空化效应在有机废水处理中的应用研究

综述了空化效应的机理及其在有机废水处理中应用的研究进展.介绍了超声降解水中有机污染物的机理、影响超声降解的因素以及超声降解与其它处理方法的联用,评述了射流和涡流空化效应产生的机理及其在有机物处理中的应用,表明射流和涡流空化比超声空化效率更高,并且在处理量上具有明显优势,还对空化效应在有机废水处理中的应用前景作了展望.     

超声-光催化降解水中有机污染物

超声-光催化是一项近年发展起来的废水处理的新型高级氧化技术。该技术利用超声的空化效应、自由基效应以及机械效应强化光催化的催化效能,实现超声和光催化对水中有机污染物的协同降解。本文从水中有机污染物的超声-光催化降解机理、降解动力学、影响因素（光催化剂类型和投加量、超声频率和强度、溶液pH值、温度、反应物初始浓度、溶解性气体和离子强度）和反应器类型（悬浮型、固定床型）4个方面介绍了相关研究进展,提出了目前存在的主要问题,并展望了超声-光催化降解水中有机污染物的发展方向。     

有毒有机污染物光化学降解及机理研究

水环境污染已成为全球性普遍关注的重要课题.Fenton氧化法和Fenton光化学氧化法由于它在处理废水中的有毒有机污染物方面呈现了其它处理方式不能取代的特点而具有广阔的应用前景.虽然Fenton氧化法是一种非常有效的废水处理方法,但是由于体系中大量的铁离子的存在,使得处理后的体系带有颜色,且沉降铁泥的处理大大增加了运行成本.此外,Fenton反应一般需要在pH小于3的酸性介质中进行及在反应过程中过氧化氢的利用率不高等不足都限制了该方法的广泛应用.在本文中,我们用铁络合物代替Fenton反应中的铁离子并首次把可见光引入到反应体系中氧化降解有机污染物,着重研究了铁络合物在可见光照射下在均相和异相反应体系中对有毒有机污染物的光催化降解动力学、光化学反应机理、微环境的影响、活性自由基的形成以及光降解产物等方面内容,并得出以下几个重要结论:     

杂多酸光催化降解有机污染物

本文综述了杂多酸对有机污染物的光催化降解,包括自身光致催化作用,半导体协同光催化作用,H₂O₂存在下的类Fenton反应和超声辅助催化作用。杂多酸与有机物反应的机理主要是电子-空穴对的产生和·OH等自由基的生成。概述了杂多酸的结构类型和杂多酸光催化作用的优点和局限性,提出利用掺杂调变杂多酸的晶体结构,降低其能带宽度,提高光催化作用反应的量子效率;探索杂多酸与其它电子受体的组合,特别是与具有可见光活性的物质的组合,以扩大光响应范围,实现可见光催化反应。     

电-Fenton及类电-Fenton技术处理水中有机污染物

传统Fenton技术是一种广泛用于水体里有机污染物降解的高级氧化技术(advanced oxidation technologies, AOTs)。它利用Fenton试剂Fe²⁺与H₂O₂反应生成具有强氧化性的羟基自由基(^·OH),从而降解有机污染物。基于相似的机理,过渡金属离子(Fe²⁺、Co²⁺和Ag⁺等)也可与过硫酸盐反应生成氧化能力较强的硫酸根自由基(SO₄^·-),而被称之为类Fenton技术。传统Fenton技术存在Fe²⁺投加量多,产生的铁污泥多等缺点,因此,有学者将Fenton技术与电化学技术结合,使Fe²⁺在阴极得以持续再生,这就是广为关注的电-Fenton技术。同样地,类Fenton技术也遇到与传统Fenton技术相似的问题。借鉴电-Fenton技术的成功应用,基于硫酸根自由基的类电-Fenton技术应运而生。本文在介绍电-Fenton和类电-Fenton技术原理的基础上,概括了电-Fenton和类电-Fenton技术的主要类型及其改进方法,并就值得深入研究的问题和热点趋势进行了展望。     

环境超声化学

环境超声化学利用超声空化效应分解液相污染物,属于高级氧化过程。介绍了环境超声化学的基本原理,包括超声空化理论、超声降解环境污染物机理及生成自由基反应。综述了近年来环境超声化学在污染物净化中的应用,对存在问题和发展趋势提出了见解。     

超声-光催化降解有机污染物的研究进展

超声-光催化联合技术是近年来废水处理的新型高级氧化技术。该技术主要利用超声波和光催化降解联合产生的协同效应来提高有机污染物的降解效率。本文主要就目前国内外超声-光催化降解有机物的降解机理、影响因素(光催化剂的性能及投加量、超声频率、超声强度及声功率、pH、温度、离子强度、污染物的浓度、溶解气体和其它添加物)以及在废水处理方面的应用等方面进行了综述,并介绍了超声-光催化技术存在的主要问题,最后展望了该技术的发展前景。     

钴催化过一硫酸氢盐降解水中有机污染物:机理及应用研究

钴/过一硫酸氢盐(Co/PMS)是为了克服Fenton技术的诸多缺陷而基于类Fenton思路(过氧化物+过渡金属)建立起来的一种高级氧化技术。该体系具有Co用量少(μg/L数量级),产生的SO₄^-·氧化还原电位高,能够在广泛的pH范围(2-9)降解有机污染物,反应后不产生污泥等优点,在环境污染治理领域具有广阔的应用前景。本文从自由基链式反应、溶液pH、阴离子效应、光照条件、反应气氛及固液两相交换六个方面分析了Co/PMS体系降解水中有机污染物的机理,并在此基础上综述了Co/PMS (黑暗条件)、UV/Co/PMS、Vis/Co/PMS三类均相Co/PMS体系以及Co氧化物催化、Co负载催化两类非均相Co/PMS体系降解水中有机污染物的国内外研究进展,并就存在的问题提出了展望。     

亚甲蓝光度法测定羟自由基

利用亚甲蓝被氧化后褪色的机理,使用Fenton试剂与亚甲蓝作用,验证了体系中起氧化作用的是羟自由基,从而建立了亚甲蓝光度法检验羟自由基的方法。试验结果表明,在过氧化氢与亚甲蓝的摩尔比为1~20范围内,亚甲蓝吸光度的降低值与Fenton试剂的加入量呈直线关系,因而可在660 nm处测定亚甲蓝的褪色程度(ΔA)对羟自由基作间接光度测定。试验同时对超声法产生的羟自由基进行了测定,表明羟自由基的生成量与超声时间成正比。     

环境污染物的光催化降解:活性物种与反应机理

以二氧化钛为代表的光催化能使许多有毒的有机污染物发生降解或矿化,产生易被生物降解的小分子和二氧化碳,过程涉及羟基自由基等活性物种.本文在作者小组的工作基础上,试图总结近年来二氧化钛、(羟基)氧化铁、杂多酸和金属酞菁光催化或光敏化在水处理方面所取得的研究进展.综述的重点是二氧化钛半导体光催化,讨论的内容包括:(1)超氧自由基、羟基自由基和单线态氧的检测和各种生成机理;(2)金属离子、杂多酸和氟离子修饰催化剂表面对活性物种产生的影响和可能机理;(3)离子交换树脂和有机膨润土负载金属酞菁对吸附和可见光敏化降解水中有机物的影响.     

Ultrasonic degradation of metal complexes with organic substances present in mineralized water,brines, and sodium chloride solutions

The applicability of ultrasound over a frequency range from 18 kHz to 2 MHz to the degradation of metal complexes with organic compounds present in water, brines, and sodium chloride solutions was studied. It was found that ultrasound over a frequency range from 18 to 100 or 200 kHz can be used for the degradation of complexes in sodium chloride solutions and brines or seawater, respectively. In this case, the best results were obtained over the frequency range 80–100 or 80–200 kHz, respectively.     

SiO_2掺杂TiO_2催化超声降解甲基橙溶液

采用实验室合成的SiO2掺杂TiO2作为催化剂,以甲基橙超声降解反应为模型,研究了各种因素对SiO2掺杂TiO2催化超声降解甲基橙的影响.结果表明在SiO2掺杂TiO2催化剂作用下超声降解甲基橙的效果明显优于非掺杂的锐钛矿型TiO2的催化效果.SiO2掺杂TiO2催化剂用量在0.5～1.0g/L之间,超声波频率25kHz,输出功率1.0W/cm2,pH为1.0～3.0时,在甲基橙水溶液初始浓度20mg/L的条件下,80min,降解率达到了98%以上,COD的去除率也达到了99.0%.因此,SiO2掺杂TiO2催化超声降解有机污染物的方法具有很好的应用前景.     

纳米金红石型TiO2催化超声降解亚甲基蓝溶液

水溶性染料是印染工业中污染治理的主要对象，由于它们大多含有苯环，目前所使用的化学和生物等处理方法效果均不佳。而以半导体为催化剂的光催化处理方法对单一染料和实际印染废水处理效果较好。本文采用高温处理过的纳米TiO2作催化剂对亚甲基蓝溶液进行降解，大大缩短了降解时间，提高了降解率，60min降解率即可达66．8％，120min降解率则可达80％以上。而且发现利用超声波来替代紫外光对亚甲基蓝进行降解时，     

TiO2催化超声降解甲基橙溶液

采用经过处理后工业生产的TiO2作为催化剂,以超声降解甲基橙反应为模型,研究了各种因素对。TiO2催化超声降解的影响。研究表明,在TiO2催化剂作用下超声降解甲基橙的效果明显。TiO2催化剂用量在0．3～0．5g／L之间,超声波频率25kHz,输出功率1．0W／cm^2,pH=1．0时,甲基橙水溶液初始浓度为20mg／L的条件下,90min左右基本可全部降解,COD的去除率达到99．0％。     

Frequency effects on the surface coverage of nitrophenyl films ultrasonically grafted onto indium tin oxide

The covalent attachment of various organic molecules on conductive supports including indium tin oxide (ITO) using diazonium chemistry has been known for many years. A commonly used method to achieve this is the electrochemical reduction of diazonium compounds leading to radicals, followed by binding of the radicals to the support. In the present report, an alternative method using ultrasound at different frequencies (20, 582, 863, and 1142 kHz) to induce the surface grafting of nitrobenzene diazonium onto an ITO surface is described. It is shown that the grafting on ITO is more efficient in the lower ultrasonic frequency range that is ascribed to changes in the balance between the physical and chemical effects of cavitation with frequency. Both the physical and chemical effects of cavitation play important roles at all frequencies, but at high ultrasound frequencies, the physical effects are relatively small. At 20 kHz, the physical component, including mass transport, is larger than at higher frequencies, and mechanisms based on these observations have been proposed. Ultrasonic grafting has an advantage over electrografting in that it may provide more control over surface coverage, thus it is suggested that the ultrasonic method is used where the surface concentration of the organic layer must be controlled.     

超声波辐照和臭氧氧化协同降解废水中的结晶紫

采用超声波辐照、臭氧氧化以及超声波辐照-臭氧氧化降解废水中的结晶紫;考察了废水初始pH、超声波功率和频率、氧气流量、反应温度等因素对降解效率的影响.结果表明:超声波和臭氧对结晶紫的降解具有协同作用;当废水溶液初始质量浓度为200mg.L-1、pH为10.0时,控制超声波功率和频率分别为100 W和30kHz,氧气流量为0.4L.min-1,反应温度为25℃,反应时间为90 min,则总有机碳(TOC)的去除率可达89.2%,相应的一级反应速率常数为2.38×10-2min-1.     

Degradation of alkylbenzene sulfonate surfactants by pulsed ultrasound

The application of pulsed ultrasound for the degradation of the nonvolatile surfactants sodium 4-octylbenzene sulfonate (OBS) and sodium dodecylbenzenesulfonate (DBS) was investigated at a frequency of 354 kHz. By comparing the degradation rate constants with those of continuous wave (CW) ultrasound, observed pulse enhancements were found to be dependent on the pulse length, pulse ratio, initial concentration, and surface activity of the surfactants. For a pulse length of 100 ms and a pulse ratio of 1:1 (equal on/off times), the degradation rate constant of 1 mM OBS was nearly twice the value for CW. Furthermore, the degradation rate constant for 1 mM DBS increased significantly when sonicated under a pulse length of 100 ms and a pulse on/off ratio of 1:50. However, the degradation rate of 0.1 mM OBS increased by only 30% with a 100 ms pulse length and pulse ratio of 1:1 as compared to CW, indicating concentration dependence. The enhanced degradation of surfactants by pulsed ultrasound was attributed to the accumulation of surfactants on cavitation bubble surfaces. In addition, as compared to shorter pulse intervals, longer pulse intervals enhanced DBS degradation, indicating that DBS, a more surface active compound, accumulated and equilibrated with the bubble interface more slowly.     

DECOMPOSITION OF BLACK LIQUOR BY ULTRASOUND PROCESS

Ultrasound (US)-induced cavitation is an effective way in oxidizing organic contaminants in wastewater either as the independent operation unit or in combination with other oxidation methods. In this paper, black liquor and filtrate after acidifying and settling were sonicated The effect of working parameters on ultrasonic degradation of black liquor, such as different combinationmethods, frequency, power supply, initial concentration, pH, duration time, ionic strength and catalyst were studied The results were as follows: (1) At the conditions of 4OkHz, IOOW, 4h, pH at 6 and temperature 30±2℃,, utilizing US/US-H2O2/US-Fenton, weak-orange filtrate turned to colloid with the increase of time and little sediment produced after settling. Especially filtrate came to be milk white collides and upper water approached to nearly achromatic by US-Fenton. Compared with the US, US-H2O2/US-Fenton COD (Chemical oxidation demand) removal ratio can increase 15%,30% respectively. Because of more hydroxyl radicals produced in tire reaction process; (2) At the condition of lOOW and 4h, the degradation efficiency of black liquor was better at 40kHz over at 20kHz. Moreover black liquor can be biodegraded easily Those based on that the big molecule of contaminants in aqueous solution can be changed into the little molecule with ultrasound (3) At the condition of 40kl-l: and 4h, the COD removal ratio of black liquor was more higher at 60W than at 80W, while the removal ratio of COD at 60W was nearly close to the ratio at 100W,“ (4) The initial concentration of black liquor influenced the effect of sonochemical degradation; (5) The variation of pH had no effect on degradation; (6) The longer the duration time, tire greater the removal ratio of COD. But this ratio increased slowly after 4h; (7) Adding 0.2g/L NaCI to change the ionic strength of the black liquor, the COD removal ratio can increase 10%; (8) The degradation rates increased by the coexistent catalysts of TiO2, Co^+2 and Ag^+.     

Identification of inhibitory components toxic toward zymomonas mobilis CP4(pZB5) xylose fermentation

Zymomonas mobilis CP4(pZB5) is a recombinant bacterium that can produce ethanol from both xylose and glucose. The ethanol-producing efficiency of this organism is substantially impeded by toxic substances present in pretreated hydrolyzates or solid biomass substrates. Acetic acid and furfural (a pentose degradation product) are highly toxic to this organism at levels envisioned for a pretreated-hardwood liquid hydrolyzate. In addition, lignin degradation products and 5-hydroxymethylfurfural (a hexose degradation product) have a moderately toxic effect on the organism. Of the compounds studied, organic acids and aldehydes were found to be more inhibitory than lignin acids or the one alkaloid studied. Acetone:water and methanol extracts of solid biomass samples from red oak, white oak, and yellow poplar are toxic toZymomonas cell growth and ethanol production, with the extracts from white oak being the most toxic.     

Investigation of PAH and other hazardous contaminant occurrence in recycled tyre rubber surfaces. Case-study: restaurant playground in an indoor shopping centre

The objective of this case study was to investigate the presence of polycyclic aromatic hydrocarbons (PAHs) and other hazardous organic chemicals in a recycled tyre playground surface (in an indoor restaurant of a shopping centre with limited ventilation). This study also aimed at underlining both the volatilisation of these compounds in the vapour phase above the sample and the partial leaching of contaminants from the playground surface to the runoff and cleaning water put in contact with the sample. Playground samples were extracted with ethyl acetate using ultrasonic energy followed by GC-MS analysis. In addition, the same samples were analysed by HS-SPME to study the volatilisation and the transfer of those organic compounds. The analysis confirmed the presence of a large number of hazardous substances. Thus, 14 of the 16 studied PAHs were identified in the extracts (including the considered most toxic PAH, benzo[a]pyrene) and nine of them were also detected in the vapour phase. Besides, nine PAHs were found in the runoff/cleaning water, yielding a total PAH concentration at the ppm level. The presence and the high concentrations of these chemical compounds in playgrounds should be a matter of concern owing to their high toxicity.