以含硫多环芳烃和金刚烷为标志物的海洋溢油鉴别新方法研究

发布时间：2018-06-19 07:22

本文选题：原油 + 含硫多环芳烃　；参考：《中国海洋大学》2015年博士论文

【摘要】：近年来,海上溢油事故频发,及时准确确定海上溢油污染源具有非常重要的意义。对于溢油指标的寻找及发展溢油鉴别新技术的研究一直是溢油鉴别领域的研究重点。本论文以我国海洋开采原油、进口原油和燃料油典型油种为研究对象,采用气相色谱-质谱联用分析技术,建立了原油中高分子含硫多环芳烃、金刚烷的表征方法,综合研究不同来源油样品中组成及分布特征,提取能体现油种固有特征的新的标志物,并通过室外风化实验筛选出抗风化、难降解并具有溯源性的特征生物标志化合物。本研究可为发展海洋溢油检测判别新技术以及提高溢油污染源判别的准确度提供理论基础和关键技术。得到的主要结果如下：(1)开展了微量固相萃取用于海面溢油鉴别快速前处理方法的研究。实验研究得到的原油微量固相萃取分离的适宜条件是：硅胶填料约20 mg,正己烷70μL洗脱下脂肪烃组分,90μL混合洗脱液(正己烷：二氯甲烷=1：1)洗脱下芳香烃组分。本方法的加标回收率为80.74～112.5%,RSD为1.59%～6.32%。(2)采用氯化钯/8-羟基喹啉硅胶配位交换色谱富集、提取油样品中含硫多环芳烃,对不同来源油样含硫多环芳烃指纹进行了分析。结果表明,原油中含硫多环芳烃总含量在140.06μg/g～51422.88μg/g之间,二苯并噻吩总含量是苯并[b]萘[2,1-d]噻吩总含量1.5～9倍：不同来源的原油中含硫多环芳烃含量的分布规律是：沾化英雄滩渤海海区涠洲岛海区进口原油。燃料油中含硫多环芳烃总浓度分别为1416.44μg/g～5461.63μg/g,二苯并噻吩浓度是苯并[b]萘[2,1-d]噻吩浓度的2-6倍。(3)采用气相色谱质谱联用技术,建立了基于谱图特征和保留指数的组分定性方法,采用内标法对油样中26种金刚烷化合物进行了定性定量分析。对不同来源海上油井平台油样中金刚烷指纹进行了分析。结果表明,原油中金刚烷总含量在46.45～2085.39μg/g之间,除了沾化英雄滩原油外(双金刚烷浓度是单金刚烷浓度2～3倍),各原油中单金刚烷的含量均占金刚烷总量的65%以上；同一海域不同采油平台原油中金刚烷指纹分布特征相似,但含量差异很大,不同来源的原油中金刚烷化合物的分布特征及含量都存在很大的差异。燃料油中金刚烷总含量为23.37～652.57μg/g,不同来源的燃料油中金刚烷含量变化没有明显的规律,金刚烷指纹特征差异很大。(4)基于文献报道定义了13个含硫多环芳烃及25个金刚烷诊断比值,所选比值在41个原油及6个燃料油样品中分布比较分散(区分度较高),而且具有较高的诊断能力值,符合溢油鉴别指标标准。基于含硫多环芳烃和金刚烷诊断比值两种不同的变量进行主成分分析,其分类的结果并不一致。将两种生物标志物指纹综合为分类变量,对油品分类更为科学合理。含硫多环芳烃诊断比值是决定原油和燃料油分类的第一关键因素,金刚烷诊断比值是决定不同来源原油分类的关键因素。聚类分析可以将油品较合理地分为几类,能反映不同来源油品间的亲疏远近关系。(5)考察了渤海原油和燃料油在室外自然风化条件下(0-100天)含硫多环芳烃和金刚烷的变化情况。结果表明：渤海原油和燃料油中二苯并噻吩的分布特征保持相对稳定,苯并[b]萘[2,1-d]噻吩在短期风化时间内(0-45天),相对丰度较稳定,但经过100天较长期的风化后,其相对丰度呈逐渐降低趋势。13个含硫多环芳烃诊断比值在风化60天内基本稳定,只有5个比值适用于风化60-100天的油品的鉴定。单金刚烷在风化过程中损失速率最快,双金刚烷受风化影响较小。经过t检验分析,9个金刚烷指标在风化20天内保持稳定,双金刚烷指标DMDI-4和DMDI-5在自然风化100天内具有较好的稳定性,适合于长时间风化条件下溢油的鉴别。
[Abstract]:In recent years, oil spill accidents are frequent, it is of great significance to determine the source of the oil spill in time and accurately. The research on the search for the oil spill index and the development of the new technology for the identification of spilled oil have always been the key points in the field of oil spill identification. This paper is based on the research object of the typical oil of China's offshore oil exploitation, imported crude oil and fuel oil. By using gas chromatography-mass spectrometry (GC-MS) analysis technique, the characterization method of polycyclic aromatic polycyclic aromatic hydrocarbons (polycyclic aromatic hydrocarbons) and adamantane in crude oil is established. The composition and distribution characteristics of oil samples from different sources are synthetically studied, and the new markers can be extracted to reflect the inherent characteristics of the oil, and the weathering resistance, hard degradation and traceability are screened out through the outdoor weathering experiment. This study provides a theoretical basis and key technology for the development of new technology for detecting marine oil spill detection and the accuracy of improving the discrimination of oil spill sources. The main results are as follows: (1) the study of rapid pre treatment for identification of oil spillage by micro solid phase extraction was carried out. The suitable conditions for the separation of crude oil by micro solid phase extraction are: the silicone filler is about 20 mg, the fatty hydrocarbon components are eluted with hexane 70 u L, and the 90 u L mixed eluent (n-hexane: methylene chloride =1:1) is eluted with aromatic hydrocarbon components. The recovery rate of this method is 80.74 ~ 112.5%, and RSD is 1.59% to 6.32%. (2) using the palladium chloride /8- hydroxyquinoline silica gel. The content of polycyclic aromatic hydrocarbons in oil samples from different sources was analyzed by the enrichment of sulfur polycyclic aromatic hydrocarbons in oil samples. The results showed that the total content of sulfur polycyclic aromatic hydrocarbons in the crude oil was between 140.06 and 51422.88 mu g/g, and the total content of two benzothiophene was 1.5 to 9 times the total content of benzothiophene [the total content of 2,1-d] thiophene]: the original of different sources. The distribution law of the content of polycyclic aromatic hydrocarbons in the oil is: the crude oil is imported from the Weizhou Island sea area of the Bohai sea area of Zhanhua hero beach. The total concentration of polycyclic aromatic hydrocarbons in the fuel oil is 1416.44 to 5461.63 g/g, respectively, and the concentration of two benzothiophene is 2-6 times of the concentration of benzo [b] naphthalene [2,1-d] thiophene. (3) the basis of gas chromatography-mass spectrometry is established. The qualitative and quantitative analysis of 26 kinds of adamantane compounds in oil samples were carried out by internal standard method. The results showed that the total content of adamantane in oil samples from offshore oil well platforms in different sources was between 46.45 and 2085.39 mu g/g, except for Zhanhua hero shoal. The content of monamadane in all crude oil accounts for more than 65% of the total amount of adamantane in the crude oil, and the distribution characteristics and content of adamantane compounds in the crude oil from different sources are very different, and the distribution characteristics and content of the adamantane compounds in different sources are very different. The total content of adamantane in fuel oil is 23.37 ~ 652.57 mu g/g, and there is no obvious change in the content of adamanes in fuel oil from different sources. (4) the diagnostic ratio of 13 sulfur polycyclic aromatic hydrocarbons and 25 adamantane is defined based on the literature report, and the selected ratio is 41 crude oil and 6 fuel oil samples. The distribution of the products is relatively dispersed (higher differentiation), and has a high diagnostic value, which conforms to the standard of the oil spill identification index. Based on the two different variables of the sulfur polycyclic aromatic hydrocarbon and the diagnostic ratio of the adamantane, the results of the classification are not consistent. The fingerprint of the two species of biomarkers is classified as the classification variable and the oil classification is classified. It is more scientific and reasonable. The diagnostic ratio of sulfur containing polycyclic aromatic hydrocarbons is the first key factor in determining the classification of crude oil and fuel oil. The Jin Gang alkane diagnostic ratio is the key factor in determining the classification of crude oil from different sources. The cluster analysis can be divided into several kinds, which can reflect the close relationship between oil products of different sources. (5) investigation of the original Bohai original The change of polycyclic aromatic hydrocarbons and adamantane in oil and fuel oil under outdoor natural weathering conditions (0-100 days). The results show that the distribution of two benzo thiophene in Bohai crude oil and fuel oil remains relatively stable, and the benzo [b] naphthalene [2,1-d] thiophene is stable in the short period of weathering (0-45 days), and the relative abundance is more stable, but after 100 days After weathering, the relative abundance of.13 is gradually decreasing. The diagnostic ratio of sulfur polycyclic aromatic hydrocarbons is basically stable within 60 days of weathering. Only 5 ratios are suitable for the identification of oil products of 60-100 days weathering. The loss rate of monamadane in the process of weathering is the fastest, and the ringing of the adamantane is smaller. After t test analysis, 9 adamantane indexes are The weathering is stable for 20 days. The BIS adamantane index DMDI-4 and DMDI-5 have good stability within 100 days of natural weathering, which is suitable for the identification of spilled oil under long weathering conditions.
【学位授予单位】：中国海洋大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：X55

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