I 摘要 本文依托联想控股（汶上）化工园区污水处理工程实例，研究高级氧化在工 业废水处理中的工程应用。主要包括以下几个方面：通过实验论证紫外线高级氧 化降解氯苯和环己酮的可行性，分析各项影响因素，选择适合的工艺流程方案、 设备设计参数和控制参数，进行实际运行测试和经济指标分析。主要结论如下： 研究了紫外线高级氧化技术处理氯苯和环己酮废水的可行性。通过对比 UV、 HO和 UV/HO对氯苯和环己酮的降解效果和动力学参数，结果表明 UV/HO 组合工艺比单独 UV 或 HO氧化的处理效果都好。对氯苯的去除率达到 90%以上， 对环己酮的去除效率较低。第一阶段氯苯主要参加羟基自由基反应，速率常数为 9.8×10 -3 s -1 ，第二阶段中间产物与氯苯竞争，速率常数为 3.7×10 -3 s -1 。UV/ HO组合 工艺处理环己酮，其降解反应速率常数为 1.2×10 -4 s -1 。 研究了 LPUV/HO和 MPUV/HO高级氧化降解氯苯和环己酮的影响因素。 主要研究了对紫外光波长、紫外光强度、HO投加量、污染物初始浓度和 pH 的 影响作用。 MPUV/HO对氯苯和环己酮的去除效果总体高于 LPUV/HO。当增 大紫外光强或增加容易被 HO、目标污染物或中间产物吸收的紫外线光波时，反 应效果和速率大幅度提高。综合分析紫外线剂量、EEO、HO消耗量与污染物去 除量之间的关系，确定了 UV/HO降解氯苯和环己酮的最佳 HO投加量为 20mg/L。 污染物浓度与反应速率呈对数增长。此外，pH 酸性偏中性条件更有利 于反应进行。 取得了工程化应用的参数，提出了工程方案。本项目设计处理规模为 420m^3/h， 中压紫外线总剂量为 216kW。选用 6 套 36kW 的中压紫外反应器，反应器设计剂 量大于 720mJ/cm^2，停留时间为 1.43s。工艺流程为二级串联三单元并联的中压 UV/HO 高级氧化工艺， HO 的投加方式为分批次投加。 HO 投加范围为 0~30mg/L，现场实际运行处理效果在 22%~37%之间。 分析了紫外线和过氧化氢高级氧化工艺的技术经济指标。以 EEO 和紫外线剂 量作为经济指标对紫外线高级氧化的投资成本进行估算，对与处理规模为 420m^3 /h，设备费用 400 万元，土建投资费用 30 万元，每吨水的运行成本为 0.638~0.774 元。中压 UV/HO组合工艺运行成本低于低压 UV/HO工艺。 关键词：紫外线高级氧化；UV/HO；氯苯；环己酮；工程应用III Abstract Based on the project of wastewater treatment for chemical industrial area in Wenshang, Shandong province, this thesis is focused on engineering application of advanced oxidation in industrial wastewater treatment. Several aspects are included as follows. The feasibility of UV-base advanced oxidation processes for the degradation of chlorobenzene and cyclohexanone is demonstrated. After analysis on each influencing factors, the process flow scheme and parameters of design and operation are optimized. In the end, we carry out analysis on operating test and economic indicators. Degradation of chlorobenzene and cyclohexanone using oxidation UV, HO and UV/ processes is investigated. The degradation efficiency of UV/HO is better than only UV and HO. The UV/HO system for chlorobenzene reaction has two distinct phases marked as phase I and phase II. In the first phase HO concentration is the controlling factor in the degradation process, whereas in the second phase concentration of intermediates is the controlling species. The reaction rate constant are 9.8×10 -3 s -1 and 3.7×10 -3 s -1 .However, A pseudo-first order kinetic model was adopted to represent the UV/HO system for cyclohexanone reaction. The reaction rate constant is 1.2×10 -4 s -1 . The effect factors such as UV wavelengths, UV intensity, HO initial concentration, pollutants initial concentration and initial pH are investigated using both LPUV/HO and MPUV/HO processes. MPUV/HO was found to degrade chlorobenzene and cyclohexanone more rapidly than LPUV/HO. The high UV intensity and the UV wavelengths that are easier to be absorbed by HO, contaminant and intermediate may improve effects and reaction rate. Through summarize the dosage of UV and HO, the EEO of chlorobenzene and cyclohexanone, the effluent concentration of chlorobenzene and cyclohexanone, it is conclusion that the optimal doses of hydrogen peroxide at this industrially relevant is 20 mg/L. Pollutants initial concentration increases with reaction rate logarithmly. The pH under acidulous and neutralconditions has advanced to increase reaction rate. This chemical industrial wastewater treatment plant of water is 10000 ton per day. The total dose of MPUV light is 216 kW. According to the design parameters, the AOP system requires three parallel trains of two MPUV reactors in series, (6 reactors in total).摘要 IV The dosage of each reactor is above 720 mJ/cm^2. The Lindustrial effluent is 1.43 s. The dosage of HO is 0~30 mg/L. Using batch feeding method makes the HO utilization rate more efficiently. In actual operation, the removal rate of COD is between 22% and 37%. The technical economic indicator of UV-based advanced oxidation process is analyzed. The Electrical Energy per order (EEO) and UV dose.The EEO of the MPUV/HO system is lower than that of the LPUV/HO system for the removal of COD in actual operation. To the treatment scale is 420 m^3/h, the equipment cost is 4 million yuan and the installation cost is 300,000 yuan. The total operation cost is 0.638~0.774 yuan. Key words: UV-based advanced oxidation process；UV/HO；chlorobenzene； cyclohexanone；Application目录 V 目录 第 1 章 引言.................................................................................................................1 1.1 研究背景及意义 .......................................................................................... 1 1.1.1 工业废水对环境的危害 .......................................................................... 2 1.1.2 工业废水处理现状 .................................................................................. 2 1.1.3 工程项目概述 .......................................................................................... 3 1.2 国内外研究状况 .......................................................................................... 5 1.2.1 高级氧化技术研究现状 .......................................................................... 5 1.2.2 UV 及 UV/HO高级氧化技术............................................................... 6 1.2.3 UV/HO高级氧化处理技术的影响因素 .............................................. 8 1.2.4 紫外线高级氧化处理技术的经济分析 ................................................ 10 1.2.5 UV/HO高级氧化的工程应用 ............................................................ 10 1.3 研究内容及技术路线 ................................................................................ 12 1.3.1 研究目的 ................................................................................................ 12 1.3.2 研究内容 ................................................................................................ 12 1.3.3 技术路线 ................................................................................................ 12 第 2 章 实验材料与方法...........................................................................................13 2.1 仪器设备 .................................................................................................... 13 2.2 试剂药品 .................................................................................................... 13 2.3 样品配制 .................................................................................................... 14 2.3.1 氯苯溶液配制 ........................................................................................ 14 2.3.2 环己酮溶液配制 .................................................................................... 14 2.3.3 原水水质 ................................................................................................ 15 2.4 分析方法 .................................................................................................... 15 2.4.1 HO的检测方法 ................................................................................... 15 2.4.2 氯苯和环己酮的检测方法 .................................................................... 16 2.4.3 紫外线高级氧化方法 ............................................................................ 17 第 3 章 紫外线高级氧化降解氯苯和环己酮的可行性研究...................................20 3.1 紫外线高级氧化降解氯苯的可行性 ......................................................