Characterization of heavy petroleum fraction by positive-ion electrospray ionization FT-ICR mass spectrometry and collision induced dissociation: Bond dissociation behavior and aromatic ring architecture of basic nitrogen compounds

LinZhou Zhang, Yahe Zhang, Suoqi Zhao, Chunming Xu, Keng H. Chung & Quan Shi^*

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

^*Corresponding Author: E-mail: sq@cup.edu.cn; Tel: +86 010 89739157

DOI: 10.1007/s11426-013-4899-4

Keywords: FT-ICR MS; CID; heavy oil; molecular structure

Abstract: This paper examined the bond dissociation behavior and aromatic ring architecture of basic nitrogen compounds in Sudan heavy petroleum fraction. Both broadband and quadrupole isolation modes positive-ion electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with collision induced dissociation (CID) techniques were used to characterize a low sulfur crude oil derived vacuum residuum (VR). The appropriate CID operating condition was selected by comparing the molecular weight distributions of the basic nitrogen compounds under various CID operating conditions. Both odd- and even-electron fragment ions were observed from the mass spectrum, indicating that the heterolytic and homolytic bond cleavages occurred simultaneously during the CID process. The odd-electron fragment ions were predominant in each class species, indicating preferential heterolytic bond cleavages. At the optimal CID condition, the alkyl groups decomposed deeply and just left the aromatic cores of the nitrogen compounds. No significant variation in double bond equivalent (DBE) value was observed between the fragment and parent ions, revealing that the domination of single core structure.