金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C.Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents.The decomposition effciency of different catalysts for this reaction depends on the nature of the metal oxide used,and Al2O3 supported La2O3 was found to be the most active one.Pe...     

沉积物中六氯苯对颤蚓(淡水单孔蚓)的毒性效应研究

以淡水底栖动物颤蚓(淡水单孔蚓)为受试生物,研究了沉积物中六氯苯(HCB)对淡水单孔蚓14 d和28 d的毒性效应.结果表明,沉积物中HCB对颤蚓致死效应较低,当HCB浓度为190 mg· kg-,连续暴露28 d时,致死率低于8％.但HCB对颤蚓具有较强的慢性毒性效应,当HCB浓度为190 mg·kg-1,连续暴露28 d时,身体自断率高达90％,并且随着浓度升高和暴露时间延长,颤蚓自断率明显增高.HCB对颤蚓自断14 d和28 d的EC50分别为＞190 mg·kg-1和97.1 mg· kg-1.HCB对颤蚓行为(运动和挖掘)产生明显抑制作用.随着HCB浓度增加和暴露时间延长,颤蚓运动强度减弱,并伴随摄食量减少与体重减轻现象.     

民用燃煤源中多环芳烃排放因子实测及其影响因素研究

民用燃煤是我国目前关注较多的多环芳烃(polycyclic aromatic hydrocarbons,PAHs)排放源.根据我国民用燃煤所涉及的煤种、燃烧方式和炉灶类型,利用全流稀释采样系统对5种不同成熟度的煤种,分别以散块煤和蜂窝煤形式在3种炉灶类型中燃烧产生的烟气进行了采样和分析,初步获取了我国民用燃煤烟气中PAHs排放因子(EFPAHs)的实测数据.结果表明,烟煤的EFPAHs在块煤燃烧方式下的变化范围为1.1～3.9 mg.kg-1,在蜂窝煤燃烧方式下的变化范围为2.5～21.1 mg.kg-1,无烟煤的EFPAHs在块煤与蜂窝煤燃烧方式下分别为0.2 mg.kg-1与0.6 mg.kg-1.在民用燃煤的EFPAHs的各种影响因素中,煤的地质成熟度起主导作用,不同成熟度煤种的EFPAHs差异幅度高达1～2个数量级.其次是燃烧形态(块煤/蜂窝煤),主要表现为同一种地质成熟度的煤在蜂窝煤燃烧方式下排放的PAHs比块煤高2～6倍.炉灶类型的影响最小.     

水中六氯苯的高级氧化降解机理及其动力学探讨

采用UV、O3、UV/O3高级氧化法对水中六氯苯(HCB)的降解效果及机理进行了研究.结果表明, UV本身对HCB的去除贡献率不大, HCB可被O3、UV/03快速降解,即UVHCB的降解,酸性条件有利于降解反应的进行,在pH=3, HCB=0.2 mg/L,反应40 min时, HCD的去除可达50%左右. O3单独作用以及UV/O3联合作用,对HCD的降解均满足准一级反应动力学规律,如果体系的pH值基本保持恒定,这一规律就更为明显.根据离子色谱(IC)、GC、GC-MS对六氯苯降解中间产物进行了测定,探讨了O3、UV/O3降解六氯苯的途径和机理.     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

Determination of PCDDs,PCDFs, PCBs and HCB emissions from the metallurgical sector in Poland

Background The aim of the project was to measure the actual emissions of PCDD/F, PCBs and HCB from 20 selected metallurgical installations in Poland, in order to update the national inventory of dioxin emission from metallurgical industry for developing a strategy for dioxins and furans emission abatement from the subject facilities (UNEP 2005). Methods Sampling methodology used in this work was developed at the Cracow University of Technology because of the complexity of simultaneous sampling and determining PCDFs, PCDDs, PCB and HCB. For the determination a GC-MS/MS system was used. Results and Discussion Results from the work indicate that the highest dioxins and PCB concentrations were recorded for iron ore sintering plants at 1.10–1.32 ng total¹ TEQ/Nm³ followed by aluminium scrap melting at 0.03–0.66 ng total TEQ/Nm³. The highest HCB concentrations at 613–1491 ng/Nm³ were also recorded for iron ore sintering plants, whereas at aluminium plants the HCB concentrations were in the range of only 10.1–22.7 ng/Nm³. Conclusions The above investigations indicate that secondary aluminium production is the most significant dioxins source, if calculated as emission factor values. However, iron ore sintering plants are operating at much higher production capacity, causing this process to become the major source of dioxins, PCB and HCB pollution to the atmosphere in Poland. Recommendations and Perspectives Based on the performed tests and the environmental reviews of selected plants several recommendations were formulated for the reduction of generation or of emission of these pollutants from iron ore sintering plants, electric arc furnace steel production processes, hot-blast furnace operations, secondary aluminium smelting and primary zinc production from zinc cathodes.     

点源排放六氯苯在多环境介质中的分布研究

研究了某化工厂排放的六氯苯在水体、沉积物、土壤和植物中的分布情况。测定了水体、沉积物、土壤、植物中的六氯苯、研究了影响六氯苯在各环境介质中分布特征的主要因素及六氯苯在环境介质中的归宿。     

污染土壤淋洗液中六氯苯的电化学法处理研究

采用电化学稳定性较好的钛基镀RuO2为阳极,以不锈钢板为阴极,对污染土壤淋洗液中的六氯苯进行电化学处理,研究了溶液初始pH值、HCB初始浓度、电解时间、电解质浓度、外加电压等因素对六氯苯处理效果的影响。所得最佳工艺条件为:用TX-100做增溶剂时,在HCB初始浓度300μg/L、溶液初始pH为3,电解质浓度为1%,外加电压为6V时,电解3hHCB去除率为60.3%。气相色谱分析表明:阴极还原脱氯是HCB电化学降解的主要途径,检出的降解产物有五氯苯、1,2,4,5-四氯苯和1,2,3,4-四氯苯。     

阴极材料对模拟土壤淋洗液中六氯苯电化学降解的影响

采用自制电解装置以RuO2/Ti为阳极,分别以锌网、不锈钢板、石墨和RuO2/Ti为阴极,对模拟土壤淋洗液中的HCB进行电化学处理,系统地研究了不同阴极材料对HCB降解效果的影响.HCB去除率由高到低依次为:锌网＞不锈钢板＞石墨＞RuO2/Ti.气相色谱分析表明:采用不同阴极材料对HCB进行电解时,其脱氯程度不同.