吴艳, 马博文, 钟金龙. 不同类型重油中碱性氮化合物分子组成及其加氢裂化转化规律[J]. 煤炭学报, 2019, (4). DOI: 10.13225/j.cnki.jccs.2018.0697
引用本文: 吴艳, 马博文, 钟金龙. 不同类型重油中碱性氮化合物分子组成及其加氢裂化转化规律[J]. 煤炭学报, 2019, (4). DOI: 10.13225/j.cnki.jccs.2018.0697
WU Yan, MA Bowen, ZHONG Jinlong. Composition analysis of basic nitrogen compounds in different heavy oils[J]. Journal of China Coal Society, 2019, (4). DOI: 10.13225/j.cnki.jccs.2018.0697
Citation: WU Yan, MA Bowen, ZHONG Jinlong. Composition analysis of basic nitrogen compounds in different heavy oils[J]. Journal of China Coal Society, 2019, (4). DOI: 10.13225/j.cnki.jccs.2018.0697

不同类型重油中碱性氮化合物分子组成及其加氢裂化转化规律

Composition analysis of basic nitrogen compounds in different heavy oils

  • 摘要: 为获得分子水平上不同类型重油碱性氮化合物结构组成,采用超高分辨率的傅里叶变换离子回旋共振质谱(ESI FT-ICR MS)等分析手段,对高温煤焦油沥青、石油常压渣油及其悬浮床加氢裂化>500 ℃尾油这4种不同类型的重油进行表征,获得原料及加氢产物的分子组成,揭示碱性氮化合物在加氢过程中的转化规律。研究结果表明,高温焦油沥青中N1类碱性氮化合物主要是二苯并喹啉和三苯并喹啉类化合物,N2类化合物主要是三苯并吡啶吡咯和四苯并吡啶吡咯类化合物。渣油中N1类碱性氮化合物呈现出从喹啉、苯并喹啉至四苯并喹啉类化合物的连续分布状态,N2类化合物主要是苯并吡啶吡咯、二苯并吡啶吡咯类化合物。渣油中N1和N2类化合物的平均缩合度低于高温焦油沥青,但其碳数重心远高于高温焦油沥青,渣油中存在相当一部分高缩合度、长侧链的喹啉类、吡啶吡咯类大分子化合物,这部分物质是渣油中最重质、最难转化的大分子结构之一。加氢裂化过程中,高温焦油沥青中碱性N1类化合物主要发生加氢饱和及烷基侧链断裂反应,N2类化合物缩合度整体下降。渣油加氢尾油中N1类和N2类化合物DBE和碳数重心明显变窄。渣油加氢尾油中难以加氢转化的高缩合度、大分子量的碱性氮化合物较多,据此可推测,其加氢裂化性能低于高温焦油沥青加氢尾油,二次加工过程中会更易于结焦。

     

    Abstract: To obtain the structural composition of basic nitrogen compounds in heavy oils at the molecular level,four heavy oils,i. e. high temperature coal tar pitch,petroleum atmospheric residue and their suspension bed hydrocrackin500 ℃ tail oil,were characterized by ultra-high resolution Fourier transform ion cyclotron resonance mass spectrome- try (ESI FT-ICR MS) and other analysis methods. The molecular compositions of the four samples were obtained,and the conversion law of basic nitrogen compounds in the hydrogenation process was revealed. The results showed that N1 basic nitrogen compounds in high temperature tar pitch were mainly dibenzoquinoline and triphenylquinoline compounds,and N2 compounds were mainly triphenylpyridinium pyrrole and tetraphenylpyridinium pyrrole compounds. N1 compounds in residual oil showed a continuous distribution state from quinoline,benzoquinoline to tetrabenzoquinoline compounds,and N2 compounds were mainly benzopyridine pyrrole and dibenzopyridine pyrrole compounds. The aver- age condensation degree of N1 and N2 compounds in residual oil were lower than that of high-temperature tar pitch, but their carbon number center of gravity were much higher than that of high-temperature tar pitch. There were quite a number of quinoline and pyridine pyrrole macromolecules with high condensation degree and long side chains in resid- ual oil,which were the most difficult to convert macromolecules in residual oil. During hydrocracking,basic N1 com- pounds in high temperature tar pitch mainly undergo hydrogenation saturation and alkyl side chain cleavage reactions, and the condensation degree of N2 compounds decreases as a whole. The DBE and carbon number of N1 and N2 com- pounds in residue hydrotreating tail oil were obviously narrowed. There were many basic nitrogen compounds with high condensation degree and large molecular weight that were difficult to be hydroconverted in residue hydrotreated tail oil. Therefore,it could be inferred that its hydrocracking performance was lower than that of high temperature tar pitch hydrotreated tail oil,and coking would be easier during secondary processing.

     

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