反应条件对渣油加氢产物中碱性氮化物的影响

利用间歇式固定床反应器对大连混合渣油进行催化加氢反应，研究氢分压和剂油比对加氢液体产物中碱性氮化物分布及类型的影响；利用电喷雾傅里叶变换离子回旋共振质谱（ESI FT-ICR MS）对原料油及产物中的碱性氮化物进行表征。结果表明：反应前后渣油中N1（含1个N原子）类的碱性化合物占绝大比例，N1S1（含1个N、1个S原子）和O1（含1个O原子）类化合物的比例次之，其它类型的相对丰度均较低；随氢分压的增大，产物中大部分碱性氮化物类别的丰度有所下降，同时发生了加氢断侧链致使N1类化合物分子的碳数减少，分子尺寸变小；随剂油质量比的增大，杂原子的相对丰度减弱，分子饱和度减小，N1类化合物的等效双键数（DBE）分布没有显著变化（DBE为9~18）；但加氢反应的断链使得分子碳数明显变小为C20~C34；反应后产物中杂原子明显减少。

EFFECT OF REACTION CONDITIONS ON BASIC NITROGEN COMPOUND CONVERSION IN RESIDUE HYDROTREATING

Hydrotreating reactions of Dalian mixed residue were studied in an autoclave to investigate the effect of hydrogen pressure and catalyst-to-oil mass ratio on distribution and types of basic nitrogen compounds in the liquid product. The nitrogen compounds in product and raw material were characterized by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT - ICR MS). The results showed that N1 (one N atom) type alkaline compounds in the residue before and after the reaction account for most proportion, N1S1 (one N atom and one S atom) and O1 (one O atom) is next, the relative abundance of the other types are low. With increase of hydrogen pressure, most of the basic N species in product decrease. At the same time, hydrogenation breaks down the side chains of the compounds and makes the carbon number in N1 species reduce and molecular size become smaller. When catalyst-to-oil ratio increase, the relative abundance of most N compounds and molecular saturation decreases, the equivalent double bond (DBE) of N1 compounds has no significant change (DBE: 9 ~ 18) and the carbon numbers of Ni compounds decrease significantly.