【作者】 宋国新；

【导师】 陈建民； 胡耀銘；

【作者基本信息】 复旦大学 ， 环境科学， 2012， 博士

【摘要】 本论文主要发展了气相色谱质谱联用技术对焦化废水及其在废水处理过程的不同阶段中的有机成分进行定性鉴别和定量测定研究。系统地研究了多种样品预处理和仪器分析手段并成功应用于焦化废水的有机物分析。主要内容如下：1)对于废水中的挥发性成分(Volatile organic compounds, VOCs),发展了吹扫捕集水样前处理技术,并结合气相色谱质谱联用技术进行了分析。在废水中一共定性检测出多种挥发性组分,包括二甲基锡、四甲基二锡、吡啶、苯、甲苯等,定量分析结果表明其含量范围为8.0μg/L-2.0mg/L。2)对于废水中的半挥发性成分(Semi-volatile organic compounds, SVOCs),发展和比较了液液萃取、大孔吸附树脂萃取、固相小柱萃取、自动固相盘萃取等样品前处理技术,系统研究了影响萃取效率的因素,分别建立了各种前处理方式的最佳实验参数和方案。利用液液萃取结合气相色谱质谱联用技术在原水中一共定性检测出超过250种半挥发性化合物,主要为苯酚类、苯胺类、联苯类、吲哚和喹啉等有毒有害物,半定量计算有机物含量的范围为1.0μg/L-100mg/L。研究了焦化废水中的有机污染物在水处理过程中的变化、迁移和降解及新的化合物的产生途径,结果表明A1/A2/O系统对于焦化废水的处理卓有成效,半挥发性有机污染物的降解率最高达到98.5%。比较了固相萃取小柱萃取方式和液液萃取对于焦化废水中的半挥发性有机物前处理的效果,结果表明,对于高浓度废水,固相萃取小柱的萃取能力和液液萃取法结果一致；对于低浓度的出水,其萃取所得的化合物种类和量都比液液萃取法要高10%-20%。研究了自动固相盘萃取仪对焦化废水的前处理新技术,对仪器和方法进行了改进,优化条件后取得的测定结果表明,自动固相盘萃取仪完全能够取代固相萃取小柱的功能,且具有工作量小、回收率高、自动化程度高的优势,在批量化检测方面有良好的应用前景。3)发展了固相微萃取技术和液相微萃取技术分析焦化废水中的有机物,首先发展了固相微萃取技术,实现同时对废水中的挥发性和半挥发性有机物进行富集、定性分析和定量分析。系统研究和优化了各种条件,发现在最佳条件下,对有机物的检出限低至0.1μg/L,在5μg/L-20mg/L范围内线性良好。固相微萃取技术大大简化了水样预处理步骤,具有检测限低,定量范围宽,环境友好、取样量少、无需有机溶剂、操作简单、快速等优点。接着我们发展了液液分散微萃取技术,并对废水中主要有机污染物及多环芳烃进行定性定量分析,在最佳条件下,各个目标化合物的富集倍数为300～900倍,取样量为5mL情况下检出限最低至0.01μg/L,液液分散微萃取的优势是检测限低,定量范围宽,操作简单、取样量少、试剂消耗少、时间消耗少等优点。更多还原

【Abstract】 This thesis mainly involved the qualitative and quantitative analysis of the organic components in the coking wastewater and the wastewater in the different stages of treatment process by gas chromatography-mass spectrometry. Several sample pretreatment methods were studied systematically and applied to the analysis of coking wastewater. The highlights were as following:1) The technology of Purge and Trap was applied in the testing of the volatile organic compounds(VOCs) in the coking wastewater.18kinds of volatile components were detected such as dimethyl selenide, tetramethyl diselenide, pyridine, benzene, toluene etc with the content ranged from8.0μg/L to1.2mg/L.2) The sample pretreatment methods such as liquid-liquid extraction, macroporous adsorption resin extraction, solid phase extraction, automatic solid-phase disk extraction were studied and compared to determined the semi-volatile organic compounds(SVOCs) in the coking wastewater. All the factors which would affect the extraction efficiency in each method were studied and optimized.By using liquid-liquid extraction coupled with gas chromatography mass spectrometry, more than250kinds of semi-volatile organic compounds were detected, mainly for phenols, anilines, biphenyls, indoles and quinolines and other toxic and harmful components, ranged of1.0μg/L-100mg/L by semi-quantitative calculation. The changes, migration, degradation and produce of organic pollutants in coking wastewater and the wastewater in the different stages of treatment process were studied. The results showed that the A1/A2/O system was effective to the treatment of coking wastewater and the degradation rates of semi-volatile organic compounds reached98.5%.Solid phase extraction was compared with the liquid-liquid extraction for the analysis of semi-volatile organic compounds in the coking wastewater. The results showed that, for the original wastewater, solid phase extraction was equal to liquid-liquid extraction; for low concentration outlet water, solid phase extraction performed better than liquid liquid extraction by acquiring10%-20%additional compounds in type and amount.Automated solid-phase disk extraction was studied for the pretreatment of coking wastewater. The apparatus and method was improved according to the real condition. After the optimization of the relative factors, the results showed that this method could completely replace the solid phase column extraction, and had the advantage of less workload, high recovery rate and good automatization. Automated solid-phase disk extraction had a good application prospect in batch detection.3) The microextration technology including solid phase microextraction and liquid phase microextraction were developed to the test of the organic compounds in coking wastewater. First, solid phase microextraction was developed to enrich volatile and semi-volatile organic compounds simultaneous in the wastewater. The qualitative analysis and quantitative analysis was reached by optimization of relative conditions. Under optimal conditions, the limit of detection was down to0.1μg/L, good linearity was got in the range of5μg/L-20mg/L. Solid phase microextraction greatly simplifies the sample pretreatment steps, has the advantage of low detection limit, long linearity range, environmental friendly, small sample size, solvent-free, quickness etc.Then we developd a liquid-liquid dispersion microextraction technique, and the qualitative and quantitative analysis of main organic pollutants and polycyclic aromatic hydrocarbons in the coking wastewater were carried out. Under optimal conditions, enrichment factors the target compounds ranged from300-900times, the limit of detection was0.01μg/L. liquid liquid dispersion microextraction had the advantage of lower limit of detection, wide quantitation range, simple operation, small sample size, less consumption of reagents, and less time consuming etc.更多还原