2,4-二氯苯氧乙酸臭氧氧化动力学研究

研究了臭氧氧化条件下2,4-二氯苯氧乙酸在鼓泡反应器内的去除动力学,考察了pH、温度、气体流量、初始浓度等因素对反应的影响,得到反应动力学速率常数与温度和pH的关系。     

Development and modeling of a flat plate serpentine reactor for photocatalytic degradation of 17-ethinylestradiol

A flat plate serpentine reactor modified from ultraviolet disinfection pool in municipal wastewater treatment plants was developed for the removal of 17-ethinylestradiol (EE2) for the first time. The photocatalytic degradation performance of EE2 was investigated in this serpentine reactor under different conditions such as inlet concentrations, loaded catalyst concentrations, incident radiations fluxes, and flow velocities. More than 98 % of EE2 was removed under certain conditions within 120 min. An integrated model including a six-flux adsorption–scattering model and a modified flow diffusion model was established to investigate the effect of radiation field and flow velocities, respectively. A satisfactory agreement was observed between the model simulation and experimental results, showing a potential for design and scale-up of photocatalytic reactor for wastewater treatment.     

Bio-remediation of pendimethalin contaminated soil by bio-slurry phase reactor: bio-augmenting with ETP micro-flora

Bio-remediation of pendimethalin contaminated soil (500 μg/g) was studied in a bio-slurry phase reactor operated in the sequencing batch mode under anoxic–aerobic–anoxic micro-environment. The effect of augmentation with ETP micro-flora on the process performance of the reactor was also evaluated. The reactor was operated with a total cycle period of 120 hours comprising 3 hours of fill, 114 hours of react and 3 hours of decant phases. The Control reactor (without ETP micro-flora) showed 23% of substrate removal efficiency, which may be attributed to the volatile nature of the substrate. The Reactor operated with native soil micro-flora showed more or less equal degradation compared to the control reactor indicating the toxic and inhibitory nature of the substrate over the slurry micro-flora. The reactor augmented with mixed ETP micro-flora showed enhanced performance with more than 90% of substrate removal efficiency within 72 hours of the cycle period. Due to augmentation, the CFU values in the slurry phase system showed a two-fold increase. Process performance during reactor operation was assessed by monitoring pendimethalin concentration and bio-chemical process parameters viz. pH, dissolved oxygen (DO), colony forming units (CFU) and oxygen consumption rate (OCR), during sequence phase operation.     

介质阻挡放电氧化降解木质素磺酸钠的动力学研究

为了有效地处理难生物降解的造纸废水,采用气相介质阻挡放电产生氧化性物质,对木质素磺酸钠进行了氧化降解研究。在不同操作条件下,对其降解动力学及矿化程度进行了研究。结果表明,介质阻挡放电能有效地降解木质素磺酸钠,其氧化降解反应遵循准一级动力学反应。当峰值电压为20 kV,被水蒸气饱和的空气为气源,流量为7 L/min时,氧化处理60 min后,木质素磺酸钠降解率达到70％。其速率常数K随峰值电压、气源、气体流量和木质素磺酸钠的初始浓度的变化而不同。气体流量越大,木质素磺酸钠的初始浓度越低,速率常数K越大,降解效果越好。随着处理时间的增加,氧化性物质能将部分木质素磺酸钠矿化使溶液TOC降低,当被水蒸气饱和的空气作为气源时,氧化处理120min,21.38%的TOC被去除。     

TiO2/Ti转盘液膜反应器光电催化处理罗丹明B

采用溶胶-凝胶法制备了TiO2/Ti电极,X射线衍射(XRD)分析表明,TiO2主要为锐钛矿,晶粒尺寸约为46 nm.以TiO2/Ti电极作阳极,Cu电极作阴极,组装成转盘液膜反应器,考察了其光电催化处理染料罗丹明B(RhB)的影响因素(转盘转速、偏压、溶液初始pH、RhB初始浓度和电解质浓度).得到最佳处理条件为:转盘转速90 r/min,偏压0.4V,溶液初始pH2.5,电解质(硫酸钠)质量浓度0.5 g/L.在最佳处理条件下,处理20 mg/L RhB染料废水90 min的脱色率和总有机碳(TOC)去除率分别达到97.2％和72.7％.结果表明,由于同时强化了激发光源的利用率和溶液的传质效率,TiO2/Ti转盘液膜反应器可高效光电催化处理染料废水.     

Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor

The photocatalytic oxidation of methyl orange under weak illumination conditions was carried out in two different types of fluidized bed reactors. TiO2 powder was employed as the photocatalysts and a 15 W low pressure mercury lamp was used as the light source and the reactor volume was 2.5 l. The parametric study of photocatalytic oxidation of methyl orange in two different types of fluidized beds was investigated; effect of catalyst loadings, pH, air flow rate, initial concentration and oxygen concentration on the oxidation reaction rate. The experimental results were analyzed in conjunction with the characteristics of fluidized bed and the reactor geometry effect on the reaction rate was analyzed.     

三维电极电吸附动态反应器的除氟特征研究

采用自制的单极性复合型三维阳极作为第三维电极对含氟水进行动态电促吸附实验,通过研究不同填充床高度、阴阳极板间距、隔膜材料对电促吸附除氟效果的影响,确定反应器的最佳结构参数为:填充床高度20 cm、阴阳极板间距4 cm、隔膜为nafion117膜。工作电压、进水pH、进水流速、共存物质对氟离子去除效果的影响结果表明:在一定范围内增大工作电压,降低进水pH或进水流速均可提高除氟效果。相应的最佳操作条件为:工作电压7 V、进水流速4 mL/min、酸性pH;腐殖酸和碳酸根离子的存在会对氟离子去除产生较强抑制作用,低浓度的氯离子可促进氟离子的电促吸附。扫描电镜(SEM)-电子能谱(EDX)的表征结果显示三维颗粒电极的表面及孔隙内部均可吸附氟离子,且电吸附后并未出现电极腐蚀现象。     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Performance evaluation of a continuous flow photocatalytic reactor for wastewater treatment

A novel photocatalytic reactor for wastewater treatment was designed and constructed. The main part of the reactor was an aluminum tube in which 12 stainless steel circular baffles and four quartz tube were placed inside of the reactor like shell and tube heat exchangers. Four UV–C lamps were housed within the space of the quartz tubes. Surface of the baffles was coated with TiO₂. A simple method was employed for TiO₂ immobilization, while the characterization of the supported photocatalyst was based on the results obtained through performing some common analytical methods such as X-ray diffraction (XRD), scanning electron microscope (SEM), and BET. Phenol was selected as a model pollutant. A solution of a known initial concentration (20, 60, and 100 ppmv) was introduced to the reactor. The reactor also has a recycle flow to make turbulent flow inside of the reactor. The selected recycle flow rate was 7?×?10^?5 m³.s^?1, while the flow rate of feed was 2.53?×?10^?7, 7.56?×?10^?7, and 1.26?×?10^?6 m³.s^?1, respectively. To evaluate performance of the reactor, response surface methodology was employed. A four-factor three-level Box–Behnken design was developed to evaluate the reactor performance for degradation of phenol. Effects of phenol inlet concentration (20–100 ppmv), pH (3–9), liquid flow rate (2.53?×?10^?7?1.26?×?10^?6 m³.s^?1), and TiO₂ loading (8.8–17.6 g.m^?2) were analyzed with this method. The adjusted R ² value (0.9936) was in close agreement with that of corresponding R ² value (0.9961). The maximum predicted degradation of phenol was 75.50 % at the optimum processing conditions (initial phenol concentration of 20 ppmv, pH?～?6.41, and flow rate of 2.53?×?10^?7 m³.s^?1 and catalyst loading of 17.6 g.m^?2). Experimental degradation of phenol determined at the optimum conditions was 73.7 %. XRD patterns and SEM images at the optimum conditions revealed that crystal size is approximately 25 nm and TiO₂ nanoparticles with visible agglomerates distribute densely and uniformly over the surface of stainless steel substrate. BET specific surface area of immobilized TiO₂ was 47.2 and 45.8 m² g^?1 before and after the experiments, respectively. Reduction in TOC content, after steady state condition, showed that maximum phenol decomposition occurred at neutral condition (pH?～?6). Figure

The schematic view of the experimental set-up     

Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism

Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen.     

电增强载铝活性炭纤维吸附除氟的效果与影响因素

以含氟地下水为研究对象,采用自制电促吸附除氟反应器,开展电增强载铝活性炭纤维吸附除氟的动态实验,研究了不同电压、极板间距、地下水碱度和流速对吸附除氟效果的影响。实验结果表明,在负载炭纤维毡的电极一端加正电,可以提高除氟效果。当电压为1.6 V时除氟效果较好,单位面积炭毡处理达标水量为56.7 L/m2;极板间距设置为4mm时电吸附反应器除氟效果最佳;通过调节pH改变地下水碱度,当地下水pH调节为5.5时,电吸附反应器除氟效果较未调节前提高50%;当采用3对电极板,流速为1.88 m/h时,达到最高表面处理负荷2 073.6 L/(m2.d);探究了反应器的反洗再生方式,并连续进行了吸附再生的动态实验;穿透的反应器以Al2(SO4)3溶液为再生液并采用反向加电1.6 V的方式,可以达到较好的再生效果,实现连续动态运行。     

电液压脉冲放电与铁屑内电解法联用处理TNT废水试验研究

TNT结构稳定,废水又具有生物毒性,难以生物降解,采用电液压脉冲放电与铁屑内电解法联用能有效处理TNT废水。研究了铁屑投加量、pH值和铁屑重复使用对TNT降解的影响。试验条件为：放电电压36 kV,废水体积7 L,TNT初始浓度90 mg/L,电极间距8 mm。结果表明,在投加铁屑700 g和pH值为6.5时,TNT降解率分别达到97.7%,铁屑重复使用6次不影响TNT降解效果;放电后静置一段时间,TNT仍然继续降解;在125 L的反应器中处理115 L废水,TNT初始浓度50 mg/L,TNT最大降解率达94.2％,TNT浓度降至2.9 mg/L。     

Experimental assessment of bio-reduction of di-2-thylhexyl phthalate (DEHP) under aerobic thermophilic conditions

The reduction of organic contaminants in sewage sludge is of great importance for a further sludge disposal or agricultural utilization. Laboratory scale batch experiments were performed to assess the potential use of the aerobic thermophilic treatment technique to reduce the concentration of difficult to degrade organic chemicals. Di-2-ethylhexyl phthalate (DEHP) was chosen as a model representative of these chemicals. The effect of the sludge temperature and aeration rate on the reduction of DEHP concentration as well as on the reduction of the organic dry solid (oDS) was investigated. With a specific air flow rate of 16 m3/m3.h and a thermophilic temperature of 63 degrees C it was possible to achieve up to 70% reduction of the DEHP concentration and 61% of oDS within 96 hours. The maximum degradation of the oDS matter occurred within the first 24 hours of operation whereby only little oDS was degraded afterward. During the experiments the reactor content was routinely monitored for pH, COD, along with the ammonia nitrogen and orthophosphate concentrations.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.     

Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron

Application of a novel Fenton-like system with zero-valent iron, EDTA and Air (ZVI/EDTA/Air) was investigated to degrade dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene (DDE) in the actual contaminated soil from an organochlorine pesticide site. It was found DDTs in the soil were effectively degraded by the system at room temperature, ambient atmosphere pressure and near neutral pH. The dosages of EDTA and ZVI were the dominant factors influencing the removal of contaminants. An increase of EDTA from 0.05 to 0.2 mM and ZVI from 1 to 5 g L^?1 improved the removal of the contaminants significantly. However, excessive amount of EDTA led to a negative effect on the degradation process. Meanwhile, EDTA was simultaneously degraded so as to avoid the secondary pollution risk on soil remediation. Only a small amount of 4,4′-DDE and 2,2-bis(4-chlorophenyl)-1-chloroethylene (4,4′-DDMU) generated as the intermediates of DDT degradation during the process. Our investigation suggests that the Fenton-like system is a promising alternative for remediation of organochlorine pesticides contaminated soils.     

Biomassbed: a biological system to reduce pesticide point contamination at farm level

A potential method for cleaning water from point-source pollution by organic compounds is using biological reactors. In this study, four reactors were tested for their ability to retain and degrade pesticides. The pesticides tested were the insecticide chlorpyrifos, the fungicide metalaxyl and the herbicide imazamox. The reactors were filled with differing mixtures of vine-branch, citrus peel, urban waste and public green compost. The reactor volume was 188 l. Forced circulation of the contaminated solution was programmed to decontaminate the solution. Both retention and degradation of the compounds by the reactors was studied. Chlorpyrifos was the best retained, due to its physico-chemical characteristics, while only one substrate effectively retained metalaxyl and imazamox (citrus peel+urban waste compost). Degradation of the pesticides in the reactors was faster than published values for degradation in soil. The half-life of all pesticides in the reactors was less than 14 days, compared to literature values of 60-70 days in soil. The combined retention and fast degradation make the biofilter a feasible technique to reduce spill-related and point environmental contamination by pesticides. The technique is most effective against persistent pesticides, while for mobile pesticides, the efficiency can be improved with several passages of the contaminated solution through biofilters.     

Enhanced degradation of bioremediation residues in petroleum-contaminated soil using a two-liquid-phase bioslurry reactor

A study was performed to determine the potential of two-liquid-phase (TLP) bioslurry reactors using silicon oil as solvent for degradation of residual contaminants in petroleum-contaminated soil. The residues were characterized by gas chromatography–mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. This allowed for the identification of a mixture of residual biomarkers, metabolic byproducts, oxygenated and hetero-polynuclear aromatic hydrocarbons in the contaminated soil. The removal amount of total extractable organics (TEO) was 15 900 mg kg⁻¹ soil in the TLP reactor within 12 weeks. However, TEO remained intact in the bioslurry reactor without the addition of silicon oil for the duration of the experiment, due to high toxicity of metabolites to the microorganisms. The availability of TEO was calculated using a mild extraction with Triton X-100, and the amount of TEO extracted was in accord with the amount of biodegraded TEO. Significantly reduced toxicity in soil was observed at week 12 through TLP remediation. Dehydrogenase activity in the bioslurry reactor was strongly suppressed. Fluorescein diacetate was significantly hydrolyzed by the composition of bioremediation residues in the contaminated soil. Microbial adhesion to the solvent was revealed by the determination of microbial activity in the water-immiscible-liquid.     

Hydraulic performance of a proposed in situ photocatalytic reactor for degradation of MTBE in water

Methyl tert-butyl ether (MTBE) groundwater remediation projects often require a combination of technologies resulting in increasing the project costs. A cost-effective in situ photocatalytic reactor design, Honeycomb II, is proposed and tested for its efficiency in MTBE degradation at various flows. This study is an intermediate phase of the research in developing an in situ photocatalytic reactor for groundwater remediation. It examines the effect of the operating variables: air and water flow and double passages through Honeycomb II, on the MTBE removal. MTBE vaporisation is affected by not only temperature, Henry’s law constant and air flow to volume ratio but also reactor geometry. The column reactor achieved more than 84% MTBE removal after 8 h at flows equivalent to horizontal groundwater velocities slower than 21.2 cm d⁻¹. Despite the contrasting properties between a photocatalytic indicator methylene blue and MTBE, the reactor efficiency in degrading both compounds showed similar responses towards flow (equivalent groundwater velocity and hydraulic residence time (HRT)). The critical HRT for both compounds was approximately 1 d, which corresponded to a velocity of 21.2 cm d⁻¹. A double pass through both new and used catalysts achieved more than 95% MTBE removal after two passes in 48 h. It also verified that the removal efficiency can be estimated via the sequential order of the removal efficiency of one pass obtained in the laboratory. This study reinforces the potential of this reactor design for in situ groundwater remediation.     

对氨基苯磺酸降解菌的分离及其特性研究

从温州地区受污染的河水中分离到一株能降解对氨基苯磺酸的菌株WZR-3,该菌株能以对氨基苯磺酸为惟一碳源、能源生长。经对其形态特征、生理生化以及16S rDNA序列分析,该菌株初步鉴定为人苍白杆菌(Ochrobactrum anthropi)。该菌株利用对氨基苯磺酸生长时最适生长温度和pH值分别为30℃和7。该菌在10 g/L对氨基苯磺酸时仍能生长,最适生长浓度为300 mg/L对氨基苯磺酸。降解底物广谱性测试表明,该菌株还能降解多种芳香类化合物。     

Model reactor for photocatalytic degradation of persistent chemicals in ponds and waste water

A laboratory scale flow-through model reactor for the degradation of persistent chemicals using titanium dioxide (TiO₂) as photocatalyst immobilized on glass beads is presented. In the test system with a volume of 18 L contaminated water is pumped to the upper part of the floating reactor and flows over the coated beads which are exposed to UV-radiation. The degradation of two dyes of different persistance was investigated. Primary degradation of methylene blue did not fit a first order kinetic due to coincident adsorption onto the photocatalyst and direct photolysis, resulting in a half-life of 6 h. A filtrate of a green algae suspension accelerated the colour removal. In contrast, reactive red 2 was degraded only by photocatalysis; neither adsorption nor direct photolysis led to a colour removal. The course of primary degradation followed a first order kinetic with a half-life of 18 h and a rate constant of 0.04 h⁻¹. Analysis of the degradation products indicated mineralization by detection of NO₂⁻ and NO₃⁻, accompanied by a decrease of pH and an increase of conductivity. A successful adaptation of the model reactor (scale 1:10) to dimensions required for surface waters and waste water treatment plants would be a costefficient and environmentally sustainable application of photocatalysis for the treatment of industrially polluted water and could be of relevance for third world contries, particularly those favoured by high solar radiation.