摘要：The transformation of nickel (Ni) porphyrins in hydrodemetallization (HDM) was investigated using 2,3,7,8,12,13,17,18-nickel-octaethylporphine (Ni-OEP) as the model compound, which was dissolved in a white oil. The HDM reactions were carried out in a high-pressure trickle-bed reactor over the oxidic and sulfided NiMo/Al2O3catalyst. The molecular formulas of Ni compounds in the feed and hydrotreated products were characterized by positive-ion electrospray ionization (+ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The hydrotreated products were separated into two subfractions by silica gel chromatography. Molecular structures of Ni-containing intermediates were investigated by ultraviolet-visible (UV-vis) spectrometry, hydrogen nuclear magnetic resonance (¹H NMR), and density function theory (DFT) calculations. The major Ni-containing intermediates of Ni-OEP were dihydrogenated (Ni-OEPH2) and tetrahydrogenated (Ni-OEPH4) porphyrins during the hydrotreating. The structure of Ni-OEPH2was speculated as 1,2-dihydro-Ni-OEPH2, which could be further hydrogenated into Ni-OEPH4. Ni-OEPH4was first detected in the Ni-OEP hydrotreated products, which should be much more unstable than Ni-OEPH2and could be easily demetallized. The main pathway of Ni-OEP conversion during the hydrotreating was the hydrodemetallization route, and Ni was removed with the porphyrin ring rapid fragmentation. The results indicate that the catalyst with high hydrogenation and hydrogenolysis activities on hydrocarbons as well as sulfur and nitrogen compounds could have a high activity on the HDM of Ni porphyrins.
© 2016 American Chemical Society.

ISSN号：0887-0624

卷、期、页：v 30,n 9,p6933-6941

发表日期：2016-09-15

影响因子：0.000000

收录情况：EI（工程索引）

发表期刊名称：Energy and Fuels

参与作者：李诗怡

通讯作者：鞠林青,刘亭亭,卢金成,丁思佳

第一作者：周亚松,魏强,张亚和,史权

论文类型：期刊论文

论文概要：鞠林青,刘亭亭,卢金成,周亚松,魏强,李诗怡,丁思佳,张亚和,史权，Transformation of Nickel Octaethylporphine in Hydrodemetallization Reactions，Energy and Fuels，2016，v 30,n 9,p6933-6941

论文题目：Transformation of Nickel Octaethylporphine in Hydrodemetallization Reactions