Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin
Separation and Characterization of Sulfur Compounds in Ultra-deep Formation Crude Oils from Tarim Basin
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塔里木盆地超深层原油中含硫化合物的分离与表征
DOI：
10.1021/acs.energyfuels.5b00897
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Shi Quan
中科院分区：
文献类型：
--
作者：
Wang Meng;Zhu Guangyou;Ren Limin;Liu Xuxia;Zhao Suoqi;Shi Quan
采用正离子电喷雾电离（ESI）傅立叶变换离子回旋共振质谱（FT-ICR MS）分析了塔里木盆地两种具有代表性的成熟度不同的深层原油（Ha 9，6598-6710 m; B1 C，6861-6944 m）中的硫化合物。通过甲基化/脱甲基化方法从原油中选择性地分离出高纯度和高回收率的噻吩类和硫化物，并通过气相色谱（GC）-硫化学发光检测器（SCD）和气相色谱-质谱（GC-MS）对其进行了详细的表征。两种原油的硫化物组成差异较大，与普通原油相比都具有独特性。在哈9原油中检测出了一系列具有高抗柴油加氢脱硫性能的有机硫化物1，1-二甲基六氢二苯并噻吩同系物。这是第一次在原油中发现这些生物标志物样化合物。在该原油的硫化物馏分中发现了结构异构体比已报道的原油多的噻二烃类化合物（1-3笼），以及各种可能由烷基硫化物衍生的无环硫化物，表明该原油具有不寻常的地质历史。选择性分离技术为原油中硫化物的地球化学研究提供了广阔的前景，包括对特定化合物的34 S和13 C分析。
Sulfur compounds in two representative deep crude oils (Ha9, 6598–6710 m; ZS1C, 6861–6944 m) with distinct levels of maturity from Tarim Basin, China, were analyzed by positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The thiophenic and sulfidic compounds were selectively separated from the crude oils with high purity and recovery by the methylation/demethylation approach and further characterized in detail by gas chromatography (GC) coupled with a sulfur chemiluminescence detector (SCD) and GC–mass spectrometry (MS). The two crude oils have a large difference in sulfur compound composition, which are both unique compared to common crude oils. A homologue series of 1,1-dimethylhexahydrodibenzothiophenes, which has been found as highly resistant organic sulfur compounds in diesel hydrodesulfurization, was detected in Ha9 crude oil. This is the first time that these biomarker-like compounds have been identified in crude oil. Thiadiamondoids (1–3 cages) with more structural isomers than reported oils as well as various acyclic sulfides, which probably derived from alkyl sulfides, were identified in the sulfidic fraction of the ZS1C crude oil, which indicates that the crude oil has an unusual geological history. The selective separation technique would offer broad prospects for geochemical research on sulfur compounds in crude oils, including their compound-specific34S and13C analyses.