【作者】 高梅鷟；

【导师】 任南琪；

【作者基本信息】 哈尔滨工业大学 ， 环境科学与工程， 2010， 博士

【摘要】 随着社会经济的不断发展和人们环境意识的提高，我国加大了对印染废水的治理。印染废水组分非常复杂，其难降解、有毒有机成分的含量也越来越多，有机物含量高、色度深、化学需氧量高，而生化需氧量相对较低，可生化性差，排放量大，有些甚至是致癌、致突变、致畸变的有机物，对环境尤其是水环境的威胁和危害越来越大。传统的印染废水生物处理方法，只能降低印染废水中的BOD5，对于COD，特别是有毒难降解有机物和色度的降低效果不明显。可见，单一的处理方法已不能满足当前印染废水发展的要求。本文通过分析印染废水水质特点和比较多种废水处理路线与工艺，提出了利用“厌氧折流板反应器（ABR）—交叉流好氧反应器（CFASR）”这一技术路线处理该种废水的中试方案，并在中试试验数据和ADM-ASM1的基础上建立了相关的数学模型以指导中试运行。针对印染废水水质特点，提出了ABR-CFASR组合工艺处理印染废水的技术路线，考察了ABR-CFASR组合工艺处理印染废水的中试运行效果，并确定了最佳工艺参数及启动运行方案。ABR运行结果表明，在进水COD为1000mg/L左右波动的情况下，对COD、BOD、SS和色度去除率平均值分别为42%、19.2%、48.6%和30%；印染废水经ABR处理后，出水略有升高，而出水TN比进水略下降，出水TP含量有所提高，同时ABR进出水B/C由0.56提高到0.68，这将有益于后续的CFASR反应器中好氧微生物的生长；确定了ABR启动和运行方案：HRT、pH、MLSS、MLVSS、容积负荷、污泥负荷在启动时应分别控制在60h、7、45g/L、30g/L、2.0kgCOD/(m3·d)、0.1kgCOD/(kgMLVSS·d)，在稳定运行时应分别控制在12h、7～9、35～50g/L、20～35g/L、6.0～18.0kgCOD/(m3·d)、0.2～0.5kgCOD/(kgMLVSS·d)。与ABR串联的CFASR中试运行结果表明：在HRT为20h、MLSS为1500～2000mg/L、污泥负荷为0.2～0.8kgCOD/(kgMLSS·d)、温度为15～37℃、pH为7.12～8.86、DO为2.0～3.0mg/L的条件下，出水COD<100mg/L，BOD<20mg/L，满足国家一级排放标准。试验结果还表明，CFASR对TN、TP、SS和色度均具有较高的去除率，分别为90%、80%、90%和80%以上。由于印染废水pH值较高（最大可达到10），而传统厌氧生物处理反应器（如UASB）最适pH范围为7.5～8.0，因此传统印染废水处理工艺应加硫酸调节pH。而本中试试验结果表明：与传统的印染废水厌氧处理工艺相比（如UASB），ABR可以承受的最大进水pH为9.5，不必加硫酸调节pH，因此节约大量药剂费用。另外，传统厌氧工艺处理印染废水HRT较长（大于20h），而本中试试验结果表明ABR可以在较短的HRT（12h）下稳定运行，可大大节约用地面积。采用GC-MS和LC-MS等分析手段，考察了ABR对印染废水中有机物和染料分子的去除效果。结果表明：ABR进水中均含大量的高级烷烃、酰胺类、有机酸、酮类、酚类和酯类，ABR反应器对其降解效果很好，出水中这些物质含量很低。经过ABR后，物质化学结构基本都发生了较大的变化，许多大分子物质都转化为小分子物质，有利于后续好氧工艺进一步降解。ABR对色酚AS-E、偶氮染料酸性橙、直接蓝、蒽醌类-酸性蓝有较好的去除效果，但对偶氮类-苏丹红1号没有去除。以国际水质污染与控制协会(IWA)推出的厌氧活性污泥数学模型（ADM1）和活性污泥数学模型（ASM1）为理论基础，并对其进行了修正和完善，建立了ABR-CFASR处理印染废水的数学模型，从而为ABR-CFASR处理印染废水的设计、优化运行、出水水质预测与控制提供理论依据。基于ADM的ABR模拟结果表明：ABR第一格室出水COD浓度的模拟值和实测值有较大的差距，相对偏差为-32.8%~30.6%，而第三格室和第六格室出水COD模拟效果较好，相对偏差为-20%~20%。另外，ABR模型也表现出对VFA、MLVSS和pH有较好的模拟结果。基于ASM1的CFASR模型模拟结果表明：不同HRT条件下，模型模拟值和试验值非常吻合，相对偏差率为-14%～14%，说明本模型可以用于CFASR出水系统预测。而ADM-ASM1组合模型对出水COD的相对偏差为-18%～19%，最终模拟结果偏差大于CFASR出水模拟结果偏差，原因可能是参数估计误差和由ADM模型所导致的ABR出水水质（即CFASR进水）估计误差所致。更多还原

【Abstract】 With the rapid development of economic and enhancement of people’senvironmental awareness, our country increases the treatment degree of the printingand dyeing wastewater. As there exists difference between raw materials, productionvarieties, production technology and management level, the quality of the printingand dyeing wastewater is different from each other. As a result, the components ofwastewater discharged by the different processes are extremely complex. Becausethere are more and more organic components that are poisonous and hard to depose.Furthermore, printing and dyeing wastewater has high organisms with high COD butlower BOD, heavy color, poor biodegradability and large emissions, some of whicheven are carcinogenic, mutagenic, distortion organic matters that have increasinglythreatens and hazards to the environment especially the aquatic environment.Traditional biological treatment for printing and dyeing wastewater has a highremoval on BOD5, but inefficient for COD, especially for toxic refractory organicmatter and chroma. It is thus clear that a single approach increasingly facing achallenge to meet the requirement of the development of the printing and dyeingindustry. After analyzing the character of printing and dyeing wastewater andcomparing the different practical wastewater treatment technology route of a sewagedisposal, we bring forward the plan through which the technology route of “anaerobicbaffled reactor (ABR)–cross flow aerobic sludge reactor (CFASR)” is utilized totreat this kind of wastewater, and modeling based on the pilot test data andADM-ASM1to instruct pilot operation.The technology of route which employs a combined process ABR–CFASR totreat the printing and dyeing wastewater was put forward on account of thewastewater characteristics. Pilot-scale operation effect of ABR–CFASR system isexamined and optimal process parameters and start running program weredetermined. The ABR results show that when the influent COD fluctuates at1000mg/L, the average removal of COD, BOD, SS and chroma were42%,19.2%,48.6%and30%, respectively. After the treatment of ABR, effluent NH4+-N raises slightly,effluent TN declines slightly compared with influent TN, and TP content in waterrises, accompany with the B/C of ABR increased from0.56to0.68, this improvements of B/C is favorable for the growth of aerobic micro-organisms in thefollow-up CFASR reactor. According to the results the startup and running programof ABR are determined: the startup HRT, pH, MLSS, MLVSS, volume-load, sludgeload were controlled at60h,7,45g/L,30g/L,2.0kgCOD/(m3·d),01kgCOD/(kgMLVSS·d), respectively;when the system being steady operationthese parameters are controlled at12h,7~9,35~50g/L,20~35g/L,6.0~18.0kgCOD/(m3·d),0.2~0.5kgCOD/(kgMLVSS·d). The result of operationeffect of pilot-scale CFASR in series with ABR show:under the condition ofHRT=20h, MLSS=1500~2000mg/L, pH=7.12~8.86, DO=2.0~3.0mg/L, sludgeload=0.2~0.8kgCOD/(kgMLSS·d), the temperature is15~37℃, the effluentCOD<100mg/L, BOD<20mg/L, which is well fitted the standard of wastewaterdischarge, the result also show that CFASR has a high potential to reduce the TN、TP、SS and chroma, which can reach more than90%,80%,90%and80%,respectively.AS printing and dyeing wastewater has a high value of pH which up tomaximum of10,so the traditional anaerobic biological treatment reactor, such asUASB, utilized to treat printing and dying wastewater must adjust pH to theoptimum pH range which is7.5~8.0by addition sulfate to the system. The result ofthe pilot-scale demonstrate that ABR has potential to treat high influent pH, whichcan attainability at9.5, compare to the traditional anaerobic treatment process, ABRsaving a large number of pharmaceutical costs as there is no need to addition sulfateto adjust pH. In addition to, ABR occupied less land as it can steady operates at ashorter HRT (12h) compare to the traditional anaerobic treatment process (morethan20h).Using the GC-MS and LC-MS analytical tools to observe the removal oforganisms and dye molecules which attribute to the ABR. The result show that ABRreactor can well degrade the influent higher alkanes, mide acids, ketones, phenols,esters which are high in the influent, but low in the effluent. by analyzing theeffluent detect that most of macromolecular materials were transferred to smallermolecules, such as cycloalkanes, quinolines, phenols, which is beneficial to thefurther degradation in the follow-up aerobic processes. The pilot-scale experimentdetection found ABR has a high reduction of naphthol AS-E, azo-dye acid orange,direct blue, anthraquinone-acid blue, but no detection of the removal of azo sudan1. Establishing the mathematical model for the printing and dyeing wastewatertreatment based on the anaerobic digestion model No.1(ADM1) and activatedsludge model No.1(ASM1) which developed by the international water association(IWA), after being amended and improved,we establish model to provide a theoretical basis for the design, optimal operation, forecast and control the effluentwater quality of printing and dying wastewater which treated by ABR-CFASR. TheABR simulated results based on the ADM indicate that the predicted date of the firstcancellus of ABR is far from the true date, the error rate is-32.8%~30.6%, while thesimulation of the third and sixth cancellus is will fitted the real date, error rate is-20%~20%. Otherwise the model of ABR show a perfect simulation for VFA、MLVSS and pH. The CFASR simulated result which based on ASM1show that inunder the different HRT, simulated dates are well inosculation with the experimentaldates at a-14%～14%error rate,which demonstrate that the model can employed topredict the effluent system of CFASR. However the ADM-ASM1combined modelpredict the effluent COD with a-18%～19%error rate, which larger than thesimulated result of CFASR account for the deviation of parameters or the deviationas the ADM simulate the ABR effluent water quality.更多还原