- I - 摘要 高盐有机废水中含有高浓度的无机盐离子,这些无机盐离子会抑制微生物 的生长和代谢,影响生物处理效果,因此高盐有机废水的处理是目前废水处理 的一大难题。生物接触氧化法是一种新型的生物处理方法,具有耐冲击负荷能 力强、微生物浓度高、不需要污泥回流等优点,在污水处理中得以广泛应用。 本研究根据生物接触氧化工艺的设计原理,设计了一段生物接触氧化工艺装置, 并将海水应用于研究过程中,探索生物接触氧化工艺处理高盐有机废水的可行 性,为生物接触氧化技术处理高盐有机废水提供理论依据。 反应器Ⅰ处理普通高盐有机废水,采用接种活性污泥法启动,以逐渐增大 进水中海水比例的方式进行耐盐性驯化,经过 48 天的运行,反应器的启动和生 物膜驯化过程完成。研究了温度、HRT 及盐度对处理效果的影响,结果显示, 在 25~30℃、HRT=7h 及进水氯化钠质量分数低于 7%的条件下,处理效果最佳; 研究了进水 COD 和盐度对系统冲击缓冲作用的影响,结果显示,当系统受到较 大冲击作用时,经过 4~5 个运行周期可以恢复。 从威海市某渔港被石油污染水域通过富集驯化的方式筛选到三株高效苯酚 降解菌,分别命名为 CTE762-2、CTE762-5 和 CTE762-10,经过 16S rDNA 的 鉴定,初步确定三株菌株分属于海单胞菌属、节杆菌属和弧菌属。研究其在纯 培养条件下的降解性能得知,在适宜的环境条件下,三株菌株对苯酚的去除率 达到 90%左右。为了研究生物接触氧化工艺处理高盐含酚废水的可行性,利用 反应器Ⅱ,采用上述渔港水样为原水进行反应器的启动,经过 60 天的运行,系 统达到稳定状态。研究了不同条件下系统对苯酚的去除率,结果表明,当运行 参数和进水水质控制在一定条件下,出水苯酚能够达到国家污水综合排放标准; 结合生物接触氧化工艺的研究特点,采用莫诺模型研究了系统降解苯酚的动力 学模型,为实际含酚废水处理提供依据。 利用运行稳定的生物接触氧化反应器研究实际废水处理,经处理后得知, 青岛污水厂污水出水 COD 和氨氮分别为 68.05mg/L 和 11.57 mg/L;上海化工厂 污水出水 COD 为 333.26mg/L;威海化工厂污水出水的苯酚、COD 和氨氮分别 为 1.83 mg/L、946.32 mg/L,21.58 mg/L,三种废水的出水指标均达到了行业废 水的排放标准。 上述研究表明,采用生物接触氧化工艺处理普通高盐有机废水及高盐含酚 废水是可行的,并在抗冲击负荷能力及处理效率高等方面有其独特的优势。 关键词:接触氧化工艺;高盐有机废水;苯酚降解菌;去除率 Abstract - II - Abstract High concentration of inorganic ions in high salinity wastewater can inhibit the growth and metabolism of microorganisms, leading to low biological treatment efficiency. So the high salinity wastewater has been considered to be one of the most difficult problems in wastewater treatment. Biological contact oxidation process is a new type of wastewater treatment technology with some capabilities of resisting impact load, high concentration of microorganisms, and without sludge backflow. So this technology has been widely used in wastewater treatment. According to the design principle, a phase biological contact oxidation process was designed with seawater used in this paper to study the feasibility of high salinity wastewater teatmment by this thechnology. ReactorⅠsarted up by inoculating activated sludge is used to treat the common high salinity wastewater without refractory compounds. The biofilm domestication was implemented by increasing the proportion of seawater in inflent. After 48 days the reactor can run smoothly. The study about effects of temperature, HRT, and salinity on treatment efficiencies showed that the high treatment performance could be achieved when the temperature was at 25~30℃, HRT was 7 hours, and the salinity was less than 7%. The impact and buffer experiment showed that the biological contact oxidation system can recover over 4~5 cycles if it encountered shock of high organic loading or high salinity. Three bacteria have been isolated from the seawater of fishing port in Weihai which was polluted by petroleum with enrichment and domestication methods, named CTE762-2, CTE762-5 and CTE762-10. The degradation performance of isolations had been studied, reaching 90% or so under optimum conditions. Through the identification by 16S rDNA, that three bacteria were identified to be Oceanimonas sp., Arthrobacter sp., and Vibrio sp. preliminarily. In order to study the treatment of hypersaline wastewater containing phenol, reactorⅡwas used to conduct the experiment using the seawater sample mentioned as original water resources. After 60 days, the system can run smoothly. The phenol removal rate under different conditions had been studied, showing that when the operation parameters and inflent quality were controled under optimum conditions, the effluent could meet the discharge standard. According to the characteristics of this process, Monod equation has been used to study phenol degradation kinetics model in order to provide some theretical basis for practical wastewater with phenol treatment. These two reactors had been used to treat the practical wastewater from Abstract - III - wastewater treatment plant of QingDao, chemical plant wastewater in Shanghai and Weihai. The efflent COD and ammonia nitrogen were 68.05mg/L and11.57mg/L of wastewater treatment plant in Qingdao, the effluent COD of Shanghai chemical plant was 333.26mg/L, and the phenol, COD, and ammonia nitrogen of chemical plant in Weihai were 1.83 mg/L, 946.32 mg/L, 21.58 mg/L respectively which all met the industry wastewater discharge standard. The study on the treatment of nomal high salinity wastewater and high salinity wastewater with phenol shows that the biological contact oxidation process is feasible in high salinity wastewater treatment, showing preference in high capability of resisting impact load and high treatment efficency. Keywords: contact oxidation process, high salinity wastewater, phenol-degrading bacteria, removal rate 目 录 - IV - 目 录 摘要....................................................................................................................... I ABSTRACT ............................................................................................................. II 第 1 章 绪 论 .........................................................................................................1 1.1 课题研究背景 ..........................................................................................1 1.2 高盐有机废水简介 ...................................................................................1 1.2.1 高盐有机废水的来源及危害 ..................................................................2 1.2.2 高盐有机废水的生物处理研究 ..............................................................3 1.3 生物接触氧化工艺概述 ............................................................................6 1.3.1 生物接触氧化工艺的工作原理和流程 ...................................................6 1.3.2 生物接触氧化工艺填料的选择 ..............................................................7 1.3.4 生物接触氧化工艺的优缺点 ..................................................................8 1.3.5 生物接触氧化工艺在实际废水处理中的应用 .......................................9 1.4 课题研究目的、意义及主要内容 ........................................................... 12 1.4.1 课题来源................................................................................................ 12 1.4.2 课题研究的目的及意义 ........................................................................ 12 1.4.3 研究的主要内容 .................................................................................... 13 第 2 章 实验材料和方法........................................................................................15 2.1 实验材料................................................................................................ 15 2.1.1 接种污泥................................................................................................ 15 2.1.2 生物载体................................................................................................ 15 2.1.3 仪器设备................................................................................................ 15 2.1.4 实验所用废水水质 ................................................................................ 16 2.1.5 实验中所用到的培养基 ........................................................................ 16 2.2 实验装置................................................................................................ 16 2.3 实验方法................................................................................................ 17 2.3.1 水质分析方法 ........................................................................................ 17 2.3.2 高效海洋苯酚降解菌的分离方法......................................................... 18 2.3.3 高效海洋苯酚降解菌菌悬液的制备方法 ............................................. 19 2.3.4 高效海洋苯酚降解菌的总 DNA 提取及 16S rDNA 扩增.................... 19 第 3 章 接触氧化工艺处理普通高盐有机废水试验.............................................20 目 录 - V - 3.1 污泥接种及反应器的启动 ...................................................................... 20 3.1.1 反应器启动过程中对 COD 的去除效果 .............................................. 20 3.1.2 反应器启动过程中对 NH4 +-N 的去除效果 .......................................... 21 3.2 耐盐性驯化 ............................................................................................ 22 3.2.1 驯化过程中对 COD 的去除效果 .......................................................... 22 3.2.2 驯化过程中对 NH4 +-N 的去除效果 ...................................................... 24 3.3 最佳工艺参数的确定 ............................................................................. 25 3.3.1 水力停留时间的影响 ............................................................................ 25 3.3.2 温度的影响 ............................................................................................ 26 3.3.3 无机盐的影响 ........................................................................................ 27 3.4 冲击缓冲试验 ........................................................................................ 28 3.4.1 进水有机物浓度对系统的冲击缓冲试验 ............................................. 29 3.4.2 进水盐度对系统的冲击缓冲试验......................................................... 30 3.5 本章小结................................................................................................ 31 第 4 章 生物接触氧化工艺处理高盐含酚废水试验.............................................32 4.1 高效苯酚降解菌的筛选 .......................................................................... 32 4.2 高效苯酚降解菌的革兰氏染色实验........................................................ 32 4.3 高效苯酚降解菌 16S RDNA 序列分析 .................................................... 33 4.4 纯培养条件下高效苯酚降解菌降解特性研究 ......................................... 33 4.4.1 氧的影响................................................................................................ 33 4.4.2 转速的影响 ............................................................................................ 34 4.4.3 温度的影响 ............................................................................................ 34 4.4.4 pH 的影响 ............................................................................................... 35 4.4.5 外加碳源的影响 .................................................................................... 36 4.4.6 外加氮源的影响 .................................................................................... 37 4.5 自然富集法启动生物接触氧化反应器 .................................................... 38 4.5.1 启动过程中对苯酚的去除效果 ............................................................ 38 4.5.2 启动过程中对 COD 的去除效果 .......................................................... 39 4.5.3 启动过程中对 NH4 +-N 的去除效果 ...................................................... 40 4.6 生物接触氧化技术处理高盐含酚废水的性能研究 .................................. 41 4.6.1 HRT 的影响 ............................................................................................ 41 4.6.2 苯酚浓度的影响 .................................................................................... 42 4.6.3 无机盐的影响 ........................................................................................ 43 4.6.4 外加碳源的影响 .................................................................................... 45 目 录 - VI - 4.6.5 中间代谢产物含量的影响 .................................................................... 46 4.7 生物接触氧化工艺苯酚降解动力学模型研究 ......................................... 47 4.7.1 模型选择................................................................................................ 47 4.7.2 模型的建立及推导过程 ........................................................................ 48 4.7.3 生物接触氧化工艺处理高盐含酚废水的模型参数确定 ..................... 50 4.8 本章小结................................................................................................ 52 第 5 章 生物接触氧化工艺处理实际高盐有机废水研究.....................................53 5.1 青岛某污水处理厂污水处理试验 ........................................................... 53 5.2 上海某化工厂污水处理试验 .................................................................. 54 5.2.1 混凝沉淀预处理 .................................................................................... 55 5.2.2 接触氧化池对 COD 的去除效果 .......................................................... 57 5.3 威海市某化工厂废水处理试验 ............................................................... 59 5.3.1 处理过程中对苯酚的去除效果 ............................................................ 59 5.3.2 处理过程中对 COD 的去除效果 .......................................................... 60 5.3.5 处理过程中对 NH4 +-N 的去除效果 ...................................................... 61 5.4 本章小结................................................................................................ 62 结 论.....................................................................................................................64