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61.
The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH3 group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH2 group is slightly easier to be abstracted than that in -CH3 group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed. 相似文献
62.
Fenton 法降解抗生素磺胺间甲氧嘧啶钠 总被引:3,自引:1,他引:2
应用Fenton高级氧化技术降解水溶液中抗生素磺胺间甲氧嘧啶钠(SMMS),系统探讨了起始pH、CSMMS、CFe2+、CH2O2和温度等因素对SMMS降解效果的影响。结果表明:CSMMS=4.53 mg/L,pH=4.0,CH2O2=0.49 mmol/L,CFe2+=19.51μmol/L,T=25℃为最佳反应条件。在最佳条件下,87.4%的SMMS可以在120 min内降解。反应动力学研究表明Fenton氧化降解SMMS分为两个阶段,快速反应阶段和慢速反应阶段,并建立了两阶段动力学模型,模型拟合结果较好。研究结果为含有SMMS的污废水处理提供了基础数据和科学参考。 相似文献
63.
研究了UV/Fenton技术对高浓度金属清洗乳化油废水的处理效果,考察了亚铁与双氧水浓度、pH、反应时间和搅拌对COD去除效果的影响。实验结果表明,UV/Fenton技术对高浓度乳化油废水(COD平均浓度为35 000 mg/L)具有较高的去除效果,最佳工艺条件为:亚铁与双氧水浓度分别为2 400 mg/L和6 000 mg/L,pH为3,经过2 h反应,COD可降低至1 050 mg/L,去除率为97%。搅拌会降低COD的去除率。研究表明,UV/Fenton技术对高浓度乳化油废水具有很好的降解效果,且药品消耗较低,为目前此类高浓度有机废水的处理提供了技术参考。 相似文献
64.
65.
通过采用铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的实验研究,分析了处理过程的COD降解动力学;同时研究了单纯活性炭吸附和微电解过程中COD去除率的变化。结果表明,铁碳微电解的初期COD降解过程近似符合一级反应动力学,并且得到微电解与活性炭吸附对铁碳微电解降解COD的关系式;Fenton反应中通过研究有机物浓度和过氧化氢初始浓度与反应进程的关系,建立了反应动力学模型;单纯吸附实验COD去除率在24h内快速下降,而微电解在相应时间内COD去除率波动较小,为实际应用提供了数据经验和理论依据。 相似文献
66.
采用Fenton试剂氧化法处理分散橙、分散紫和分散蓝3种染料结晶废母液。研究了H2O2加入量、n(H2O2)#x02236;n(Fe2+)和废母液pH对COD去除率或TOC去除率的影响。对TOC去除反应分段进行了动力学方程拟合,并探讨了反应机理。实验得到的分散橙、分散紫和分散蓝的废母液处理工艺条件:H2O2加入量分别为264.4,352.9,441.2mmol/L;n(H2O2)#x02236;n(Fe2+)分别为20,10,20;废母液pH=3。3种废母液在0~20min和20~120min两个阶段的反应与二级动力学拟合方程的相关性最好。3种废母液经Fenton试剂氧化处理后,部分有机物降解为小分子有机酸,部分有机物完全矿化。 相似文献
67.
用絮凝#x02014;微波辐射#x02014;Fenton试剂氧化法深度处理焦化废水,研究了微波辐射时间、微波功率、FeSO4加入量、H2O2加入量和废水pH对废水处理效果的影响。实验结果表明:在聚合氯化铝加入量为350mg/L、聚丙烯酰胺加入量为12mg/L、废水pH=5、FeSO4加入量为250mg/L、H2O2总加入量为1400mg/L、H2O2分3次投加、微波功率为400W、微波辐射时间为60min的条件下,处理后出水的浊度、色度和COD去除率分别为98.59%,97.62%,86.21%。处理后出水澄清透明,COD为50.34mg/L,满足GB50050#x02014;2007《工业循环冷却水处理设计规范》的要求。 相似文献
68.
Fenton process, as a pretreatment method, was found to be effective in the primary treatment of mature/medium landfill leachate. However, the main problem of the process is the large amount of produced sludge that requires an accurate feasibility evaluation for operational applications. In this study, the response surface methodology was applied for the modeling and optimization of Fenton process in three target responses, (1) overall COD removal, (2) sludge to iron ratio (SIR) and (3) organics removal to sludge ratio (ORSR), where the latter two were new self-defined responses for prediction of sludge generation and applicability assessment of the process, respectively. The effective variables included the initial pH, [H2O2]/[Fe2+] ratio and Fe2+ dosage. According to the statistical analysis, all the proposed models were adequate (with adjusted R2 of 0.9116–0.9512) and had considerable predictive capability (with prediction R2 up to 0.9092 and appropriate adequate precision). It was found that all the variables had significant effects on the responses, specifically by their observed role in dominant oxidation mechanism. The optimum operational conditions obtained by overlay plot, were found to be initial pH of 5.7, [H2O2]/[Fe2+] ratio of 17.72 and [Fe2+] of 195 mM, which led to 69% COD removal, 2.4 (l sludge/consumed mole Fe2+) of SIR and 16.5 (gCOD removed/l produced sludge) for ORSR in verification test, in accordance with models-predicted values. Finally, it was observed that [H2O2]/[Fe2+] ratio and Fe2+ dosage had significant influence on COD removal, while Fe2+ dosage and [H2O2]/[Fe2+] ratio had remarkable effects on SIR and ORSR responses, respectively. 相似文献
69.
Valeria CassonDavid George Lister Maria Francesca MilazzoGiuseppe Maschio 《Journal of Loss Prevention in the Process Industries》2012,25(1):209-217
Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared. 相似文献
70.