臭氧及催化臭氧化降解2,4-滴丙酸动力学研究

对臭氧及催化臭氧氧化降解2,4-滴丙酸(DCPP)的效率进行了研究,并利用竞争动力学法算得了DCPP与臭氧及羟基自由基的反应速率常数,参比有机物为硝基苯(NB).结果表明,DCPP与臭氧的反应速率常数K-DCPP为(0.733±0.163)L·mol-1·s-1,与羟基自由基的kOH-DCPP为2.367×109L·mol-1·s-1.在单独臭氧和Mn(Ⅱ)催化臭氧化降解DCPP过程中,基于上述结果计算所得的速率常数与实际所测的表观反应速率常数具有较好的吻合度.以上结果对臭氧化处理含DCPP废水具有很好的理论指导意义.     

Experimental study on oxidative decomposition of nitrobenzene in aqueous solution by honeycomb ceramic-catalyzed ozonation

The ozonation of nitrobenzene in aqueous solution was carried out in a semi-batch reactor to investigate the degradation efficiency, the effect factors, and the reaction mechanism, where honeycomb ceramic was used as a catalyst. The presence of honeycomb ceramic could improve the degradation rate of nitrobenzene by 15.46% compared to the results of ozonation alone. Under the conditions of this experiment, the degradation rate of honeycomb ceramic-catalyzed ozonation increased by 12.94% with the increase of the amount of catalyst from 1 to 5 blocks. The degradation rates all increased greatly with the increase of temperature and pH of the solution in the processes of honeycomb ceramiccatalyzed ozonation and ozonation alone. But, when the pH of the solution increased to 9.50, the advantage of the honeycomb ceramic-catalyzed ozonation process would be lost. The experimental findings indicated that in the processes of ozonation alone and honeycomb ceramic-catalyzed ozonation, nitrobenzene was primarily oxidized by ·OH free radical in aqueous solution. The adsorption of nitrobenzene was too limited to have an important influence on the degradation rate of nitrobenzene. With the same total dosage of applied ozone, the multiple step addition of ozone showed much higher removal efficiency than that obtained by one step in the two processes.     

催化臭氧化饮用水中甲草胺的研究

利用Fe2+、Mn2+和腐殖酸对水中甲草胺进行了催化臭氧化研究.实验表明,少量的催化剂就可促进甲草胺的降解,过量则会产生抑制作用.深入研究表明,甲草胺的降解与具有极强氧化能力的羟基自由基有关.     

Mechanistic study of ozonation of p-nitrophenol in aqueous solution

Introduction p Nitrophenolhasbeenwidelyusedintheproductionof pesticides,herbicides,dyes,andotherindustrialchemicals.Asaresultofthesewidespreadapplications,wastewatersandwaterresources,includinggroundwaterandsurfacewaters,havebecomecontaminatedwiththiscomp…     

臭氧氧化产物甲醛的产生机理研究

对3类含不同碳链结构的有机物进行臭氧氧化,研究了氧化过程中的甲醛浓度变化情况,并对臭氧单独氧化、臭氧和羟基自由基混合氧化和羟基自由基氧化特性进行了分析.以丙烯酸为目标物,分别研究了不同进气流量、气态臭氧浓度和双氧水投加量对甲醛浓度的影响.结果表明:苯环上不同的取代基对甲醛产量有较大影响,单烯烃的α-C上连接的基团对甲醛浓度影响更大;在氧化过程中,甲醛浓度表现出先增后减的变化趋势,出现峰值.增大进气流量和进气臭氧浓度会使峰值减小,并使出峰时间缩短,但会提高初始产出速率;对不同有机物,羟基自由基氧化对甲醛产量的影响不同,氧化丙烯酸和反丁烯二酸时,甲醛积累量减小,而氧化壬基酚和水杨酸等芳香族化合物时,甲醛积累量提高.     

催化臭氧化降解磺基水杨酸

选用3种固体催化剂催化臭氧化降解磺基水杨酸.结果表明,MnO₂和V₂O₅催化活性并不明显,而自制的钒氧化物(VO)催化剂具有较好的催化臭氧化性能.在本实验条件下与单独臭氧化相比,30min后VO/O₃体系的COD和TOC去除率由原来的58%和25%提高到86%和61%.VO催化剂的作用机理是催化臭氧分解产生了高活性氧化剂(如羟基自由基等).     

臭氧氧化深度处理二级处理出水的研究

以某城市污水处理厂二级处理出水为原水,研究了臭氧氧化深度处理对水中残留有机物以及病原微生物的降解和去除效果.结果表明,臭氧投加量达到6mg/L时,DOC、UV254、色度的去除率分别为15.49%、36.36%、73.61%,环境激素类痕量有机物邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)的去除率分别为37.29%和14.6%,三维荧光光谱荧光峰的各区域有机物质平均去除率在80%以上,DBP出水浓度为2.64mg/L,DEHP出水浓度为1.4mg/L,满足《城市污水再生利用地下水回灌水质》(GB/T 19772-2005)的标准.臭氧投加量达到10mg/L时,出水中指示性微生物粪大肠菌群仍接近103CFU/L,5mg/L有效氯消毒后出水粪大肠菌群仍接近10CFU/L,6mg/L臭氧与5mg/L有效氯组合消毒出水的粪大肠菌群下降至3CFU/L,满足《城市污水再生利用景观环境用水水质》(GB/T 18921-2002)的标准.三卤甲烷(THMs)的生成量随着有效氯投加量的增加而增加,臭氧与氯组合消毒过程与氯单独消毒过程相比,THMs生成量减少了78.08%.     

MgO催化臭氧氧化降解苯酚机理研究

对氧化镁(MgO)催化臭氧氧化降解苯酚的机理进行了探讨,并验证其与现有的3种催化臭氧氧化机理的吻合性.同时,研究了羟基自由基(·OH)抑制剂对苯酚去除效果的影响,·OH的产生量,以及臭氧在该体系中的存在位置及苯酚在该体系中的作用.结果表明,O_3和MgO/O_3两种反应体系中都存在·OH,MgO/O_3体系中的·OH是O_3体系中的2.14倍.O_3和MgO/O_3体系中的·OH与臭氧浓度的比值分别为1.47×10~(-9)和3.15×10~(-9).苯酚在MgO催化臭氧氧化体系中起到了促进臭氧吸附在MgO表面的作用,臭氧吸附到MgO表面后,分解产生·OH,一部分释放在溶液中降解苯酚,一部分则留在其表面增加表面羟基密度.     

臭氧化芳香族化合物中生物毒性的演变规律研究

臭氧工艺越来越广泛地应用于难降解废水的处理,但由于臭氧的部分氧化特性,可能会导致高毒性中间产物的生成.为了揭示臭氧工艺的生态安全性,研究了不同工艺条件下,臭氧化苯酚、邻甲酚、对甲酚、间甲酚、苯胺和对氯苯胺时急性生物毒性的变化.结果表明,尽管母体污染物与总有机碳(TOC)的浓度在臭氧化过程中持续下降,但生物毒性随着反应时...     

Genotoxicity removal of reclaimed water during ozonation

Genotoxicity in wastewater and reclaimed water now is gaining increased attention because of genotoxins' potential damage to the ecosystem and human health. The effect of ozonation on genotoxicity in reclaimed water was investigated. It was found that ozonation decreased the genotoxicy dramatically in three tertiary treatment plants. In the further batch ozonation experiment in laboratory,secondary effluent sample used exhibited the genotoxicity of(41.1 ± 4.1) μg 4NQO/L. Ozonation with a dose of 10 mg O3/L completely removed the genotoxicity in secondary effluent. However,after ozonation, the dissolved organic carbonvalue of the sample didn't change much but the specific ultraviolet absorbance(SUVA) value dropped sharply. With the help of Fourier transform infrared spectroscopy, ozonation was found to change chemical aliphatic carbon and C–O of the dissolved arganic matter, which might be the reason of the significant decreases of SUVA and genotoxicity.     

镍铜氧化物对吐氏酸废水臭氧氧化的催化作用

染料中间体废水等难生物降解废水是目前水处理研究的焦点。用浸渍法和附着沉淀法制备了以γ-Al₂O₃为载体的负载型镍、铜氧化物催化剂,并以催化吐氏酸废水的臭氧氧化。研究结果表明,镍、铜单组分和双组分氧化物催化剂能不同程度地提高臭氧的利用效率,其中附着沉淀法制备的Ni-Cu-Urea-1催化剂活性最高,当臭氧投加量为0.82g/L时,其臭氧化指数为1.1;助剂钾对催化剂活性的影响与制备方法有关,当用浸渍法制备时,助剂钾能提高催化剂活性,而附着沉淀法时则不利。     

水/载O3有机溶剂两相臭氧氧化法降解水体中2,4-二氯苯氧乙酸

以水/载O3有机溶剂(全氟萘烷)为新型两相臭氧氧化体系,研究了臭氧在全氟萘烷中的溶解度和稳定性,并以水体中2,4-二氯苯氧乙酸(2,4-D)为研究对象,考察了初始pH值、臭氧投加量、自由基抑制剂对两相臭氧氧化体系降解2,4-D效果的影响.结果表明:臭氧在全氟萘烷中有很高的溶解度和很好的稳定性;碱性pH环境有利于2,4-D的降解,随着水相初始pH的增加,2,4-D在水/载饱和O3全氟萘烷两相体系中的去除率明显增加;随着初始全氟萘烷载O3量与2,4-D物质的量比的增加,2,4-D总去除率明显增加;叔丁醇(20mg·mL-1)对两相体系中2,4-D降解影响不显著.     

城市污水再生处理过程中臭氧氧化脱色及稳定性研究

针对城市污水再生处理臭氧氧化脱色效果及稳定性开展了相关研究.结果表明,臭氧氧化处理可以有效降低二级出水的表色与真色.在自然条件模拟过程中,不同臭氧投加量的水样22 d后真色并没有明显变化,表色、叶绿素a和浊度变化呈现出良好的一致性.当臭氧投加量小于6 mg·L-1时,水样表色在12 d内缓慢增加,之后快速上升直至22 d后达到最大.低剂量的臭氧处理(小于6 mg·L-1)反而会促进藻类的繁殖,加剧水体色度的不稳定性.然而,当臭氧投加量大于8 mg·L-1时,可以明显延长水样的复色时间,表色在18 d后才略微上升.水体的色度和浊度变化主要由藻类的生长和繁殖引起的,高的臭氧剂量能够维持水体色度稳定性.因此,推荐城市污水再生处理过程臭氧投加量为8 mg·L-1.     

羟基化锌催化臭氧氧化去除水中痕量磺胺嘧啶

以实验室制备的羟基化锌(ZnOOH)为催化剂,研究了其催化臭氧化去除水中痕量磺胺嘧啶(SD)的效能,通过研究叔丁醇对催化效果的影响,推断了催化反应机理,探讨了臭氧投加量、水质因素、催化剂投加量和使用次数对催化性能的影响因素.结果表明,ZnOOH对臭氧氧化水中的SD有较强的催化活性.催化剂表面结合的羟基基团有利于催化反应.在优化的实验条件下,蒸馏水中反应30min时,催化臭氧化比单独臭氧化对SD的去除率提高了47.7%.催化过程遵循自由基反应机理,SD的去除效果随催化剂投加量的增加而提高,催化剂在重复使用后催化效果基本不变,水中的氯离子可以明显降低催化剂的活性,偏碱性条件下,催化效果更佳.     

A VUV photoionization mass spectrometric study on the OH-initiated photooxidation of isoprene with synchrotron radiation

The gas-phase organic compounds resulting from OH-initiated photooxidation of isoprene have been investigated on-line by VUV photoionization mass spectrometry based on synchrotron radiation for the first time. The photoionization efficiency curves of the corresponding gaseous products as well as the chosen standards have been deduced by gating the interested peaks in the photoionization mass spectra while scanning the photon energy simultaneously, which permits the identification of the pivotal gaseous products of the photooxidation of isoprene, such as formaldehyde (10.84 eV), formic acid (11.38 eV), acetone (9.68 eV), glyoxal (9.84 eV), acetic acid (10.75 eV), methacrolein (9.91 eV), and methyl vinyl ketone (9.66 eV). Proposed reaction mechanisms leading to the formation of these key products were discussed, which were completely consistent with the previous works of different groups. The capability of synchrotron radiation photoionization mass spectrometry to directly identify the chemical composition of the gaseous products in a simulation chamber has been demonstrated, and its potential application in related studies of atmospheric oxidation of ambient volatile organic compounds is anticipated.     

污水生化出水有机物对氯贝酸臭氧降解的影响研究

常规水处理技术无法有效去除痕量的药品和个人护理品(PPCPs),臭氧工艺因具有效果可观、二次污染小等优势,尤其适合用于生化尾水的深度处理.而污水生化出水有机物(EfOM)对臭氧降解PPCPs起着至关重要的作用.本文选取腐殖酸(HA)、牛血清蛋白(BSA)、海藻酸钠(AGS)和葡聚糖(Dextran)作为模拟EfOM 4种代表物质,以氯贝酸(CA)为PPCPs模板化合物,考察了模拟EfOM化合物浓度、反应时间及溶液初始pH对臭氧降解效果的影响规律和机制.结果表明,CA臭氧降解速率符合假一级动力学方程,模拟EfOM化合物为10 mg·L~(-1) TOC时,对CA臭氧降解效果呈现出HADextran≈DW(超纯水)≈AGSBSA的规律.HA可提高HO·的生成速率从而加快CA降解效率,反应速率常数提升了3倍,去除率提高了17.5%;而BSA则明显抑制HO·的生成,从而降低CA降解速率.HA的存在对CA臭氧降解影响较为复杂,研究发现当HA浓度为1 mg·L~(-1) TOC时,能促进HO·的生成和CA的降解,而当浓度升高时会表现出抑制作用.CA臭氧降解速率和反应过程中HO·生成均随着溶液初始pH的增加而增大.pH的变化还会影响HA对臭氧降解CA的作用效果.溶液初始pH为4时,HA投加可促进HO·生成和臭氧降解;但随着pH的升高,HA的存在形态会发生改变,从而表现出对CA臭氧降解效果的抑制作用.     

电-多相臭氧催化工艺深度处理焦化废水

本文采用新型电-多相臭氧催化（E-catazone）工艺深度处理焦化废水生化二级出水,开展工艺可行性研究.通过与O₃/TiO₂纳米花（TiO_2-NF）与O₃/TiO_2-NF/H₂O₂及单独电化学氧化工艺相比较,对E-catazone工艺技术优势及氧化机理进行探究.结果表明：在相同条件下（O₃浓度84mg/L）,电-多相臭氧催化获得的COD和TOC的去除率（分别为67.9%,50.0%）显著优于O₃/TiO_2-NF获得的去除率（25.8%,20.9%）,即便在O₃/TiO_2-NF体系中投加5g/L的H₂O₂以促进臭氧均相催化效果,但COD和TOC去除率也仅分别提高到63.6%,43.6%.     

粒径与前驱体对活性炭催化臭氧氧化的影响

利用煤质、木质、椰壳3种前驱体活性炭制得6种粒级共18种活性炭样品,作为催化剂进行催化臭氧降解草酸的效果研究.结果表明,减小活性炭粒径对催化臭氧氧化效率提升效果显著,160~300目活性炭催化臭氧氧化降解草酸速率常数是10~20目颗粒活性炭的9.2~19.0倍.煤质160~300目活性炭催化臭氧氧化降解效果最佳.活性炭粒径的倒数与催化臭氧氧化伪一级动力学速率常数呈线性关系.对官能团的滴定表明,活性炭表面的羟基数量与催化臭氧氧化一级动力学速率常数存在较为明显的指数关系.     

Degradation of benzophenone in aqueous solution by Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation

Comparative studies of ozonation alone, ceramic honeycomb-catalyzed and Mn-Fe-K modified ceramic honeycomb catalyzed ozonation processes have been undertaken with benzophenone as the model organic pollutant. The experimental results showed that the presence of Mn-Fe-K modified ceramic honeycombs significantly increased the removal rate of benzophenone and TOC compared with that achieved by ozonation alone or ceramic honeycomb-catalyzed ozonation. The electron paramagnetic resonance （EPR） experiments verified that higher benzophenone removal rate was attribute to more hydroxyl radicals generated in the Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation. Under the conditions of this experiment, the degradation rate of all the three ozonation processes are increasing with the amount of catalyst, temperature and value of pH increased in the solution. We also investigated the effects of different process of ozone addition, the optimum conditions for preparing catalyst and influence of the Mn-Fe-K modified ceramic honeycomb after multiple-repeated use.     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H2O2在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O3和Fe^2＋/O3对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H2O2产生时,必须考虑类Fenton反应对臭氧化效率的影响。