UV/H_2O_2高级氧化技术在水处理中的研究进展

本文主要讨论了UV/H2O2高级氧化技术去除有机物的机理,在有机废水、饮用水处理中的应用进展。UV/H2O2工艺对水中生物难降解的有机污染物具有很好的处理效果,其主要影响因素包括污染物的初始浓度、紫外光波长及强度、H2O2投加浓度、pH、光照时间、浊度、水中存在的阴离子等。     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

Comparison of Diuron degradation by direct UV photolysis and advanced oxidation processes

The rates of Diuron elimination by some advanced oxidation processes (AOPs) such as Fe(III)/UV, Ferrioxalate/UV, Fe(III)/H(2)O(2)/UV, Ferrioxalate/UV/H(2)O(2) and Fe(III)/H(2)O(2) have been compared. Experiments have been conducted at pH=2.3+/-0.1 with a batch reactor equipped with a low-pressure mercury lamp emitting mainly at 253.7nm. Data obtained under the following experimental conditions ([H(2)O(2)](0)=10(-3)M, [Diuron](0)=5x10(-5)M and [Fe(III)](0)=10(-3)M) have shown that rates of Diuron oxidation were higher with the systems Fe(III)/H(2)O(2)/UV and Ferrioxalate/UV/H(2)O(2) than with Fe(III)/UV and Fe(III)/H(2)O(2). On the other hand, Fe(III)/UV was found to be very efficient in mineralization of Diuron solution in comparison to direct UV photolysis. The experimental results showed that radical ()OH is the major pathway in the process of Diuron degradation.     

光化学氧化法对阴离子表面活性剂降解的初步研究

本试验采用UV/H2O2光氧化法处理含有较高浓度阴离子表面活性剂（LAS）的模拟废水，研究了H2O2投加量、pH值、光照时间、紫外灯光强对LAS降解率的影响。     

Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.     

车载巡回式UV／Fenton装置处理小城镇垃圾渗滤液

为了研究车载巡回处理装置对小城镇垃圾渗滤液的处理效果,采用自制的UV-Fenton试验装置研究了pH值、FeSO_4剂量、反应时间等因素对处理效果的影响,结果表明:最佳pH值为4.0,进水中COD为825 mg/L时,FeSO_4和H_2O_2的投加量分别为0.008 mol/L和0.08 mol/L,此时COD去除率72.22%,出水COD为216 mg/L;随着FeSO_4投加量缓慢增加到一定程度后转而下降,FeSO_4最佳投加量为0.008 mol/L;不同H_2O_2和Fe~(2+)配比对COD去除效果具有影响,(10:1)时为最佳配比。经过氨吹脱和混凝沉淀预处理的渗滤液采用UV/Fenton处理工艺,出水中COD可以达到《生活垃圾填埋场污染控制标准》(GB 16889-1997)中二级标准。     

A study on oxidative degradation of polyacrylamide in wastewater with UV/FENTON/C4H4O62−

The degradation of polyacrylamide (PAM) in simulate wastewater was studied in UV/Fenton/C₄H₄O₆^2? system. The factors such as molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2?, pH, and the dosage of Fenton reagent that could affect the PAM degradation in the UV/Fenton/C₄H₄O₆^2? system were investigated. The experimental results showed that adding C₄H₄O₆^2? to UV/Fenton system could form photosensitive ferrous complexes, which led to higher degradation efficiency of PAM. The degradation rate of PAM could be up to 95.2% under the following conditions: the concentration of H₂O₂, Fe²⁺, and C₄H₄O₆^2? were 22.5, 2.25, and 2.25 mmol/L, respectively (i.e., molecular ratio of H₂O₂/Fe²⁺/C₄H₄O₆^2? was 10:1:1), the pH value was 3.0.     

用二氧化钛光催化氧化法降低丙烯腈污水中的化学需氧量

在开放的光催化反应器中,以紫外(UV)光为光源,以二氧化钛为催化剂,研究了不同水质条件下对模拟丙烯腈(AN)污水中化学需氧量(COD)的控制效果及主要影响因素。结果表明,UV光-TiO2催化体系对AN污水中COD具有良好的去除效果。当在浓度为300mg/L模拟AN污水中投加浓度为20mg/L的二氧化钛及紫外光照射180min时,污水体系中的COD残存率为7.9%。同时,反应过程中不会对环境产生二次污染。     

UV/Fenton法处理高浓度香料废水的试验研究

研究了UV/Fenton法处理高浓度废水的新技术以及有关影响因素。试验:pH在2－4，COD／H2O2＝1：1.5,Fe^2 浓度为1.7g／L的条件下，反应时间90min，COD去除率可达99.6%。     

光助氧化技术在水处理中应用

对UV／H2O2技术、UV／O3技术、UV／O3／H2O2技术、photo—Fenton技术以及UV／TiO2技术进行了总结,对不同技术的原理、研究进展及应用进行了评述,并对今后光助氧化技术的研究方向提出了一些建议。     

Intensification of degradation of aqueous solutions of rhodamine B using sonochemical reactors at operating capacity of 7 L

In the present work, degradation of rhodamine B, a typical dye effluent commonly observed in chemical processing wastewaters has been investigated using a sonochemical reactor with capacity of 7 L. The reactor consists of an ultrasonic bath equipped with a single large transducer having longitudinal vibrations with operating frequency of 25 kHz and rated power output of 1 kW. The effect of operational conditions such as the rhodamine B initial concentration, operating pH and use of additives such as H(2)O(2), CCl(4) and TiO(2) has been investigated initially. A mathematical model has also been fitted to estimate the rate constant for rhodamine B removal under different operating conditions. Intensification studies have been carried by combining sonochemical oxidation with photocatalytic oxidation under optimized conditions. In all the investigated systems, complete removal of rhodamine B (10 ppm initial concentration) was obtained using a combination of sonochemical reactor and CCl(4). Sonocatalysis (in the presence of TiO(2)) of rhodamine B showed 92% degradation, while sonophotocatalysis gave degradation of 93%. TOC analysis at various optimum conditions was also performed to quantify the extent of mineralization and it was observed that the extent of mineralization is always lower than the extent of removal of parent compound.     

Para-chlorophenol containing synthetic wastewater treatment in an activated sludge unit: effects of hydraulic residence time

Due to the toxic nature of chlorophenol compounds present in some chemical industry effluents, biological treatment of such wastewaters is usually realized with low treatment efficiencies. Para-chlorophenol (4-chlorophenol, 4-CP) containing synthetic wastewater was treated in an activated sludge unit at different hydraulic residence times (HRT) varying between 5 and 30 h while the feed COD (2500 mg l(-1)), 4-CP (500 mg l(-1)) and sludge age (SRT, 10 days) were constant. Effects of HRT variations on COD, 4-CP, toxicity removals and on settling characteristics of the sludge were investigated. Percent COD removals increased and the effluent COD concentrations decreased when HRT increased from 5 to 15 h and remained almost constant for larger HRT levels. Nearly, 91% COD and 99% 4-CP removals were obtained at HRT levels above 15 h. Because of the highly concentrated microbial population at HRT levels of above 15 h, low effluent (reactor) 4-CP concentrations and almost complete toxicity removals were obtained. High biomass concentrations obtained at HRT levels above 15 h were due to low 4-CP contents in the aeration tank yielding negligible inhibition effects and low maintenance requirements. The sludge volume index (SVI) decreased with increasing HRT up to 15 h due to high biomass concentrations at high HRT levels resulting in well settling sludge with low SVI values. Hydraulic residence times above 15 h resulted in more than 90% COD and complete 4-CP and toxicity removals along with well settling sludge.     

Combined chemical and biological oxidation of penicillin formulation effluent

Antibiotic formulation effluent is well known for its important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study, the chemical treatability of penicillin formulation effluent (average filtered COD(o)=830 mg/l; average soluble COD(o)=615 mg/l; pH(o)=6.9) bearing the active substances penicillin Amoxicillin Trihydrate (C(16)H(19)N(3)O(5)S.3H(2)O) and the beta-lactamase inhibitor Potassium Clavulanate (C(8)H(8)KNO(5)) has been investigated. For this purpose, the penicillin formulation effluent was subjected to ozonation (applied ozone dose=2500 mg/(lxh)) at varying pH (2.5-12.0) and O(3)+H(2)O(2) (perozonation) at different initial H(2)O(2) concentrations (=2-40 mM) and pH 10.5. According to the experimental results, the overall Chemical Oxygen Demand (COD) removal efficiency varied between 10 and 56% for ozonation and 30% (no H(2)O(2)) and 83% (20 mM H(2)O(2)) for the O(3)+H(2)O(2) process. The addition of H(2)O(2) improved the COD removal rates considerably even at the lowest studied H(2)O(2) concentration. An optimum H(2)O(2) concentration of 20 mM existed at which the highest COD removal efficiency and abatement kinetics were obtained. The ozone absorption rate ranged between 53% (ozonation) and 68% (perozonation). An ozone input of 800 mg/l in 20 min was sufficient to achieve the highest BOD(5)/COD (biodegradability) ratio (=0.45) and BOD(5) value (109 mg/l) for the pre-treated penicillin formulation effluent. After the establishment of optimum ozonation and perozonation conditions, mixtures of synthetic domestic wastewater+raw, ozonated and perozonated penicillin formulation effluent were subjected to biological activated sludge treatment at a food-to-microorganisms (F/M) ratio of 0.23 mg COD/(mg MLSSxd), using a consortium of acclimated microorganisms. COD removal efficiencies of the activated sludge process were 71, 81 and 72% for pharmaceutical wastewater containing synthetic domestic wastewater mixed with either raw, ozonated or perozonated formulation effluent, respectively. The ultimate COD value obtained after 24-h biotreatment of the synthetic domestic wastewater+pre-ozonated formulation effluent mixture was around 100 mg/l instead of 180 mg/l which was the final COD obtained for the wastewater mixture containing raw formulation effluent, indicating that pre-ozonation at least partially removed the non-biodegradable COD fraction of the formulation effluent.     

Biological treatment of 2,4,6-trichlorophenol (TCP) containing wastewater in a hybrid bioreactor system with effluent recycle

Due to the toxic effects of trichlorophenol (TCP) on microorganisms, biological treatment efficiencies of TCP containing wastewaters are usually low. Synthetic wastewater containing 2,4,6-TCP was biologically treated in a hybrid-loop bioreactor system consisting of a packed column biofilm and an aerated tank bioreactor with effluent recycle in order to improve COD and TCP removals. Effects of the feed TCP concentration on COD, TCP and toxicity removal performance of the system were investigated for the feed TCP between 50 and 450 mg L(-1) while the sludge age (solids retention time, SRT) and hydraulic residence time (HRT) were kept constant at 20 d and 25 h, respectively. Biomass concentrations in the packed column and in the aeration tank decreased with increasing feed TCP concentrations due to toxic effects of TCP on the organisms. Low biomass concentrations in the system at high feed TCP contents resulted in low COD, TCP and toxicity removals. Therefore, percent TCP, COD and toxicity removals decreased with increasing feed TCP concentrations especially above 400 mg L(-1). The effluent TCP concentrations were lower than 20 mg L(-1) for the feed TCP concentrations below 390 mg L(-1) resulting in TCP and COD removals above 90%. Specific rates of TCP and COD removals increased with the feed TCP due to low biomass concentrations at high TCP contents. The system should be operated at a feed TCP lower than 400 mg L(-1) in order to obtain more than 90% TCP, COD and toxicity removals under the specified experimental conditions.     

Photocatalytic degradation of disperse blue 1 using UV/TiO2/H2O2 process

The photocatalytic degradation of a dye derivative, C.I. disperse blue 1 (1), has been investigated under UV light irradiation in the presence of TiO2 and H2O2 under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique as a function of irradiation time. The degradation was studied under different conditions such as different types of TiO2, reaction pH, catalyst and substrate concentration containing hydrogen peroxide (H2O2), besides molecular oxygen in the presence of TiO2. The degradation of dye was also investigated under sunlight and the efficiency of degradation was compared with that of the artificial light source. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient for the degradation of the dye.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

光催化氧化处理低浓度含醇废水实验

室内实验了TiO2紫外光催化氧化处理废水中的低浓度甲醇。通过对TiO2催化剂活性及添加方式、溶液pH、紫外光强与催化剂加量等参数优化,在TiO2加入浓度为300mg/L和120 W紫外灯照射条件下,对6.8L甲醇浓度为2.77%的低浓度含醇废水持续处理70min后,废水中的甲醇去除率可达98.31%。该实验为进一步处理低浓度含醇废水提供了方法依据。     

Photo-oxidation of NO using an exterior paint--screening of various commercial titania in powder pressed and paint films

The present work aims to evaluate the photocatalytic activity of photo-TiO(2) from various producers (Evonik, Kemira, Kronos, Millennium, Sachtleben and Tayca), in the form of powder pressed films and upon incorporation in a water-based paint, for outdoor NO abatement. The photocatalytic activity of the different samples was evaluated in terms of NO conversion and selectivity towards nitrite and nitrate ions following approximately the ISO 22197-1:2007(E) standard. The highest yields obtained for powder pressed films were achieved with VLP7000 (0.70), followed by VLP7101 (0.55) and UVLP7500 (0.55), all from Kronos. On the other hand, when incorporated in paint films, the highest yields were obtained with PC500 and PC105 from Millennium and UV100 from Sachtleben (ca. 0.15). The paint matrix plays an important role on the photocatalytic activity. In particular, the time for steady state is one or two orders of magnitude higher when the photocatalysts are incorporated in paint films in relation to the powder pressed films. The paint films were activated following the procedure recommended by the above-mentioned standard. However, the photocatalytic activity of films incorporating P25 (Evonik) was displayed only when higher power radiation and higher humidity conditions were used. This allowed for similar levels of photocatalytic activity as the other paint films.     

H2O2／Fe^2＋氧化偶合混凝法处理干膜废水的研究

本文研究了H2O2／Fe^2＋氧化偶合混凝法处理印刷电路板厂干膜废水。讨论了包括过氧化氢浓度、亚铁离子浓度、pH值、时间和混凝pH值等影响因素,试验结果表明,当过氧化氢浓度为457.0mg/L、铁离子浓度为400mg/L、氧化pH值4.0、反温度为40℃、反应时间180min时,COD去除率达84.7%,出水的水质达到排放标准。