应用化学 ›› 2011, Vol. 28 ›› Issue (05): 542-548.DOI: 10.3724/SP.J.1095.2011.00273

• 研究论文 • 上一篇    下一篇

水介质对有机硫化物形成影响的模拟实验

岳长涛1*,李术元1,徐明2,钟宁宁3   

  1. (1.中国石油大学重质油国家重点实验室 北京 102249;
    2.大庆油田有限责任公司新能源办公室 大庆;3.中国石油大学资源与信息学院 北京)
  • 收稿日期:2010-05-10 修回日期:2010-11-04 出版日期:2011-05-10 发布日期:2011-05-10
  • 通讯作者: 岳长涛,副教授; Tel:010-89733265; Fax:010-89733048; E-mail:yuect@cup.edu.cn; 研究方向:应用化学
  • 基金资助:
    国家自然科学基金(40702019)资助项目

The Effcet of Water on the Formation of Organic Sulfides from Petroleum in Simulated Experiments

YUE Changtao1*, LI Shuyuan1, XU Ming2, ZHONG Ningning3   

  1. (1.State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249;
    2.New Energy Office in Daqing Oilfield Co.,Ltd,Daqing;
    3.Faculty of Natural Resource and Information Technology,China University of Petroleum,Beijing)
  • Received:2010-05-10 Revised:2010-11-04 Published:2011-05-10 Online:2011-05-10

摘要:

利用高压釜反应装置在高温高压下开展了汽油-硫酸镁化学还原反应含水和无水体系的模拟实验,通过气相色谱仪、微库仑仪、毛细管气相色谱/脉冲火焰光度检测器、红外光谱仪及X射线衍射仪对气、油、固三相产物分别进行了分析并对动力学进行了解析,表明主要生成氧化镁、硫、焦炭、硫化氢、二氧化碳以及硫醇、硫醚和噻吩类等有机硫化物;随反应温度升高,反应体系中无机硫转化为有机硫的趋势增强,并主要生成热稳定性高的噻吩硫。 动力学解析表明,含水和无水条件硫酸镁转化反应的活化能分别为68.9和78.5 kJ/mol,证明水存在有利于无机硫向有机硫转化。

关键词: 有机硫化物, 汽油, 硫酸镁, 模拟实验, 水介质

Abstract:

To study on the formation mechanism of organic sulfides, simulated experiments for the reaction between gasoline and magnesium sulfate were carried out to study the effect of water on the formation of organic sulfides in petroleum. The products were analyzed by some advanced analytical methods including gas chromatography, microcoulometry, capillary gas chromatography combined with a pulsed flame photometric detector(GC-PFPD), FT-IR and X-ray diffraction. Moreover, the kinetics of the reactions between gasoline and magnesium sulfate were investigated. It is shown that solid magnesium sulfate could react with gasoline to produce magnesium oxide, hydrogen sulfide, coke, carbon dioxide, and organic sulfides as the main products. With the increase of reaction temperature, the oxidation effect of magnesium sulfate were enhanced, the average molecular mass of hydrocarbon components dropped and the overall trend of inorganic sulfur transformed into organic ones were enhanced in the system. With temperature growing, sulfur was prone to convert to thiophenes with higher thermal stability. According to the kinetic results, the conversion in hydrous system is high than that of anhydrous system. The apparent activation energies for hydrous system and anhydrous system are 68.9 kJ/mol and 78.5 kJ/mol, respectively.

Key words: organic sulfur compounds, gasoline, magnesium sulfate, simulation experiment, water

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