辽河常压渣油中含氮化合物悬浮床加氢过程转化与分布规律研究

Conversion and distribution of nitrogen-containing compounds of Liaohe atmospheric residue in slurry-bed hydrocracking

  • 摘要: 采用傅里叶变换红外光谱(FT-IR)、气相色谱-质谱等手段,研究了辽河常压渣油中的含氮化合物在悬浮床加氢反应过程中的转化规律。研究表明,辽河常压渣油轻蜡油(350~400 ℃)中的碱性含氮化合物主要为喹啉类,还有一部分吡啶类及吖啶类,非碱性含氮化合物主要为C1~5咔唑和吲哚类。重蜡油(400~450 ℃)中含氮化合物主要是吖啶及吡啶类物质。辽河常压渣油加氢反应后的轻蜡油馏分中碱性含氮化合物主要是C1~7喹啉和苯并喹啉类物质,以及C1~2吖啶类物质,非碱性含氮化合物主要是C2、C3、C7-吲哚。在反应后的重蜡油馏分中含氮化合物主要为吖啶类和咔唑类物质。喹啉类物质在反应前后常压渣油馏分中的含量随着沸点升高而降低,且加氢反应后常渣中的喹啉类物质浓度高于加氢反应前。在悬浮床加氢反应过程中,含氮杂环化合物减少,部分非碱性含氮化合物向碱性含氮化合物转化。

     

    Abstract: The transformation of nitrogen-containing compounds of Liaohe Atmospheric Residue (LHAR) during slurry-bed hydrocracking was investigated using Fourier transform infrared spectroscopy (FT-IR) and gas chromatography-mass spectrometry (GC-MS). It was turned out that the major basic nitrogen containing compounds were quinoline in light VGO (350~400 ℃), while some part of pyridine and acridine existed as well. C1~5 carbazole and indole were dominating non-basic nitrogen containing compounds. For heavy VGO (400~450 ℃), the major nitrogen containing compounds were acridine and pyridine. After hydrogenation, the major basic nitrogen containing compounds of the light VGO became C1~7 quinoline, benzoquinoline, and C1~2 acridine, while the major non-basic nitrogen compounds were C2, C3 and C7 indole. For the heavy VGO, the major nitrogen containing compounds had become acridine and carbazole. The content of quinoline before and after the hydrogenation reaction in the atmospheric residue fraction decreased with the elevation of boiling point. In addition, after hydrogenation the concentration of quinoline in LHAR had become higher. During the slurry bed hydrocracking reaction, the nitrogen-containing heterocyclic compounds were reduced and part of the non-basic nitrogen containing compounds was converted to basic nitrogen containing compounds.

     

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