镍和钒在塔河原油中存在状态的分析

Study on Existence of Nickel and Vanadium in Tahe Crude Oil

摘要: 塔河原油是典型的重质原油，密度大，粘度高，重金属Ni和V的含量多。本文采用四组分分析法、沥青质分离法、溶剂萃取法以及柱色谱分离法等研究了塔河原油中Ni和V的存在状态。实验结果表明，塔河原油中94.28%(wt.)的Ni和92.14%(wt.)的V都集中于沥青质和胶质中，而塔河原油中只有11.35%(wt.)的Ni和27.65%(wt.)的V是以金属卟啉的形态存在的，其余则是以复杂结构的非卟啉形态存在的，通过紫外–可见光光谱和质谱发现塔河原油中V卟啉主要以ETIO-VO存在，其次是DPEP-VO和Rhodo-VO。另外，塔河原油沥青质中40.91%(wt.)的Ni和43.85%(wt.)的V集中于芳香性更大的A1组分中，其余的Ni和V则集中于A2组分中，并推断A2组分包裹A1组分形成沥青质胶状物，而胶质、芳香烃和饱和烃依次包裹沥青质胶核形成了凝胶-溶胶形态的塔河原油，使得位于沥青质胶核的Ni和V难以被脱除。

Abstract: Tahe crude oil is catalogued into heavy crude oil with high density and viscosity, which contains much Ni and V. The present work studied the existence of Ni and V in Tahe crude oil by SARA, separation of asphaltene, extrac-tion and column chromatography. Experimental results indicate that, in Tahe crude oil, 94.28% of nickel and 92.14% of vanadium are concentrated in the asphaltene and resins, but 11.35% of nickel and 27.65% of vanadium exist as metal-loporphyrins, the rest exist as non-porphyrins. Meanwhile, most of vanadyl porphyrin are of the etioporphyrin (ETIO) type, with remaining fractions attributed to deoxophylloerythroetioporphyrin (DPEP) and benzo types. In addition, in the asphaltene, 40.91% of nickel and 43.85% of vanadium are concentrated in A1 that contains molecules having con-densed aromatic and naphthenic rings. It is proposed that A1 and A2 molecules form the asphaltene colloids in crude oil, where A1 is the colloidal core. Resins and aromatics as well as saturates entrapped asphaltenes in turn and formed gel-sol crude oil, which makes Ni and V difficult to remove in asphaltenes.