"热水洗+臭氧氧化"联合工艺处理大颗粒油基岩屑

针对油基岩屑处理过程中的大颗粒部分(0.5—1 cm),研究了以"热水洗+臭氧氧化"为核心的联合工艺的处理效果,并分别对热水洗、臭氧氧化环节的工艺参数进行了优化.结果表明,在最优条件下,经过处理后的油基岩屑的含油率可由15.8%降低到0.24%,达到了GB 4284-2018中规定的处置要求,处理过程中回收的油分可重新用于配制钻井液.通过对油基岩屑固相的表征发现,其具备臭氧催化氧化催化剂的明显特征,是一种天然的臭氧催化氧化催化剂,并从反应动力学角度对臭氧氧化环节的反应特性进行了定量分析.结果表明,其满足准一级反应动力学特征,反应活化能为14.421 kJ·mol~(-1).以"热水洗+臭氧氧化"为核心的联合工艺为大颗粒油基岩屑的无害化、资源化处理提供了一种参考.     

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.     

ZnO-MgO/Al2O3吸附-臭氧催化氧化处理难降解有机废水

以活性氧化铝为载体,采用浸渍法制备催化剂,对甲基橙及草酸模拟废水进行处理.在中性条件下,臭氧催化氧化比单独臭氧氧化能提前30 min使得甲基橙溶液褪色,反应105 min时,臭氧催化氧化对TOC的去除率高达96.53%,比单独使用臭氧氧化对甲基橙TOC去除率提高了47.19%,在处理草酸废水时臭氧催化氧化对TOC去除率高达80.59%,比单独使用臭氧氧化对草酸TOC去除率提高了59.14%.在处理甲基橙及草酸的小试实验中催化剂对有机污染物的吸附作用起到了加快反应进行的作用.在对垃圾渗滤液超滤出水时,O₃与COD质量比为1:1时,臭氧催化氧化对COD去除率为49.09%,比单独使用臭氧氧化提高36.37%,臭氧催化氧化对TOC的去除率是单独使用臭氧氧化的2.54倍,在处理垃圾渗滤液纳滤浓水时,臭氧催化氧化对COD去除率高达88.72%,比单独使用臭氧氧化提高37.60%,并且臭氧催化氧化对TOC的去除率是单独臭氧氧化的1.6倍.臭氧催化氧化反应过程中产生的羟基自由基对有机物更快的反应速率.     

臭氧氧化脱除硫化氢的动力学

本文探讨了臭氧氧化法脱除硫化氢,构建了详细的臭氧氧化硫化氢的反应机理,包含24个物种和74个基元反应.通过臭氧热分解和臭氧低温氧化硫化氢的实验结果进一步验证了本反应机理的可靠性.实验发现,在温度为25℃,物质的量之比为3时,硫化氰的脱除效率达到93%.由模拟结果看出,在停留时间为2s,物质的量之比为1时,氧化最佳温度为150℃-200℃.反应温度为25℃,物质的量之比为1时,把反应时间延长到20s,H2S的脱除率能达到90.9%.     

催化臭氧氧化降解罗丹明B的初步研究

研究了过渡金属硝酸盐及Al2O3为载体担载催化剂在罗丹明B臭氧氧化过程中的催化作用,考察了温度、pH值以及催化剂浓度等因素对反应的影响.结果表明,过渡金属离子可显著地提高罗丹明B的脱色速率,而担载型过渡金属氧化物催化剂活性较低.较低的pH值和反应温度有利于罗丹明B的催化臭氧化.罗丹明B溶液经过催化臭氧氧化后COD去除率可提高24%.     

臭氧降解乐果机理探讨

研究了臭氧对乐果的降解效果及其影响因素。试验结果表明,当初始臭氧浓度为10mg·L-1时,5min内可使乐果降解80%左右,延长反应时间,乐果降解率无明显增加。同时,通过在乐果和臭氧的反应液中再分别添加重碳酸盐与叔丁醇,探讨臭氧降解乐果的反应机理,结果表明臭氧降解乐果是分子反应。GC-MS检测经臭氧处理的水样发现有氧化乐果存在,表明若臭氧处理不完全,水样中可产生毒副产物。     

催化臭氧氧化去除垃圾渗滤液中难降解有机物的研究

研究了Fe(Ⅱ),Mn(Ⅱ),Cu(Ⅱ)作用下,均相催化臭氧氧化去除垃圾渗滤液中高浓度的腐殖质.分析催化剂用量、溶液pH值对腐殖质催化臭氧氧化降解的影响.结果表明,与单纯臭氧氧化比较,催化臭氧氧化对UV254和色度去除率无明显改善,但可明显提高以TOC和CODCr表征的有机物去除率;当投加催化剂过量时,以TOC和CODCr表征的有机物去除率虽降低,但仍有促进作用.但Fe2 的过量投加将明显抑制UV254和色度的去除效果.在碱性条件下,催化臭氧氧化法具有更好的去除效果.三种催化剂催化效果为Cu(Ⅱ)＞Mn(Ⅱ)＞Fe(Ⅱ).采用Cu(Ⅱ)催化臭氧氧化处理实际渗滤液生化处理出水,对CODCr,色度和UV254都显示出较好的去除效果.     

1甲-基环己烯气相臭氧氧化生成二次有机气溶胶产物的研究

采用烟雾箱实验模拟了大气中1-甲基环己烯臭氧氧化生成二次有机气溶胶的化学过程.采用衍生化方法和气质联用仪对反应中生成的低挥发性有机酸产物进行了定性定量研究.通过研究.OH自由基清除剂和相对湿度对产物产率的影响,检验了文献中提出的假设反应机理,并提出了各产物的详细形成机理.     

臭氧氧化降解水溶液中1—萘酚的动力学研究

本文研究了水溶液中１－萘酚在鼓泡反应釜内臭氧氧化的消失动力学,考察了ｐＨ值、温度、自由基清除剂和１－萘酚的起始反应浓度等因素对反应的影响。结果表明,ｐＨ值、反应温度的提高有利于１－萘酚的降解。１－萘酚初始浓度低时其消失速率较高。该反应是有自由基反应贡献的分子臭氧氧化反应。在重碳酸盐存在下,１－萘酚的臭氧氧化降解符合一级反应动力学。     

烯烃气相臭氧化反应机理的研究进展

气相条件下的烯烃臭氧化反应是大气中极其重要的反应之一,是多种自由基以及二次有机气溶胶的重要来源,与大气环境和人类生活密切相关.综合以往的研究成果,对早期提出的Criegee机理做了简介,着重阐述了Criegee中间体(CI)的结构及其相关反应、羟自由基的形成机理及萜烯臭氧化形成二次有机气溶胶产物的机理.最后,对未来的研究方向进行了探讨.     

臭氧污泥减量过程中混合液各参数的变化

实验用污泥的初始浓度(MLSS)分别限定为4g/L、7g/L和11g/L,用以探讨不同浓度下臭氧氧化过程中COD、N和P浓度的变化。结果表明:臭氧氧化过程中,MLSS和MLVSS基本呈线性下降;臭氧对污泥细胞的溶解可以引起混合液中COD、N和P浓度的升高,升高速率受污泥浓度和臭氧浓度影响较大;TKN和硝态氮是N的主要存在形式,TKN和TN随时间均呈先增加后趋缓的变化规律;臭氧对氨氮和亚硝酸盐氮有较强的氧化能力,二者浓度均呈先增大后减小的规律;而硝酸盐氮呈一直增加趋势;臭氧对COD的氧化也很明显,表现为COD的增加速率随氧化时间的增加而不断降低;总磷的浓度基本呈线性增加,单位质量污泥的总磷释放量差异不大;臭氧对MLSS的彻底减量会引起臭氧溶胞利用率的降低,因此应该合理控制臭氧化反应的时间。     

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.     

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.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl^? formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH? radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH? radicals together. With the inhibition of OH? radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH? were proposed in this study.     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation.     

腐植酸臭氧氧化和过氧化氢催化氧化处理特性比较

以TOC和UV254为指标,比较了不同条件下腐植酸的臭氧氧化和过氧化氢催化氧化效果,运用HPLC和热裂解-GC-MS分析考察了氧化前后有机物分子量分布和官能团构造的变化情况．研究结果表明：过氧化氢和臭氧单独作为氧化剂对水中TOC基本上没有去除作用,但均能导致水中UV254浓度的降低;在几种催化剂的作用下,过氧化氢对TOC和UV254的去除效果明显提高,其中以O3作为催化剂的效果最好,Fe^2＋次之,而Mn^2＋和Cu^2＋的催化效果较差;过氧化氢催化氧化和臭氧化均导致有机物分子量分布向小分子的方向转移,氧化后水中以羧酸、醇、胺、酯、醚、烷烃为代表的含氧基团和饱和构造基团明显增多;过氧化氢催化氧化和臭氧氧化均有助于改善混凝处理和活性炭吸附处理的效果．关键词腐植酸,臭氧,过氧化氢,催化氧化．     

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。     

给水深度处理中臭氧副产物的产生及控制

就给水深度处理中臭氧副产物的产生及其化学过程、控制臭氧副产物生成的技术措施等问题进行了探讨。采用臭氧深度处理时,会产生以甲醛为代表的有机副产物,以溴酸根为代表的无机副产物。副产物的形成与溴离子浓度、水中有机物种类和浓度、pH值、臭氧投加量、温度和碱度等因素有关。在应用臭氧进行深度处理时,应根据不同条件,采取适宜的措施,以减少臭氧副产物的生成。     

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru–Ce/Al₂O₃ on catalytic activity.