【作者】 赵俊杰；

【导师】 祁佩时；

【作者基本信息】 哈尔滨工业大学 ， 环境科学与工程， 2013， 博士

【摘要】 随着工业废水二级处理设施的建设和运行，水中大量的污染物被去除，但是，随之而来的是难生物降解有机物问题日趋突出，直接影响着水质安全，对人体健康产生危害。抗生素制药行业尤其是发酵类制药是排放难降解污染物的主要行业之一，具有量大面广的特点，对该废水进行深度处理已成为人们关注的热点问题。本研究通过对比分析，选择了臭氧复合催化体系处理难降解污染物的研究，提出的复合改性颗粒活性炭和过氧化氢共同作用的O₃/GAC/H₂O₂复合工艺，对生化处理出水中难降解有机物具有较好的降解效果，充实了臭氧催化氧化处理难降解有机物的理论知识，为开展工业废水中难降解有机物的深度处理提供了技术支持。本研究采用气相色谱质谱（GC-MS）分析了抗生素废水生化处理出水（BTE）中存在的难降解有机物，其中酯类化合物和芳香烃类化合物种类最多。利用高效液相色谱（HPLC）分析得到环境内分泌干扰物邻苯二甲酸二丁酯（DBP）在废水中含量最高。根据理论化学需氧量ThOD和化学需氧量COD的相关关系，评价了废水中难降解有机物对污染的贡献程度，发现邻苯二甲酸二丁酯和邻苯二甲酸二异辛酯对废水污染贡献最大，为典型特征污染物。O₃/GAC/H₂O₂复合工艺由臭氧联合氨化改性颗粒活性炭和过氧化氢复合构成。经比表面积（BET）和扫描电子显微镜（SEM）、傅里叶变换红外（FTIR）和X射线衍射（XRD）分析发现，改性颗粒活性炭比表面积为1010m2/g，具有复杂的管状结构，表面碱性基团浓度为9.83410-6mol/m2，可有效促进臭氧催化氧化效果。O₃/GAC/H₂O₂复合工艺对DBP具有较好的降解效果，DBP降解效率随着臭氧投加浓度、臭氧投加速率、初始pH、反应温度、改性活性炭投加量的升高而增加，呈现正相关性，随着过氧化氢投加量的升高呈现先增加后降低的趋势。氧化剂的连续或多次投加方式有利于提高DBP的去除效率。O₃/GAC/H₂O₂复合工艺中DBP降解符合二级反应动力学过程。DBP的表观降解反应速率常数kapp随着臭氧投加浓度、初始pH、反应温度和改性活性炭投加量的增加而提高，随着过氧化氢投加量呈现先增长后降低的相关关系。初始pH对kapp影响最大，改性颗粒活性炭投加量的影响最小。通过多元线性回归分析，建立了O₃/GAC/H₂O₂复合工艺处理DBP的二级表观降解反应动力学模型：dC_DBP/dt=k_appC_DBP²=1.2317×10^-8[O₃]^0.7413[H₂O₂]^0.8935[pH]^1.1069[T]^0.8090[GAC]^0.3753 C_DBP²O₃/GAC/H₂O₂复合工艺催化氧化DBP的体系中臭氧的液相扩散速率DO3为6.0010^-10m²/s，Henry系数He为11261.28Pa mol/L，臭氧的液相传质系数kL为2.4010^-5m/s， kLa=8.8210^-4s^-1。氧化体系的Hatta为0.04<Ha<0.10，反应因子E=1，整体反应处于慢速动力学体系，由臭氧与羟基自由基共同作用于DBP的降解过程。对DBP的降解中间产物进行固相萃取的GC-MS分析，提出了DBP在氧化体系中的降解途径，认为DBP在臭氧复合催化氧化体系中经历了同分异构化反应、酯类取代基的亲电取代降解、亲电基团的取代反应、芳香环的羟基化、芳香环的开环等反应过程并生成了大量的中间产物，然后经过芳香环的羟基化和开环作用进一步生成简单的羧酸物质并得以完全矿化。O₃/GAC/H₂O₂复合工艺可有效氧化抗生素废水二级出水中难降解有机污染物，有机物中间产物种类呈现先增加后降低的趋势。芳香烃类、酯类物质被大幅度降解，中间产物以酸酐、羧酸、酮类、酚类、醇类等污染物为主。废水中大分子有机物被氧化成小分子有机物。通过分析不同氧化阶段废水中有机物的化学结构特点，结合废水处理的COD和TOC污染指标，采用有机物碳的平均氧化数建立了臭氧复合催化氧化处理难降解有机物的评价方法。在实验条件下，废水中有机物碳形成更高比例的碳氧键，碳的平均氧化数MOC从-1.58提高到-0.13。废水可生化性被有效改善，可生化性能指标BOD₅/COD比值从0.11提高到0.78，有利于后续的稳定化生态处理。更多还原

【Abstract】 With the construction and operation of industrial wastewater secondarytreatment facilities, most of the pollutants in wastewater are degraded. However,the concern on the corresponding problem of refractory organics contaminationincreases significantly. The refractory organics could affect the safety of waterresource and damage the health of human. The advanced treatment of wastewaterfrom antibiotic pharmaceutical industries, especially from fermentationpharmaceutical plants as one of the most seriously polluting industries has beenthe concern focus. By comparation, the catalytical ozone oxidation technologywas chosen to oxidize the non-biodegradable organics. The catalytical ozonationtechnology （O₃/GAC/H₂O₂） composited by modified granular activated carbonwith hydrogen peroxide was proposed in this study, while it can degrade therefractory organics in biologically treated effluent significantly. It can enrich thetheory of catalytical ozone oxidation about refractory organics and providetechnical support for advanced treatment of them in industry wastewater.The refractory organics in antibiotic pharmaceutical biologically treatedeffluent （BTE） were analyzed by Gas Chromatograph-Mass Spectrum （GC-MS）analysis. The highest amounts of organics were esters and aromatic hydrocarbonsin wastewater. According to High Performance Liquid Chromatography （HPLC）analysis, the dibutyl phthalate as one typical kind of Endocrine DisruptingChemicals （EDC） was the main pollutant in wastewater. Based on therelationship of Chemical Oxygen Demand （COD） and Theoretical OxygenDemand （ThOD）, the contributions of different organics to COD was evaluated,while the dibutyl phthalate and bis（2-ethylhexyl） phthalate were determined asthe typical pollutants because of their most contributions to COD in effluent.The O₃/GAC/H₂O₂technology was composited by ozone, modified GACand hydrogen peroxide. According to the analysis of BET, Scanning ElectronicMicroscope （SEM）, Fourier Transform Infrared Spectroscopy （FTIR） and X-raydiffraction （XRD）, the high specific surface area of1010m2/g and theconcentration of surface basic groups of9.83410-6mol/m2were determined,while the complex tubular structures were found with amorphous carbon status in the modified GAC.The significant effect for DBP degradation was found by compositedprocess of O₃/GAC/H₂O₂. The positive effects of factors of ozone concentration,gas flow rate, initial pH, reaction temperature and modified GAC dosage for DBPdegradation were investigated, respectively. The degradation efficiency increasedfirst, then decreased along with the increase of H2O2dosage. With the samedosage of applied ozone and H2O2, the multiple steps addition showed the higherdegradation efficiency than that obtained by adding within one step before thestart of the experiment.The degradation process of DBP in the catalytical ozone systemO₃/GAC/H₂O₂was investigated to follow a second-order kinetic model. Theeffects of influencing factors, ie. ozone concentration, gas flow rate, H2O2dosage,initial pH, reaction temperature and modified GAC dosage, on the apparentreaction rate constant kappwere evaluated in the study. The positive correlationrelationships of kappwith influencing factors above were investigated, while thekappincreased first, then decreased along with the increase of H2O2dosage. Bycomparison analysis the initial pH was found to have greatest influence on thekappwith moderate influence of H2O2dosage and ozone concentration. However,the GAC dosage has the lowest influence on kapp.By means of multiple linearregression fitting, the kinetic practical equation of second-order apparent kineticsabout DBP degradation was determined as follows:dC_DBP/dt=k_appC_DBP²=1.2317×10^-8[O₃]^0.7413[H₂O₂]^0.8935[pH]^1.1069[T]^0.8090[GAC]^0.3753 C_DBP²In view of the kinetic theory of ozone consumption, the diffusion coefficientDO3, the Henry coefficient He and the liquid phase mass transfer coefficient kL,kLa of ozone in DBP oxidation system were determined as6.0010⁽-100m²/s,11261.28Pa mol/L,2.4010^-5m/s and8.8210^-4s^-1，respectively. The Hattanumber Ha was calculated in the range of0.04to0.1, and the reaction factor Ewas1, which indicated that the catalytical ozonation was in low kinetic regime.The organic pollutants were degraded by competitive oxidations of ozone-directreactions with ozone-indirect reactions, ie. reactions with hydroxyl radicals.Many intermediate products of organics during catalytical ozonation wereidentified by GC-MS using of solid phase extraction. The oxidation pathway of DBP in system was investigated that the DBP was oxidated by series reactions ofisomerization, electrophilic substitution, the hydroxylation and opening ofaromatic rings. Many intermidate compounds were produced and then furtheroxidized by hydroxylation and opening of aromatic rings to short chain aliphaticacids, such as acetic acid, oxalic acid, malonic acid and so on. The aliphatic acidswere finally mineralized completely.The refractory organics existing in biologically treated effluent of antibioticpharmaceutical wastewater were effectively oxidized by composited ozoneheterogeneous catalytical oxidation （O₃/GAC/H₂O₂）. The kinds of organics inwastewater increased first and then decreased during oxidation process. Aromatichydrocarbons and esters were degraded substantially to form by-products of acidanhydrides, carboxylic acids, ketones, phenols, alcohols compounds.Macromolecular organics were oxidized to micromolecular ones during reactions.By the analysis of organic characters at different oxidation status, the evaluationmethodology for organics degradation by ozone catalytical oxidation wasestablished by use of the Mean Oxidation Number of Carbon （MOC）, which wascalculated by COD and TOC indexes. Under the oxidation condition in this study,the more carbon-oxygen bonds were formed in organics, so that the MOC oforganic pollutants was increased from-1.58to-0.13. The biodegradability ofwastewater was improved obviously with the indicator index of BOD₅/CODincreasing from0.11to0.78, which was suitable for following stabilizationbiological treatments.更多还原