本文選題：原油 + 含硫多環(huán)芳烴��； 參考：《中國海洋大學(xué)》2015年博士論文

【摘要】：近年來,海上溢油事故頻發(fā),及時準(zhǔn)確確定海上溢油污染源具有非常重要的意義。對于溢油指標(biāo)的尋找及發(fā)展溢油鑒別新技術(shù)的研究一直是溢油鑒別領(lǐng)域的研究重點(diǎn)。本論文以我國海洋開采原油、進(jìn)口原油和燃料油典型油種為研究對象,采用氣相色譜-質(zhì)譜聯(lián)用分析技術(shù),建立了原油中高分子含硫多環(huán)芳烴、金剛烷的表征方法,綜合研究不同來源油樣品中組成及分布特征,提取能體現(xiàn)油種固有特征的新的標(biāo)志物,并通過室外風(fēng)化實(shí)驗(yàn)篩選出抗風(fēng)化、難降解并具有溯源性的特征生物標(biāo)志化合物。本研究可為發(fā)展海洋溢油檢測判別新技術(shù)以及提高溢油污染源判別的準(zhǔn)確度提供理論基礎(chǔ)和關(guān)鍵技術(shù)。得到的主要結(jié)果如下：(1)開展了微量固相萃取用于海面溢油鑒別快速前處理方法的研究。實(shí)驗(yàn)研究得到的原油微量固相萃取分離的適宜條件是：硅膠填料約20 mg,正己烷70μL洗脫下脂肪烴組分,90μL混合洗脫液(正己烷：二氯甲烷=1：1)洗脫下芳香烴組分。本方法的加標(biāo)回收率為80.74～112.5%,RSD為1.59%～6.32%。(2)采用氯化鈀/8-羥基喹啉硅膠配位交換色譜富集、提取油樣品中含硫多環(huán)芳烴,對不同來源油樣含硫多環(huán)芳烴指紋進(jìn)行了分析。結(jié)果表明,原油中含硫多環(huán)芳烴總含量在140.06μg/g～51422.88μg/g之間,二苯并噻吩總含量是苯并[b]萘[2,1-d]噻吩總含量1.5～9倍：不同來源的原油中含硫多環(huán)芳烴含量的分布規(guī)律是：沾化英雄灘渤海海區(qū)潿洲島海區(qū)進(jìn)口原油。燃料油中含硫多環(huán)芳烴總濃度分別為1416.44μg/g～5461.63μg/g,二苯并噻吩濃度是苯并[b]萘[2,1-d]噻吩濃度的2-6倍。(3)采用氣相色譜質(zhì)譜聯(lián)用技術(shù),建立了基于譜圖特征和保留指數(shù)的組分定性方法,采用內(nèi)標(biāo)法對油樣中26種金剛烷化合物進(jìn)行了定性定量分析。對不同來源海上油井平臺油樣中金剛烷指紋進(jìn)行了分析。結(jié)果表明,原油中金剛烷總含量在46.45～2085.39μg/g之間,除了沾化英雄灘原油外(雙金剛烷濃度是單金剛烷濃度2～3倍),各原油中單金剛烷的含量均占金剛烷總量的65%以上；同一海域不同采油平臺原油中金剛烷指紋分布特征相似,但含量差異很大,不同來源的原油中金剛烷化合物的分布特征及含量都存在很大的差異。燃料油中金剛烷總含量為23.37～652.57μg/g,不同來源的燃料油中金剛烷含量變化沒有明顯的規(guī)律,金剛烷指紋特征差異很大。(4)基于文獻(xiàn)報(bào)道定義了13個含硫多環(huán)芳烴及25個金剛烷診斷比值,所選比值在41個原油及6個燃料油樣品中分布比較分散(區(qū)分度較高),而且具有較高的診斷能力值,符合溢油鑒別指標(biāo)標(biāo)準(zhǔn)�；诤蚨喹h(huán)芳烴和金剛烷診斷比值兩種不同的變量進(jìn)行主成分分析,其分類的結(jié)果并不一致。將兩種生物標(biāo)志物指紋綜合為分類變量,對油品分類更為科學(xué)合理。含硫多環(huán)芳烴診斷比值是決定原油和燃料油分類的第一關(guān)鍵因素,金剛烷診斷比值是決定不同來源原油分類的關(guān)鍵因素。聚類分析可以將油品較合理地分為幾類,能反映不同來源油品間的親疏遠(yuǎn)近關(guān)系。(5)考察了渤海原油和燃料油在室外自然風(fēng)化條件下(0-100天)含硫多環(huán)芳烴和金剛烷的變化情況。結(jié)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對穩(wěn)定,苯并[b]萘[2,1-d]噻吩在短期風(fēng)化時間內(nèi)(0-45天),相對豐度較穩(wěn)定,但經(jīng)過100天較長期的風(fēng)化后,其相對豐度呈逐漸降低趨勢。13個含硫多環(huán)芳烴診斷比值在風(fēng)化60天內(nèi)基本穩(wěn)定,只有5個比值適用于風(fēng)化60-100天的油品的鑒定。單金剛烷在風(fēng)化過程中損失速率最快,雙金剛烷受風(fēng)化影響較小。經(jīng)過t檢驗(yàn)分析,9個金剛烷指標(biāo)在風(fēng)化20天內(nèi)保持穩(wěn)定,雙金剛烷指標(biāo)DMDI-4和DMDI-5在自然風(fēng)化100天內(nèi)具有較好的穩(wěn)定性,適合于長時間風(fēng)化條件下溢油的鑒別。
[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.
【學(xué)位授予單位】：中國海洋大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：X55

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