Determination and indentification of oxygen-containing compounds in Longkou shale oil
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摘要: 用酸碱分离和萃取色谱分离相结合的方法将龙口页岩油分离为酸性组分、碱性组分和五个中性组分(饱和烃、芳香烃、含氮化合物、含氧化合物1、含氧化合物2)。采用GC-MS和负离子ESI FT-ICR MS鉴定了龙口页岩油中酸性组分、中性组分4和中性组分5中含氧化合物的组成。GC-MS分析结果表明,龙口页岩油酸性组分含氧化合物主要包括苯酚类、茚满酚类、萘酚类、联苯酚类、芴酚类、菲酚类,以及C5~16烷酸;龙口页岩油中性组分4和中性组分5中含氧化合物主要包括C9~32脂肪酮和酯类化合物。FT-ICR MS分析结果表明,龙口页岩油中含氧化合物主要有O1、O2、O3、N1O1、N1O2类化合物,其中,O1和O2类化合物种类较多。龙口页岩油重均相对分子质量集中在150~600 Da,说明龙口页岩油是由小分子化合物组成的。其表现出来的某些大分子化合物的性质,是由小分子化合物通过范德华力或氢键聚合在一起而形成的。龙口页岩油中O1、O2、O3类化合物中DBE主要分布在1和4,说明龙口页岩油中O1、O2、O3类化合物不饱和度和缩合度较低,因此,龙口页岩油是生物降解程度较低的油。Abstract: The methods of acid-base separation and extraction-chromatography were used to separate Longkou shale oil into acid fractions, basic fractions and five neutral fractions. The molecular structure and mass distribution of oxygen compounds in Longkou shale oil were investigated using gas chromatography-mass spectrometry (GC-MS) and negative-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The results of GC-MS show that the oxygen compounds in acid fractions involve phenols, indanols, naphthols, phenylphenols, fluorenols, phenanthrenols, and carboxylic acids ranging from C5 to C16. The oxygen compounds in neutral fraction 4 and 5 involve aliphatic ketones ranging from C9 to C32 and lipid compounds. The results of ESI FT-ICR MS show that the class species of O1, O2, O3, N1O1, N1O2 are found. The O1 and O2 have the higher ion intensity among the species in shale oil. The m/z range of shale oil is from 150 to 600. It is obviously that Longkou shale oil is mainly composed of small molecular compounds which are polymerized by Van der Waals force and hydrogen bonding. The properties of shale oil are similar to macromolecular compounds. Longkou shale oil has O1, O2, O3 compounds mainly with DBE of 1 and 4, suggesting that Longkou shale oil can be regarded as a less biodegraded oil.
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Key words:
- shale oil /
- oxygen compounds /
- GC-MS /
- FT-ICR MS
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