【作者】 周立；

【导师】 钟宏；

【作者基本信息】 中南大学 ， 化学工程与技术， 2013， 博士

【摘要】 摘要：随着石油化工、塑料、合成纤维、焦化等工业的迅速发展,排向环境的各类含酚废水也相应增加。由于酚的毒性大,具有致癌、致畸、致突变的潜在性,越来越受到广大研究人员的高度关注。清除或降解水中的酚类污染物,不仅涉及水生生物及陆生植物的生长繁殖,更影响人类及陆生动物的食品饮水安全,因此,研究含酚废水的高效处理技术,对保护环境具有极大的现实意义。目前,国内外处理含酚废水的常用方法有物化法、化学氧化法以及生化法三大类。经工业应用证明采用任何单一的方法都有其优势和局限性,而集几种方法的优点形成一种新的组合工艺用来处理含酚废水是含酚废水处理技术的一种发展方向。本文是以实验室模拟含酚废水为研究对象,在分别单独采用树脂吸附法处理和Fenton氧化法处理的基础上,集合吸附与Fenton试剂氧化技术的优点,开发一种吸附-氧化组合联用处理含酚废水的新工艺。同时,利用三相流化床反应器的优点,研究了反应器对新工艺处理实验室模拟含酚废水和实际工业废水的强化作用,分析和探讨了处理效果及其影响因素,为这种新工艺的工业化应用提供了理论依据。本文主要研究结果如下：(1)考察了三种常用吸附树脂对于苯酚吸附性能的影响。比较研究发现,H-103大孔吸附树脂性能最优。深入地研究了H-103大孔吸附树脂对苯酚的吸附性能；系统地考察了苯酚水溶液初始浓度、pH值、反应时间及反应温度对树脂吸附性能的影响。实验结果表明,当苯酚水溶液初始浓度为1000mg/L时,树脂吸附过程在30min内基本达到平衡,其吸附动力学可用拟二级动力学模型描述,苯酚在H-103大孔树脂上的吸附等温线完全符合Langmuir吸附等温方程。在25℃的温度下,其平衡吸附量和Langmuir常数分别为86.00mg/g和0.2719L/mmg；采用70%(ω)乙醇作为脱附剂,其脱附率可达94.5%。(2)比较研究了MnO2、KMnO4及Fenton试剂对苯酚溶液的氧化性能,实验结果表明Fenton试剂氧化性能最好。系统地研究了Fenton试剂氧化处理模拟含酚废水,探讨了Fe2+初始浓度、摩尔浓度比n(Fe2+)/n(H2O2)、溶液pH值、反应温度和反应时间等因素对苯酚去除率的影响。确定了其适宜氧化条件为：pH=6,[Fe2+]=3mmol/L,[H2O2]=80mmol/L,反应温度为25℃,反应时间为60mmin。在此实验条件下苯酚去除率可达95%。(3)研究了吸附-氧化组合工艺处理模拟含酚废水。考察了溶液pH值、反应温度、反应时间和树脂固含率等因素对苯酚去除率的影响。实验结果表明,采用吸附-氧化组合工艺处理模拟含酚废水其效果明显优于单一的树脂吸附法和Fenton试剂氧化法。当含酚废水浓度为1000mg/L,反应温度为25℃、溶液pH=4,[Fe2+]=3mmol/L,[H2O2]=80mmol/L,树脂固含率为1%,反应5min后,苯酚去除率即可达到98.6%。对组合工艺除酚的作用机理进行了探讨,通过拟合实验数据建立了吸附-氧化组合工艺协同降解苯酚的动力学方程式。(4)在气液固三相流化床内,分别进行了吸附-氧化组合新工艺对模拟含酚废水和实际工业废水的处理研究。分析了树脂颗粒在三相流化床内的混合与离析行为,确定了树脂颗粒实现完全流态化的工艺参数；设计了结构尺寸不同、气体分布器类型不同的六种流化床反应器,比较研究其主要结构参数及操作参数对苯酚去除效果的影响,从而确定了流化床主要结构参数；在自行设计的三相流化床内,研究了树脂颗粒流态化对组合工艺除酚效果的强化作用,并系统探讨了pH值、H202和Fe2+的初始浓度、反应时间、树脂固含率、通气量等因素对苯酚去除率的影响。实验结果表明,树脂颗粒流态化能起到强化组合工艺除酚效果的作用。当苯酚溶液初始浓度为1000mg/L、溶液pH=4、反应温度为25℃、通气量为0.12m3/h、树脂固含率为1%、[Fe2+]=3mmol/L, n(H2O2)/n(Fe2+)=20:1的条件下,模拟含酚废水苯酚去除率达到了99.6%；在实际工业废水含酚浓度为878mg/L,其它条件与上述相同的情况下,实际工业废水处理后溶液中末检出苯酚。更多还原

【Abstract】 Abstract:With the rapid development of petroleum, plastics, composites and coking industries, the phenolic wastewater has been significantly increased recently. The phenols have been attracted attentions by the majority of researchers due to their toxicity, carcinogen and potential genetic mutagen. The removal and/or degradation of phenolic pollutants from wastewater have a great impact on aquatic life and terrestrial plant growth and reproduction, as well as human society including food and drinking water safety. Therefore, technology development for phenolic removal with high efficiency is a great practical significance to the environmental protection.At present, there are mainly three types of common methods used for treatment of phenolic wastewater including physical adsorption, chemical oxidation and biochemical degradation. It has been found that no single method can accomplish the phenol removal from wastewater with a great satisfactory in industries. The development of technology combining two or more removal methods hence becomes focus in the field.This paper is based on laboratory simulated phenol-containing wastewater. In the separate treatment by resin adsorption process and Fenton oxidation method, an innovation of phenol removal from wastewater has been developed using Fenton oxidation process and the adsorption through macroporous resin beads. At the same time, the study was tested on the strengthening action of reactor for the simulated phenolic wastewater and actual industrial wastewater treatment taking advantages of three phase fluidized bed reactor. The treatment effect and its influencing factors have been analysised and discussed. It provides the theory basis for the industrial application of this new technology.The major results of this research are briefly described below.After comparative study of three kinds of adsorption resins for phenol adsorption properties, H-103macroporous adsorption resin is of optimal performance. The removal of phenol from aqueous phenol solution was investigated using H-103macroporous resins. The effects of solution initial concentration, pH, reaction time and temperature on phenol removal were studied. The experimental results indicated that the adsorption reached equilibrium within30min and adsorption kinetics could be well described by the pseudo-second-order kinetic model, and Langmuir isotherm model was better to describe the isothermal adsorption of phenol onto the macroporous resin, At this point the concentration of phenol was1000mg/L. The equilibrium adsorption capacity (Qm) and Langmuir constant (KL) were86.00mg/g and0.2719L/mg, respectively,when the tempreture is25℃. Using70%(ω) ethanol as desorption agent, the desorption ratio was94.5%.Comparative study on the oxidation resistance of MnO2, KMnO4and Fenton reagent on phenol solution, the experimental results showed that Fenton reagent oxidation is of the best performance. The efficiency of Fenton agent was examined using phenol as a model compound in simulated wastewater. Batch studies were conducted to optimize the parameters such as the Fe2+initial concentration, the molar ratio of n(H2O2)/n(Fe2+), pH, temperature and reaction time governing the Fenton process. It was found that optimal operating conditions existed as:Fe2+initial concentration of3mmol/L, H2O2initial concentration of80mmol/L, pH=6, T=25℃and reaction time of60min. Under these conditions, the phenol removal ratio was95%.The efficiency of Fenton agent combined with macroporous resin H-103was examined using phenol as a model compound in simulated wastewater. A batch study was conducted to optimize parameters like the pH, reaction temperature, reaction time and solid holdup governing the process. The experimental results indicated that the phenol removal rate was98.6%using the oxidation-adsorption combination process at25℃, pH=4, Fe2+initial concentration of3mmol/L, H2O2initial concentration of80mmol/L, resin mass percent of1%, after a reaction time of5min. At this point the concentration of phenol was1000mg/L. It is obvious that the efficiency of phenol removal by using the oxidation-adsorption process is better than any of the single methods. Fitting the experimental data, kinetic model was established for the adsorption-oxidation combined process of synergetic degradation of phenol. The efficiency of Fenton agent combined with macroporous resin H-103was examined using phenol as a model compound in simulated wastewater in a gas-liquid-solid three-phase fluidized bed. A batch study was conducted to optimize parameters like the pH, reaction time, the resin solid holdup rate, H2O2initial concentration, Fe2+initial concentration and ventilation volume governing the process. The experimental results indicated that resin particle fluidization can strengthen the combination process of phenol removal effect, the phenol removal ratio was99.6%using the oxidation combined with adsorption process at25℃, pH=4, Fe2+initial concentration of3mmol/L, n(H2O2)/n(Fe2+)=20:1, resin mass percent of1%, ventilation volume of0.12m3/h, after reaction time of5min, At this point the concentration of phenol was1000mg/L. Other conditions are the same, no detection of phenol in solution, at this point the concentration of industrial phenol-containing wastewater was878mg/L.更多还原