因发展需要，H 制药厂将搬迁至哈尔滨市利民经济开发区内，由于制药行 业废水排放要求的严格化，治理达标将需要更多成本。一方面为了保证出水稳 定达标，另一方面为了节省 H 制药厂二沉池出水的深度处理成本，与工程上大 多数将城市污水引入药厂的做法不同，本课题将 H 制药厂二沉池出水排入搬迁 地现有污水处理厂，与污水厂进水（即城市污水）混合处理。 为了掌握 H 制药厂二沉池出水水质基本状况，在对常规指标进行分析的基 础上，利用气相色谱质谱（GC-MS）手段对二沉池出水中的有机物进行定性检 测，结果表明，H 制药厂二沉池出水的化学需氧量 COD 浓度在 500 mg/L 左右， 氨氮浓度值较高，在 80 mg/L 左右，五日生化需氧量/化学需氧量（B/C）值非 常低，不到 0.05，并且其特征污染物主要是一些难降解的单环双环杂环类芳香 烃，长链烷烃以及胺类物质。由于此二沉池出水可生化性极差，必须引入深度 处理技术，改善可生化性。在前期工作基础之上，选择了臭氧催化氧化对其进 行预处理，试验结果表明，利用臭氧催化氧化技术可有效改善废水的可生化性， 同时三维荧光检测结果表明，臭氧催化氧化技术有效降低了废水中特征污染物 的浓度。 哈尔滨市利民污水厂采用的主要工艺是水解酸化+CAST 工艺，对其长期监 测结果表明，水厂各季节进水情况基本一致，进水 COD 浓度在 500 mg/L 左右， 氨氮浓度在 35 mg/L 左右，总磷浓度在 3 mg/L 左右，SS 浓度在 120 mg/L 左右。 冬季出水 COD 浓度在 50 mg/L 左右，氨氮浓度在 9 mg/L 左右，总磷（TP）浓 度在 0.5 mg/L 左右，SS 浓度在 25 mg/L 左右；其他季节出水 COD 浓度在 36 mg/L 左右，氨氮浓度在 5 mg/L 左右，总磷浓度在 0.5 mg/L 左右，悬浮颗粒物（SS） 浓度在 14 mg/L 左右。为保证冬季出水达标，需增加滤布滤池工艺。 在实验室利用杯罐实验方法对 H 制药厂二沉池出水与城市污水的混合配比 进行试验研究，研究结果证明，无预氧化条件下二者以低比例（1:20、1:25、1:30） 配比混合，出水可以达标排放，有预氧化条件下二者以中低比例（1:12、1:16、 1:20）配比混合，出水可以达标排放；根据 H 制药厂排水及利民污水厂不同季 节的进水情况，结合混合配比试验结果，最终确定配比为最不利情况下的 1:9、 实际运行高负荷下的1:15、实际运行常负荷下的1:20；并且根据最不利配比（1:9） 下的出水水质情况，进一步确定增加过滤工艺的的必要性。 根据改进的工艺流程，设计中试装置，进行中试试验，中试试验结果表明哈尔滨工业大学工学硕士学位报告 - II - 最不利情况 1:9 配比、高负荷 1:15 配比条件下需要开启臭氧催化氧化，常负荷 1:20 配比下可以不开启臭氧催化氧化，三种情况下出水水质均能达到国家排放 标准；同时根据利民污水厂进水水质规律的研究，确定每天上午 8:00 为 H 制药 厂二沉池出水引入的最佳时间点，水解酸化池为其引入的最佳工艺点；根据中 试结果提出工程化改造方案，利民污水处理厂需增加污水事故池、臭氧催化氧 化间、过滤间，确定采用“臭氧催化氧化+废水混合+水解酸化+CAST+过滤” 工艺处理 H 制药厂二沉池出水，最后进行技术经济分析。 关键词，制药废水；城市污水；混合处理；预氧化和生物处理哈尔滨工业大学工学硕士学位报告 - III - Abstract For development, H Pharmaceutical Factory will move to Limin Economic Development Zone in Harbin. But as the pharmaceutical industry wastewater discharge standard become more strict, it will need to cost more money to meet the discharge regulation. In order to guarantee the effluent quality and save the costs, in this paper, the secondary sedimentation tank effluent from the above pharmaceutical factory discharged into the existing sewage treatment plant-Limin Sewage Treatment Plant-in Li min Economical Development Zone, in which it would mix with the influent of Limin Sewage Treatment Plant water, before flowing the sewage treatment facility in Li min Sewage Treatment Plant. The secondary sedimentation tank effluent from H pharmaceutical factory were qualitative detected by GC-MS based on the routine detection and analysis, in order to know the particular pollutants. The results showed that concentration of COD of this wastewater was about 500 mg/L, the concentration of ammonia nitrogen was about 80 mg/L, and its B/C was very low and the value was litter than 0.05.And its particular pollutants were refractory materials such as Monocyclic, polycyclic, heterocyclic aromatic hydrocarbons and long chain alkane, et al. To improve its biodegradability, ozone catalytic oxidation was introduced as advanced method, the experimental results showed this technology was effective to improve biodegradability. And according to the fluorescence spectroscopy detection results, ozone catalytic oxidation was also effective to lessen the concentration of particular pollutants. Limin Sewage Treatment Plant adopted hydrolysis acidification+CAST process to treat sewage wastewater, the results of long-term monitoring showed that the influent quality was consistent in different seasons, the concentration of COD, ammonia, total phosphorus, SS was respectively 500 mg/L, 35 mg/L, 3 mg/L, 120 mg/L. And in winter, the effluent COD concentration was about 50 mg/L, ammonia nitrogen concentration was about 9 mg/L, total phosphorus concentration was about 0.5 mg/L, SS concentration was about 25 mg/L; and COD concentration was about 35 mg/L, ammonia nitrogen concentration was about 5 mg/L, total phosphorus concentration was about 0.5 mg/L, SS concentration was about 14 mg/L, in the other seasons. So to guarantee the effluent quality in winter, the filtering process was needed to be built. The jar test was tried to study the proper mixed appropriation of the secondary sedimentation tank effluent from H Pharmaceutical Factory and the inflow of Li min哈尔滨工业大学工学硕士学位报告 - IV - Sewage Treatment Plant, the conclusion showed that with no-preoxidation, effluent could meet the discharge regulations under the low ratio of 1:20,1:25,1:30, with preoxidation, effluent could meet the discharge regulations under the medium and low ratio of 1:12,1:16,1:20. According to the actual inflow of LiMin and the actual outflow of H Pharmaceutical Factory, the mix proportion of 1:9,1:15,1:20 were finally deter mined.At the same time, the filtering process was adopted to improve the effluent quality at the worst-case ratio of 1:9. The pilot-scale experiment was tried to verified the conclusion of mixed treatment experiment, and its conclusion was accordance with the mixed treatment experiment: under the worst-case and the high-load-case, ozone catalytic oxidation were needed; under the normal-load-case, ozone catalytic oxidation could be omitted; and all the above situations, the effluent could meet the regulations. And newly-buliding of the preoxidation room, the filtering room and the wastewater storage tank and the best time and location for funneling the secondary sedimentation tank effluent was advised in engineering project. Then the process of ozone catalytic oxidation+mixed wastewater+hydrolysis acidification+ CAST + filter was adopted to treatment the secondary biochemical effluent from H Pharmaceutical Factory, in the last, technology and economy evaluation were drawn. Keywords:Pharmacuetical wastewater, Urban sewage, Mixed treatment, Preoxidation and biotreatment哈尔滨工业大学工学硕士学位报告 - V - 目 录 摘要............................................................................................................................... I ABSTRACT....................................................................................................................III 目 录..............................................................................................................................V 第 1 章 绪 论................................................................................................................1 1.1 课题研究背景、目的及意义...............................................................................1 1.1.1 课题来源.........................................................................................................1 1.1.2 课题背景.........................................................................................................1 1.1.3 课题研究的目的及意义................................................................................2 1.2 抗生素制药废水....................................................................................................3 1.2.1 抗生素制药废水来源及特点........................................................................3 1.2.2 抗生素制药废水毒性及危害........................................................................3 1.3 抗生素制药废水处理方法...................................................................................4 1.3.1 物化处理方法.................................................................................................5 1.3.2 生化处理方法.................................................................................................7 1.4 抗生素制药废水深度处理方法...........................................................................8 1.4.1 深度处理方法.................................................................................................8 1.4.2 复合处理方法...............................................................................................10 1.5 现有技术存在问题分析..................................................................................... 11 1.5.1 外加碳源的必要性.......................................................................................11 1.5.2 城镇污水处理厂作为深度处理工艺......................................................... 12 1.6 研究内容及技术路线......................................................................................... 12 1.6.1 研究内容.......................................................................................................12 1.6.2 技术路线.......................................................................................................13 第 2 章 试验材料与方法..............................................................................................14 2.1 试验材料与设备..................................................................................................14 2.1.1 试验材料.......................................................................................................14 2.1.2 试验设备及仪器...........................................................................................14 2.2 课题研究方法......................................................................................................15 2.2.1 水质指标检测方法...................................................................................... 15 2.2.2 特征污染物检测方法.................................................................................. 15 2.2.3 臭氧催化氧化试验方法..............................................................................16哈尔滨工业大学工学硕士学位报告 - VI - 2.2.4 三维荧光检测方法...................................................................................... 17 2.2.5 不同配比混合试验方法..............................................................................17 2.2.6 中试试验方法...............................................................................................18 2.2.7 废水最佳引入点试验方法..........................................................................21 第 3 章 H 制药厂二沉池出水分析及深度处理效能研究........................................22 3.1 引言.......................................................................................................................22 3.2 H 制药厂简介......................................................................................................22 3.2.1 H 制药厂概况...............................................................................................22 3.2.2 H 制药厂水质...............................................................................................22 3.2.3 H 制药厂现有污水处理站简介..................................................................23 3.3 H 制药厂二沉池出水水质特性分析.................................................................24 3.3.1 水质变化情况...............................................................................................24 3.3.2 H 制药厂二沉池出水水质分析..................................................................24 3.3.3 特征污染物分析...........................................................................................27 3.4 臭氧催化氧化试验..............................................................................................36 3.4.1 预处理方法的选择...................................................................................... 36 3.4.2 臭氧催化氧化试验...................................................................................... 37 3.4.3 结构性催化剂处理效果研究......................................................................40 3.4.4 氧化对废水主要物质的影响......................................................................42 3.5 本章小结..............................................................................................................43 第 4 章 H 制药厂二沉池出水与城市污水混合处理试验研究................................ 44 4.1 引言.......................................................................................................................44 4.2 利民污水厂现有工艺效能研究.........................................................................44 4.2.1 利民污水厂现有工艺介绍..........................................................................44 4.2.2 主要工艺效能分析...................................................................................... 45 4.2.3 进出水水质分析...........................................................................................47 4.3 混合处理试验......................................................................................................49 4.3.1 无预氧化混合处理试验..............................................................................50 4.3.2 预氧化条件投配试验.................................................................................. 51 4.3.3 混合配比的确定...........................................................................................52 4.3.4 最不利配比下混合试验..............................................................................53 4.4 本章小结..............................................................................................................54 第 5 章 混合处理中试试验及工程化方案................................................................ 55 5.1 引言.......................................................................................................................55哈尔滨工业大学工学硕士学位报告 - VII - 5.2 混合处理中试试验..............................................................................................55 5.2.1 最不利情况配比下中试试验......................................................................55 5.2.2 高负荷配比下中试试验..............................................................................58 5.2.3 常负荷配比下中试试验..............................................................................61 5.3 废水最佳引入时间点及工艺点.........................................................................63 5.3.1 最佳时间点的确定...................................................................................... 64 5.3.2 最佳工艺点的确定...................................................................................... 65 5.4 工程化改造方案..................................................................................................66 5.4.1 工程化改造方案...........................................................................................66 5.4.2 工程技术经济分析...................................................................................... 66 5.5 本章小结..............................................................................................................67 结 论.............................................................................................................................68