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研究生:吳素慧
研究生(外文):Suh-Huey Wu
論文名稱:油氣岩對比技術應用理論研究-分子內碳穩定同位素比值分析及甲菲異構化反應
論文名稱(外文):The studies of the oil/gas/rock correlations–Intramolecular carbon isotope ratio analysis and methylphenanthrene isomerization
指導教授:黃得時黃得時引用關係
指導教授(外文):Ded-Shih Huang
學位類別:博士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:90
中文關鍵詞:分子內異構化油氣岩對比甲菲同位素
外文關鍵詞:intramolecularisotopeoil/gas/rock correlationmethylphenanthreneisomerization
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在第一部分丙酮與異丙醇分子內碳同位素分佈研究中,我們運用氣相層析燃燒串聯同位素比值質譜儀(Gas Chromatography - Combution - Isotope Ratio Mass Spectrometer簡稱GC-C-IRMS)進行不同品牌的丙酮與異丙醇個別位置上碳的同位素組成分析。分析結果試驗性的將丙酮與異丙醇區分成兩個來源類型:一類為在 與 值上並無重要差異,源自觸媒煉製而得的丙烯;另一類則為在甲基位置上的比值相對於帶氧的碳之同位素比值為重,來自於蒸汽裂解之丙烯。分析結果同時說明甲基碳同位素含有較多重質碳同位素。此一結果也可應用於丙烷分子內碳穩定同位素的比值分析上。
在第二部分甲菲異構物水合熱裂的降解與異構化反應研究中,我們則以水合熱裂實驗模擬地層熱成熟度作用,將甲菲異構物於270-350oC條件下加熱,以探討石油地球化學中,以甲菲異構物相對濃度為主要依據的熱成熟度指標MPI1,在%Ro約為 1.35時出現反折點的因素,並探討甲菲異構化反應的反應機構。
在一系列甲菲異構物的水合熱裂實驗中,β-位置取代異構物之2-甲菲與3-甲菲的濃度相對於α-位置取代異構物1-甲菲與9-甲菲的濃度,會隨著熱裂溫度的增加而有逐漸上升的趨勢,此一現象在%Ro小於1.38時與MPI1的趨勢相當。然而於%Ro達到1.38以上時,甲菲脫甲基生成菲的反應有明顯增加的趨勢。此去甲基的反應導致β-位置取代異構物的濃度相對於α-位置取代異構物的濃度,會隨著溫度的上升反而有逐漸下降的趨勢,這顯示出我們的結果與文獻上的報導,即%Ro超過1.35時成熟度指標MPI1會出現反轉的現象是一致的。此一結果亦說明以甲菲異構物濃度作為成熟指標參數時,要避免涵蓋菲的濃度因素。
在水合熱裂實驗中也同時觀察到甲菲異構物異構化反應主要發生於熱成熟度%Ro值超過1.07時。當%Ro值介於1.20與1.53時,2-甲菲與9-甲菲二者之間出現高比例的互轉異構化現象,若為單純的分子間甲基轉移,則其他甲菲異構物也會有相同的異構化反應。因此2-甲菲與9-甲菲間的高轉換率,推測是經由分子內[1,5]移轉的重排反應的結果。
In part I, we report the analysis of the isotope compositions of individual carbon positions of commercial acetones and isopropanols using gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS). It has tentatively classified both acetones and isopropanols into two source types: those with no significant difference in δ13CMe and δ13CCO values are from refinery propylene; while other samples with less negative δ13CMe values than the corresponding δ13CCO values are from steam pyrolysis propylene. These results also suggest that the isotopic methyl-carbon in favor of the heavy isotope. This intramolecular stable carbon composition analysis technique is also applicable to propane.
In part II, a simulation of the chemical transformations of methylphenanthrenes in sediment was performed using hydrous pyrolysis technique. The results indicate that isomerization is not the primary cause of the change in the MPI1 index. Rather, the degradation reaction of methylphenanthrenes to phenanthrene is one of the most likely causes reversing the trend of the MPI1 index with increasing heating temperature. An unusual isomerization between 2-methylphenanthrene and 9-methylphenanthrene was also observed during the course of heating experiments. A plausible mechanism involving [1,5]-methyl shifts was proposed for this isomerization reaction.
中文摘要 i
英文摘要 iii
致 謝 v
表 目 錄 ix
圖 目 錄 x

第一部分 丙酮與異丙醇分子內碳同位素分佈研究 1
第一章 前言 2
第二章 實驗部分 8
一、樣品與藥品 8
二、儀器分析方法 9
﹙一﹚氣相層析純化分離 9
﹙二﹚燃燒成二氧化碳 11
﹙三﹚同位素比值質譜分析 11
三、異丙醇標準品的製備 11
四、丙酮與異丙醇的降解反應 12
﹙一﹚丙酮經碘仿反應生成醋酸 12
﹙二﹚異丙醇經鉻酸氧化與碘仿反應生成醋酸 13
﹙三﹚醋酸經還原反應生成乙醇 14
五、甲酸甲酯水解反應 15
﹙一﹚甲酸的生成 15
﹙二﹚甲酸還原成甲醇 16
六、同位素組成標記及計算 17
第三章 結果與討論 18
一、異丙醇標準樣品的碳同位素比值分析 19
二、丙酮與異丙醇樣品的碳同位素比值分析 20
三、丙酮與異丙醇樣品來源探討 22
四、在油氣對比應用探討 24
第四章 結論 28
第五章 參考文獻 29

第二部分 甲菲異構物水合熱裂-降解與異構化反應研 33
第一章 前言 34
一、背景 34
二、甲菲異構物的熱穩定度及生成速率 37
三、甲菲異構物為主的熱成熟度指標 39
第二章 實驗部分 42
一、甲菲異構物樣品 42
二、水合熱裂實驗 42
﹙一﹚熱成熟度模擬 42
﹙二﹚甲菲異構物的水合熱裂 42
三、儀器分析 43
﹙一﹚氣相層析分析 43
﹙二﹚氣相層析質譜分析 44
第三章 結果與討論 46
一、熱裂溫度與熱成熟度的對應分析 46
二、甲菲異構物水合熱裂 48
三、甲菲異構化與降解反應 50
﹙一﹚成熟度指標MPI1探討 50
﹙二﹚2-甲菲與9-甲菲間的異構化反應 51
第四章 結論 53
第五章 參考文獻 55

附 錄
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