I 摘要 超细银粉由于具有特异的量子尺寸效应和表面效应以及银本身优异的导电、 导热性和化学稳定性,因而广泛应用于各个工业领域。工业上多以液相还原法制 备银粉，液相还原法制备银粉也成为银粉制备的研究热点之一，而其制备过程中 所产生的废水中含有极高浓度的 COD、硫酸盐、氨氮、硝态氮还含有难降解有 机物，是一种难处理的工业废水，并且对其的处理研究也鲜有报道。 课题以某银粉生产企业的两个系列银粉生产废水为研究对象，结合企业提供 的水量及主要污染物成分信息对原水中主要污染物的检测结果进行分析，发现两 个系列废水中的反应母液 S3-1、S5-1 含总体废水 90%以上的污染物而水量为总 水量的 40%。因此针对两股反应母液的水质特点采用吹脱/蒸发和蒸发工艺对 S3-1、S5-1 两股废水分别进行预处理，去除废水中绝大多数的污染物质及有毒物 质，并对 S3-2 废水采用离子交换法降低其水中硫酸根浓度，提高废水的可生化 性，再与其余的清洗水混合后进一步进行生物处理，并通过高级氧化法进一步去 除出水中剩余的难降解有机物，减轻后期深度处理的难度。 通过小试对整套工艺进行研究，一方面探讨该工艺处理银粉废水的可行性， 另一方面优化运行参数在保证处理效果的同时控制能源及药品的消耗，为后期的 工程应用提供参考。整体工艺研究成果如下： (1)S3-1 氨氮吹脱段进水 pH 设置为 12，温度 20℃、气液比为 3000、进水氨 氮浓度为 16800mg/L,处理后出水能降至 600-850mg/L,去除率达到 94.9%以上。 S3-1 吹脱后出水进行的蒸发处理，在无需进行 pH 调节，直接进行蒸发处理，其 COD、总氮、硫酸根的去除率能够达到 99.01%、95%、99.65%。而 S5-1 蒸发段 的 pH 调节至 4 后氨氮及 COD 去除率分别为 93.03%和 96.4%。都能够有效去两 股反应母液中大部分的污染物，采用离子交换法降低 S3-2 中硫酸根浓度，最终 混合水中 COD、氨氮、硫酸根、总氮浓度分别为 2580.8mg/L、243.82mg/L、 103.5mg/L、579mg/L。 (2)进入一体式 ABR+A/O 反应器进行处理。整体反应器出水 COD、氨氮及 总氮浓度分别为 1170mg/L、43mg/L、245mg/L，反应器对 COD 及总氮的去除率 分别在 50%、60%左右，主要是由于混合水中仍有较高浓度的难生物降解有机物。 (3)采用芬顿氧化法对生物段出水中的难降解有机物做进一步的去除，最终出 水 COD、总氮、氨氮分别能够降至 141mg/L、170mg/L、37mg/L，达到在深 度处理前的去除目标（COD<300mg/L、总氮<200mg/L、氨氮<50mg/L）。 关键词：银粉废水，吹脱，蒸发，ABR+A/O 工艺，芬顿氧化苏州科技大学硕士报告 Abstract II Abstract Ultrafine silver powder is widely used in various industrial fields due to its special quantum size effect and surface effect, as well as its excellent electrical conductivity, thermal conductivity and chemical stability. In industry, silver powder is mostly produced by liquid phase reduction method.Due to the wide application in industry, the liquid phase reduction method is also known as one of the research hotspots in the production of silver powder, but the wastewater treatment technology generated in the production process is rarely reported. This paper takes waste water from two series of silver powder production in a silver powder production enterprise as the research object,the detection results of main pollutants in raw water are analyzed by combining the information of water quantity and main pollutant composition provided by enterprises,it was found that the reaction mother liquor s3-1 and s5-1 in the two series of wastewater contained more than 90% of the pollutants in the total wastewater, and the water amount was 40% of the total water amount.Therefore, according to the water quality characteristics of the two reaction mother liquor, stripping/evaporation and evaporation processes were adopted to pretreat the wastewater of s3-1 and s5-1 respectively to remove most of the pollutants and toxic substances in the wastewater and improve the biodegradability of the wastewater, then mixed with low concentration cleaning water for further anaerobic and aerobic combined biological treatment. Finally, advanced oxidation method was used to further treat the remaining refractory organic matter in the biological water to reduce the difficulty of advanced treatment at later period. The whole process was studied through the laboratory tests, the feasibility of treating silver powder wastewater by this process was discussed,On the other hand, the optimized operation parameters can not only ensure the treatment effect, but also control the consumption of energy and drugs, providing reference for the later engineering application.The laboratory tests results showed as follows. (1) The pH of inflow water at S3-1 ammonia nitrogen blowoff segment is set as 12, temperature is 20 ℃, gas liquid ratio is 3000, and the ammonia nitrogen concentration of inflow water is 16800 mg/L, after this process, effluent can drop to 600-850 mg/L, and the removal rate can be up to 94.9% or more.After s3-1 is blown off, the effluent is evaporated directly without pH adjustment, and the removal rate of COD, total nitrogen and sulfate can reach 99.01%, 95% and 99.65%.The removal rates of ammonia nitrogen and COD in the S5-1 evaporation section were 93.03% and苏州科技大学硕士报告 Abstract III 96.4% respectively after the pH was adjusted to 4,both effectively removed most of the contaminants from the mother liquor.The concentration of sulfate in s3-2 was reduced by ion exchange method, and the final concentration of COD, ammonia nitrogen, sulfate and total nitrogen in the mixed water were 2580.8mg/L, 243.82mg/L, 103.5mg/L and 579mg/L, respectively. (2) The mixed water is treated in an integrated ABR+A/O reactor.The overall effluent COD, ammonia nitrogen and total nitrogen concentrations of the reactor were 1170mg/L, 43mg/L and 245mg/L respectively.Mainly due to the high concentration of nitrogen-containing organics that were difficult to be biodegraded in the mixed water,The removal rates of COD and total nitrogen in the reactor were about 50% and 60% respectively. (3) Fenton oxidation method was used to further remove the refractory organic compounds in the effluent of the biological section. COD, total nitrogen and ammonia nitrogen in the effluent were reduced to 141mg/L, 170mg/L and 37mg/L, respectively.Finally, the removal target (COD<300mg/L, total nitrogen <200mg/L, ammonia nitrogen <50mg/L) before the deep treatment was achieved. Key words:Silver Powder Wastewater ,Ammonia stripping, Evaporation, ABR+A/O, Fenton oxidation苏州科技大学硕士报告 目录 IV 目 录 摘要..............................................................................................................I Abstract......................................................................................................II 第一章 绪论............................................................................................... 1 1.1 研究背景.........................................................................................................1 1.2 高浓度工业废水工艺研究现状.....................................................................2 1.2.1 高浓度氮废水的预处理.......................................................................2 1.2.2 高浓度硫酸盐废水的预处理...............................................................4 1.2.3 高浓度有机废水的预处理...................................................................6 1.2.4 生物处理工艺.......................................................................................8 1.3 课题的研究目的和研究意义..........................................................................9 1.4 研究内容及研究路线....................................................................................10 1.4.1 研究内容.............................................................................................10 1.4.2 研究路线.............................................................................................11 第二章 银粉生产废水的处理工艺选择与检测方法............................12 2.1 银粉生产废水特点.......................................................................................12 2.1.1 银粉生产流程以及废水主要来源.....................................................12 2.1.2 废水日产生水量.................................................................................12 2.1.3 废水水质指标及主要污染物.............................................................13 2.2 废水排放标准及处理目标的提出...............................................................13 2.3 银粉废水处理工艺选择...............................................................................14 2.3.1 物化预处理的选择.............................................................................14 2.3.2 生物处理段.........................................................................................15 2.3.3 生物段出水的进一步物化处理........................................................16 2.3.4 组合工艺流程及工艺特点................................................................16 2.4 检测方法.......................................................................................................18 2.4.1 废水中常规指标检测方法................................................................18 2.4.2 溶解性有机物三维荧光测定............................................................18 第三章 银粉废水的物化预处理研究.....................................................19 3.1 吹脱法处理 S3-1 废水优化试验研究.........................................................19 3.1.1 试验水样、试剂及设备....................................................................19苏州科技大学硕士报告 目录 V 3.1.2 单因素优化实验................................................................................19 3.2 蒸发法处理吹脱后 S3-1 废水试验研究.....................................................24 3.2.1 试验水样、试剂及设备....................................................................24 3.2.2 实验方案............................................................................................25 3.2.3 实验结果与分析.................................................................................25 3.3 蒸发法处理 S5-1 废水试验.........................................................................28 3.3.1 试验水样、试剂及设备.....................................................................28 3.3.2 实验方案.............................................................................................29 3.3.3 试验结果与分析.................................................................................29 3.4 预处理后出水与清洗水混合.......................................................................31 3.4.1 混合水水质指标................................................................................31 3.4.2 离子交换法去除 S3-2 废水中硫酸根试验....................................... 32 3.5 本章小结........................................................................................................34 第四章 预处理后混合废水的生物处理研究........................................ 36 4.1 混合水水质指标...........................................................................................36 4.2 试验装置及试验的仪器及药剂....................................................................36 4.2.1 试验装置.............................................................................................36 4.2.2 试验设备与药剂.................................................................................37 4.3 反应器运行...................................................................................................37 4.3.1 接种污泥主要特性............................................................................37 4.3.2 反应器的运行....................................................................................38 4.4 试验结果与讨论............................................................................................38 4.4.1 反应器对 COD 处理的运行情况分析..............................................38 4.4.2 反应器对氮处理的运行情况分析....................................................41 4.4.3 对驯化完成后反应器进出水中溶解性有机物的三维荧光分析....42 4.5 反应器的影响因素.......................................................................................43 4.5.1ABR 反应器影响因素........................................................................43 4.5.2A/O 反应器影响因素.........................................................................45 4.6 本章小结........................................................................................................46 第五章 生物段出水的物化处理研究.....................................................47 5.1 芬顿氧化试验...............................................................................................47 5.1.1 试验材料与方法................................................................................47 5.1.2 试验结果与分析.................................................................................48苏州科技大学硕士报告 目录 VI 5.2 本章小结........................................................................................................50 第六章 结论与建议.................................................................................51 6.1 结论................................................................................................................51 6.2 建议................................................................................................................52