超临界水氧化去除含酚废水TOC的动力学研究

本文利用自行设计的一套连续式超临界水氧化实验装置,以过氧化氢为氧化剂,处理实验室模拟含酚废水。在超临界条件下(P=30MPa,T=400℃,440℃,480℃,520℃)进行超临界水氧化实验。结果表明,TOC去除速率在氧化剂过量10倍的情况下,对TOC是2.15级反应。速率常数与温度的关系符合阿仑尼乌斯公式。反应的实验活化能为171.7kJ/mol,前置因子A为2.99×1011。     

苯胺的超监界水氧化研究

苯胺的超临界水氧化表明，氧化剂H2O2、试验温度、压力和停留时间以及水样的起始TOC值对TOC的去除率有显著影响。在本试验中，选取了硫酸铜、硫酸铁、硫酸锰等金属盐进行苯胺的均相催化氧化试验研究，结果表明，这些金属盐对苯胺的氧化有不同的催化活性，筛选出硫酸锰和硫酸亚铁进行了进一步研究，以硫酸猛作催化剂为例，在450℃，28MPa，K＝1．1，pH＝4．0的条件下，当停留时间为46s时，TOC去除率达到100％。     

催化超临界水氧化偏二甲肼

采用CuO/γ-Al_2O_3和MnO_2/γ-Al_2O_3为催化剂,H_2O_2为氧化剂,在固定床反应器中进行催化超临界水氧化偏二甲肼实验.结果表明,CuO和MnO_2对偏二甲肼的氧化降解具有显著的促进作用.偏二甲肼的去除率随反应温度和压力的升高、停留时间的延长而提高.在24—26MPa、400—450℃条件下,数秒钟内COD去除率可达到99%以上.显示出催化超临界水氧化技术的高效性.催化剂CuO/γ-Al_2O_3的催化效果优于MnO_2/γ-Al_2O_3.进一步研究表明,偏二甲肼催化超临界水氧化为·OH引发的自由基反应,最终氧化产物为CO_2,N_2和H_2O.     

合成有机化学品的超临界水氧化

研究了超临界水氧化系统中合成有机化学品 ,如酚、间苯三酚、对叔丁基酚、间甲酚、3 ,5-二甲酚、苯胺、硝基苯、叔丁醇、三氯乙醛等的氧化作用。在实验条件下 ,上述化学品均能显著降解。酚和苯胺的去除随氧化剂过氧化氢加入量增加而增加。较优的K值 (实验中加入的H2 O2 量与按反应方程化学计量的量的比值 )对酚和苯胺分别为 1 .5和 1 .1。实验结果显示 ,当系统的压力为 3 0MPa ,温度为 4 50℃ ,停留时间为 1 90s,K =2 .0 (对酚 )和系统压力为 2 5MPa,温度为 50 0℃ ,停留时间为 3 0s,K =1 .2 (对苯胺 ) ,氧化效率都接近 1 0 0 %。含酚废水处理结果表明温度、压力、停留时间 3种因素中 ,温度是主要影响因素     

活性橙7在亚临界/超临界水中的结焦反应试验研究

针对印染污染物的超临界水氧化处理系统中,有机物在预热过程中结焦积碳引起的系统设备及管线堵塞问题,本文提出了对典型印染污染物活性橙7染料在亚临界/超临界水中的水热反应进行研究,考察了操作参数对染料有机物向焦油转化过程的影响机制.研究结果表明,反应温度为350℃时,焦油的转化率最大,部分氧化以及添加剂NaOH有利于气化反应路径的进行,进而可有效地抑制焦油生成,另外增加物料浓度,促进了染料化合物向焦油积碳的转化,而这不利于系统运行.研究结果可以为优化印染污染物的超临界水氧化系统提供理论依据.     

苯胺的超临界水氧化研究1

苯胺的超临界水氧化表明,氧化剂Ｈ２Ｏ２、试验温度、压力和停留时间以及水样的起始ＴＯＣ值对ＴＯＣ的去除率有显著影响．在本试验中,选取了硫酸铜、硫酸铁、硫酸锰等金属盐进行苯胺的均相催化氧化试验研究,结果表明,这些金属盐对苯胺的氧化有不同的催化活性,筛选出硫酸锰和和硫酸亚铁进行了进一步的研究．以硫酸锰作催化剂为例,在４５０℃,２８ＭＰａ,Ｋ＝１．１,ｐＨ＝４．０的条件下,当停留时间为４６ｓ时,ＴＯＣ去除率达到１００%．     

活性炭负载TiO2催化臭氧氧化去除水中酚的研究

本文采用活性炭负载TiO2作催化剂对臭氧氧化去除含酚废水进行了研究．研究了不同的酚初始浓度、pH值及臭氧浓度对苯酚去除率的影响，获得了反应动力学常数．实验结果表明：苯酚初始浓度越小，去除率越高．在本实验条件下，向150mL苯酚溶液中通入浓度为3．48mg/L、流量为0．05m^3／h的臭氧化空气反应30min去除率即可达到99％以上。     

TiO2-AC-PTFE光阳极的制备及光电催化降解苯酚

采用溶胶-凝胶法制备载钛活性炭,研究了钛酸丁酯、无水乙醇、去离子水、硝酸和活性炭的用量以及热处理温度对载钛活性炭的吸附性能和光催化性能的影响,优化载钛活性炭的制备条件,用载钛活性炭制备光阳极,以苯酚为目标污染物研究了光阳极的吸附性能、在紫外光照射下的光催化氧化性能、阳极电氧化性能和光电组合氧化性能.发现光阳极良好的吸附性能可以大幅度地提高苯酚的总去除率,光电组合氧化有明显的协同作用且宜在酸性条件下进行.     

臭氧对气体中甲硫醇的氧化降解

甲硫醇是主要恶臭污染物之一,研究甲硫醇的降解技术对于恶臭异味的治理具有重要意义.为了获得臭氧对气体中甲硫醇的氧化降解性能,实验研究了臭氧对气体中甲硫醇的均相氧化过程,考察了氧含量、臭氧投加量、反应时间、温度和湿度等因素的影响.结果表明,氧气可将甲硫醇部分氧化为二甲二硫.甲硫醇去除率随臭氧投加量、反应时间的增加而升高,且臭氧对气体中甲硫醇的氧化降解过程符合伪一级动力学反应模型.甲硫醇的去除率随温度升高而增大,该趋势在温度高于50℃时不再明显;氧化反应的最佳相对湿度为45%—62%.采用原位红外光谱、气相色谱-质谱联用和离子色谱技术对甲硫醇氧化降解过程的研究证明,考察条件下,臭氧不能将全部甲硫醇矿化为二氧化碳和水,而是生成了部分醛类和酮类中间产物,且甲硫醇中硫的主要氧化产物是硫单质.综合考虑臭氧氧化甲硫醇的最佳反应条件和降解产物,该工艺存在能耗高、易造成二次污染等不足,在实际应用中不建议采用臭氧直接氧化工艺对含甲硫醇臭气进行净化.     

催化湿式氧化法预处理显影废水的研究

考察了催化湿式氧化法对医院显影废水进行预处理的可行性.紫外扫描结果表明,对甲氨基苯酚硫酸盐、对苯二酚等特征污染物被降解为小分子物质,在催化剂Ru/TiO2存在下,催化湿式氧化法与湿式氧化相比,有机物的降解更加彻底.通过考察催化剂用量、温度、压力及pH值等条件对CODCr去除率的影响,确定适宜的反应条件为:催化剂用量为2g·l-1,温度为220℃,压力为1.5MPa,pH为8.9.在上述反应条件下,CODCr去除率达62.5%,色度去除率达98%,BOD5/CODCr值由原来的0.07提高到0.45.     

Catalytic TiO2 oxidation of ethanethiol for environmentally begnin air pollution control of sulphur compounds

Volatile organic compounds containing reduced sulphur such as thiols and thioethers are released mostly from biological activities and a number of manufacturing processes, such as papermaking and petroleum refining. Environmentally benign and cost-effective air pollution control technology for reduced sulphur compounds is still a topic of research, e.g., in pulp and paper industry. Due to its advantages, photocatalytic oxidation over titanium dioxide presents a potential alternative for the air treatment strategies. The temperature influence on the reaction pathway and kinetics of gas-phase photocatalytic oxidation and thermal catalytic decomposition of ethanethiol over Degussa P25 TiO₂ was established by a continuous flow method in a simple tubular reactor at temperatures from 373 to 453 K. Kinetic parameters for ethanethiol were: adsorption enthalpy −45 kJ mol⁻¹ and activation energy 42 kJ mol⁻¹. Sulphur dioxide, carbon monoxide, carbon dioxide, acetic acid and water were identified as by-products.     

Catalytic wet air oxidation of phenol,nitrobenzene and aniline over the multi-walled carbon nanotubes (MWCNTs) as catalysts

Wet air oxidation (WAO) is one of effective technologies to eliminate hazardous, toxic and highly concentrated organic compounds in the wastewater. In the paper, multi-walled carbon nanotubes (MWCNTs), functionalized by O₃, were used as catalysts in the absence of any metals to investigate the catalytic activity in the catalytic wet air oxidation (CWAO) of phenol, nitrobenzene (NB) and aniline at the mild operating conditions (reaction temperature of 155°C and total pressure of 2.5 MPa) in a batch reactor. The MWCNTs were characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), gas adsorption measurements (BET), fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The functionalized MWCNTs showed good catalytic performance. In the CWAO of phenol over the functionalized MWCNTs, total phenol removal was obtained after 90 min run, and the reaction apparent activation energy was ca. 40 kJ·mol^-1. The NB was not removed in the CWAO of single NB, while ca. 97% NB removal was obtained and 40% NB removal was attributed to the catalytic activity after 180 min run in the presence of phenol. Ca. 49% aniline conversion was achieved after 120 min run in the CWAO of aniline.     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.     

Exposure and Health Effects of Cadmium

The results of a study of photocatalytic degradation of phenol using aqueous oxygenated TiO₂ (anatase) suspensions in a batch Pyrex photoreactor are reported. The influence on the photodegradation rate of various parameters as pH, phenol and TiO₂ content, oxygen partial pressure, anions present in the dispersions was investigated. A complete oxidation of phenol was observed. Intermediate compounds, catechol and quinone, were detected. It was observed that the photodegradation also proceeded with sunlight radiation. A mechanistic and kinetic model, which accounts for the results obtained, is given. Likely reasons for inactivity of the rutile modification for this reaction are also given.     

Effect of dilution rate on dynamic and steady-state biofilm characteristics during phenol biodegradation by immobilized Pseudomonas desmolyticum cells in a pulsed plate bioreactor

Continuous pulsed plate bioreactor (PPBR) was used for phenol biodegradation. Pseudomonas desmolyticum cells immobilized on granular activated carbon was used. Dynamic and steady state biofilm characteristics depend on dilution rate (DR). Lower DR favour phenol degradation and uniform, thick biofilm formation. Exo polymeric substance production in biofilm are favoured at lower dilution rates. Pulsed plate bioreactor (PPBR) is a biofilm reactor which has been proven to be very efficient in phenol biodegradation. The present paper reports the studies on the effect of dilution rate on the physical, chemical and morphological characteristics of biofilms formed by the cells of Pseudomonas desmolyticum on granular activated carbon (GAC) in PPBR during biodegradation of phenol. The percentage degradation of phenol decreased from 99% to 73% with an increase in dilution rate from 0.33 h?1 to 0.99 h?1 showing that residence time in the reactor governs the phenol removal efficiency rather than the external mass transfer limitations. Lower dilution rates favor higher production of biomass, extracellular polymeric substances (EPS) as well as the protein, carbohydrate and humic substances content of EPS. Increase in dilution rate leads to decrease in biofilm thickness, biofilm dry density, and attached dry biomass, transforming the biofilm from dense, smooth compact structure to a rough and patchy structure. Thus, the performance of PPBR in terms of dynamic and steady-state biofilm characteristics associated with phenol biodegradation is a strong function of dilution rate. Operation of PPBR at lower dilution rates is recommended for continuous biologic treatment of wastewaters for phenol removal.     

发光菌的流动注射分析体系及其应用

本文以明亮发光杆菌作为污染物质毒性检测的指示生物，探讨了有机磷农药、酸、碱、分配等污染物对发光细菌的毒性作用；研究了ｐＨ值、温度对有机磷农药降解的影响；测定了该本系对水体中的部分重金属离子，无机离子、阴离子洗涤剂ＳＤＳ和大肠杆菌的检测灵敏度；并对采自于厦门市区的若干水样进行监测分析。     

Combined treatment of phenolic wastewater by wet air oxidation and activated sludge

Wet air oxidation (WAO) is employed in this work for treating high concentration chemical wastewater containing phenol and/or phenolic compounds. Experimental results indicate that over 90% removal of phenol or phenolic compounds can be efficiently achieved in the WAO process. Despite of the high treatment efficiency of the WAO process, the treated wastewater, however, still retains relatively high chemical oxygen demand (COD) concentration and does not meet the safe discharge standard. Hence further treatment of the WAO treated wastewater by an aerobic biological treatment using acclimatized activated sludge is necessary. It is found in the present studies that the combined process, if appropriately operated, is capable of drastically reducing the COD concentration of the high concentration chemical wastewater to meet the safe discharge requirement. The operating conditions of the combined process are investigated to determine their respective effects on the overall treatment efficiency. The experimental data also indicate that the oxidation reaction can be represented by a first order kinetics in terms of the component or COD concentration. For both single component and multicomponent wastewaters, the WAO process was found to have different activation energy for oxidation below and above 200°C, suggesting possibly different reaction mechanisms between these temperature ranges. The experimental results provided in the present work can provide significant and practical information for optimizing the combined treatment method.     

Catalytic ozonation of reactive red X-3B in aqueous solution under low pressure: decolorization and OH· generation

Catalytic ozonation of Reactive Red X-3B in aqueous solution had been carried out in an ozone oxidation reactor where Mn-Fe-ceramic honeycomb was used as the catalysts. The presence of Mn-Fe-ceramic honeycomb catalyst could obviously improve the decoloration efficiency of Reactive Red X-3B and the utilization efficiency of ozone compared to the results from non-catalytic ozonation. Adsorption of Reactive Red X-3B had no obviously influence on the degradation efficiency. Addition of tert-butanol significantly decreased the degradation efficiency, indicating that the degradation of Reactive Red X-3B followed the mechanism of hydroxyl radical (OH·) oxidation. The operating variables such as reaction pressure and ozone supply had a positive influence on the degradation efficiency, mainly attributing to facilitate the ozone decomposition and OH· formation.     

Performance of a hybrid anaerobic-contact oxidation biofilm baffled reactor for the treatment of decentralized molasses wastewater

A novel hybrid anaerobic-contact oxidation biofilm baffled reactor （HAOBR） was developed to simultaneously remove nitrogenous and carbonaceous organic pollutants from decentralized molasses wastewater in the study. The study was based on the inoculation of anaerobic granule sludge in anaerobic compartments and the installation of combination filler in aerobic compartments. The performance of reactor system was studied regarding the hydraulic retention time （HRT）, microbial characteristics and the gas water ratio （GWR）. When the HRT was 24h and the GWR was 20：1, total ammonia and chemical oxygen demand （COD） of the effluent were reduced by 99% and 91.8%, respectively. The reactor performed stably for treating decentralized molasses wastewater. The good performance of the reactor can be attributed to the high resistance of COD and hydraulic shock loads. In addition, the high solid retention time of contact oxidation biofilm contributed to stable performance of the reactor.     

Oxygen supply in aquatic ectotherms: partial pressure and solubility together explain biodiversity and size patterns

Aquatic ectotherms face the continuous challenge of capturing sufficient oxygen from their environment as the diffusion rate of oxygen in water is 3 x 10(5) times lower than in air. Despite the recognized importance of oxygen in shaping aquatic communities, consensus on what drives environmental oxygen availability is lacking. Physiologists emphasize oxygen partial pressure, while ecologists emphasize oxygen solubility, traditionally expressing oxygen in terms of concentrations. To resolve the question of whether partial pressure or solubility limits oxygen supply in nature, we return to first principles and derive an index of oxygen supply from Fick's classic first law of diffusion. This oxygen supply index (OSI) incorporates both partial pressure and solubility. Our OSI successfully explains published patterns in body size and species across environmental clines linked to differences in oxygen partial pressure (altitude, organic pollution) or oxygen solubility (temperature and salinity). Moreover, the OSI was more accurately and consistently related to these ecological patterns than other measures of oxygen (oxygen saturation, dissolved oxygen concentration, biochemical oxygen demand concentrations) and similarly outperformed temperature and altitude, which covaried with these environmental clines. Intriguingly, by incorporating gas diffusion rates, it becomes clear that actually more oxygen is available to an organism in warmer habitats where lower oxygen concentrations would suggest the reverse. Under our model, the observed reductions in aerobic performance in warmer habitats do not arise from lower oxygen concentrations, but instead through organismal oxygen demand exceeding supply. This reappraisal of how organismal thermal physiology and oxygen demands together shape aerobic performance in aquatic ectotherms and the new insight of how these components change with temperature have broad implications for predicting the responses of aquatic communities to ongoing global climate shifts.