，臭氧化后的污泥液回流反而不利于生物单元的脱氮处理。综合考虑TN、TP及水相重金属浓度增加的危害性，臭氧反应时间应控制在30 min，臭氧实际投加量应为123.1 mg O₃/g SS。     

畜禽养殖废水生物处理剩余污泥臭氧减量过程中的重金属释放

采用臭氧氧化污泥减量法对畜禽养殖废水SBR中的剩余污泥进行处理。当臭氧反应时间控制在30min时，污泥的溶解比例在30％左右（以MLSS计）。上清液中一定量的SCOD溶出可为生物处理单元提供充足的碳源，同时在上清液中，TN、TP及水相重金属浓度增加有限，臭氧氧化后的污泥液回流污水处理系统后造成的N、P处理负荷较小，重金属对污泥微生物的活性抑制风险较低。若继续延长臭氧的反应时间，上清液SCOD、TN、TP以及重金属cu、Pb的释放速率明显增加，同时上清液的C／N降低，臭氧化后的污泥液回流反而不利于生物单元的脱氮处理。综合考虑TN、TP及水相重金属浓度增加的危害性，臭氧反应时间应控制在30min，臭氧实际投加量应为123．1mg O3／gSS。     

原位臭氧氧化污泥减量工艺的运行效能

采用ASBR/SBR原位臭氧污泥减量工艺,重点研究了原位臭氧氧化对SBR段污泥产率和出水水质的影响。两个相同的ASBR/SBR组合工艺同时运行,每隔3个周期向臭氧投加组SBR的曝气阶段原位间歇投加臭氧,臭氧投加量为0.027 g O3/g MLSS,连续运行40 d;对照组不投加臭氧作为对比。结果表明,原位臭氧氧化实现污泥减量约43.9%,臭氧投加组SBR段平均污泥产率系数为0.1447 g SS/g SCOD,而对照组为0.2580 g SS/g SCOD,投加组没有惰性污泥的累积,并且污泥沉淀性能得到改善。原位臭氧氧化对出水水质影响不大,投加组与对照组相比,臭氧投加3周期后的出水COD、NH4+-N、TN和TP平均值分别为47.8、0.76、14.1和6.4 mg/L,去除率分别下降了4%、2%、3%和7.7%,其中COD、NH4+-N和TN均能达到《城镇污水处理厂污染物排放标准》(GB18918-2002)一级A标准。     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H，0，能提高臭氧氧化RO浓水的效果，O3／H2O2初始摩尔比在0～0．8范围内，COD的去除率先增加后下降，O3／H2O2初始摩尔比为O．5时COD去除率最大；pH从6．84增加到9．01，COD去除率逐渐增大，pH为10．03时COD去除率反而降低；在14～28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H：0：／0，初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下，对COD为90～140mg／L的RO浓水氧化处理4～10h，出水COD维持在39．9～49．9mg／L，达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准；去除1gCOD消耗031．4～3．3g，消耗0，与H，02的总氧量为2．2～4．4g。     

Improved solubilization of activated sludge by ozonation in pressure cycles

The generation of a large volume of activated sludge (AS) from wastewater treatment has increasingly become a great burden on the environment. Anaerobic digestion is routinely practiced for excess waste sludge; however, the process retention time is long because of kinetic limitation in the hydrolysis step. We tested the feasibility of applying ozone in pressure cycles to enhance the disintegration and solubilization of AS with the goal to prepare them for digestion using reduced ozone dose and contact time. The AS was subjected to repetitive pressure cycles in a closed vessel in which an ozone gas mixture was compressed into the slurry to reach 1040 kPa in the headspace to be followed by rapid venting. For a returned AS with total COD (tCOD) of 8200 mg L(-1), a dose of 0.01 gO(3)g(-1) total suspended solids (TSS) delivered via 20 pressure cycles within 16 min resulted in a 37-fold increase of the sCOD/tCOD ratio (due to increased soluble COD, i.e. sCOD) and a 25% reduction of TSS, in comparison to a dose of 0.08 gO(3)g(-1) TSS via bubbling contact over 15 min that resulted in a 15-fold increase of the sCOD/tCOD ratio and a 12% reduction of TSS. Sludge solubilization was evidenced by increased dissolved contents of total phosphorous (from 10 to 64 mg L(-1)), total nitrogen (from 14 to 120 mg L(-1)), and protein (from <15 to 39 mg L(-1)) in the sludge suspension after treatment, indicating significant solubilization of AS.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

The enhancement of the biodegradability of phenolic solution using preozonation based on high ozone utilization

In this research, the effects of preozonation on the biodegradability of 4-cresol, 4-nitrophenol and 2-chlorophenol solutions were investigated using a new gas-inducing reactor with high ozone utilization rate. The extent of preozonation may be monitored by determining the characteristic ozonation behaviors of preozonized phenolic solutions, such as residual phenolic concentration, ADMI value and ozone gas outlet concentration. Experimental results showed that as the initial phenolic compounds decomposed completely, the ozone gas outlet concentration rapidly increases. In addition, at pH 7, a peak ADMI value appears during the preozonation of 4-cresol and 2-chlorophenol, while for 4-nitrophenol the ADMI value decreases monotonically. Based on the characteristic ozonation behaviors and the ozone utilization rate, three characteristic times were chosen in order to have better control on the extent of preozonation. The effect of preozonation on the biodegradability of preozonized phenolic solution was studied based on these characteristic times. The intermediate products during the preozonation were also identified. The variation of BOD5 is strongly dependent on the accumulation of intermediate products. It is suggested that the best characteristic time is as the rapid increase of ozone gas outlet concentration in this study. The biodegradability (BOD5/COD) of preozonized 4-cresol, 2-chlorophenol and 4-nitrophenol solutions increase to 0.18, 0.26 and 0.33, respectively, for the best characteristic time.     

Enhanced anaerobic biodegradability and inactivation of fecal coliforms and Salmonella spp. in wastewater sludge by using microwaves.

During continuous operation of three mesophilic-anaerobic digesters, the effect of microwave irradiation, as sludge thermal pretreatment (60 to 65 degrees C), was studied. The fecal coliforms log inactivation for microwaved/digested sludge was 4.2 +/- 0.4, whereas for conventionally heated/digested sludge and control were 2.9 +/- 0.5 and 1.5 +/- 0.5, respectively. In the case of Salmonella spp., no colonies were detected in 85% of the microwaved/digested samples. Considering the detection limit, the log inactivation of these samples was greater than 2.0 +/- 0.3. The conventionally heated/digested sludge and control showed log inactivations of 1.9 +/- 0.2 and 1.1 +/- 0.3, respectively. At the 95% confidence level, microwaved/digested sludge increased the biogas production by 16.4 +/- 5.6% and 6.3 +/- 2.4%, as compared to control and conventionally heated/digested sludge, respectively. When thermally treated sludge was analyzed for soluble chemical oxygen demand, microwaved waste-activated sludge showed considerable solubilization between 37 and 60 degrees C. Microwaved/digested sludge showed a reduction of capillary suction times by 11.1 +/- 5.9% and 10.7 +/- 5.6%, as compared to control and conventionally heated/digested sludge, respectively.