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摘要: 以四川广元岩沥青为研究对象，分离出不同性质的亚组分，通过元素分析、紫外可见光谱、高温气相色谱、高分辨率质谱等手段研究钒卟啉类化合物的分子组成，并与塔河稠油中的卟啉化合物进行对比。结果表明，岩沥青中含有大量的金属元素，钒元素含量高达3888 μg/g，检测到大量钒卟啉类化合物，以C28-C34初卟啉（ETIO）和脱氧叶红初卟啉（DPEP）为主；与塔河原油相比，DPEP具有明显的相对优势，说明尽管岩沥青具有很高的分子缩合度，但其地质热成熟度较低。青川岩沥青储量巨大、金属含量丰富，具有重要的潜在利用价值。Abstract: A gilsonite from Qingchuan (Sichuan province, China) was separated into several fractions and characterized by various techniques. The vanadyl porphyrins were determined by inductively coupled plasma optical emission spectrometer, ultraviolet-visible, high-temperature gas chromatography atomic emission detection, and positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results show that the gilsonite contains a large amount of metal elements, especially the vanadium content is as high as 3888 μg/g. A large number of vanadyl porphyrins are detected, in which the deoxophylloerythroetio porphyrins are the most abundant, indicating high molecular condensation but low thermal maturity. The huge reserves and high metal content imply important utilization value for this natural source.
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Key words:
- gilsonite /
- vanadium /
- porphyrins /
- high resolution mass spectrometry
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图 1 岩沥青饱和分、芳香分GC-MS总离子流图及饱和分提取离子流图
Figure 1 Total ion GC-MS chromatogram of the saturates and aromatics, and mass chromatogram of m/z 217 and m/z 191 for the saturates
图 2 岩沥青及其胶质、沥青质UV-vis光谱谱图
Figure 2 UV-vis spectra of the gilsonite and its resins and asphaltenes
图 3 岩沥青及其胶质、沥青质高温GC-AED谱图
Figure 3 High temperature GC-AED chromatograms of the gilsonite and its resins and asphaltenes
图 4 塔河稠油和岩沥青(+)ESI FT-ICR MS谱图
Figure 4 Positive-ion ESI FT-ICR mass spectra of Qingchuan gilsonite and Tahe heavy oil
图 5 塔河稠油和岩沥青中N4VO类化合物DBE与碳数分布图
Figure 5 Relative ion abundance plots (DBE versus carbon number) of N4VO of Qingchuan gilsonite and Tahe heavy oil from positive-ion ESI FTICR MS analysis
表 1 岩沥青中各元素含量
Table 1 Element content of the gilsonite
Element Ultimate analysis w/% H/C
(atomic ratio)w/(μg·g-1) C H O N S V Ni Fe Ti Content 81.82 7.81 2.72 2.27 4.06 1.14 3888 366 491 133 
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表 2 四组分收率及钒元素收率
Table 2 SARA composition and vanadium content in these fractions
Yield w/% V/(μg·g-1) V/% Saturates 0.82 - Aromatics 6.43 - Resins 9.35 1895 4.48 Asphaltenes 81.5 4642 95.5 Sum 98.1 100
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