Determination of Structural Building Blocks in Heavy Petroleum Systems by Collision-Induced Dissociation Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

• Published in: Analytical chemistry (Washington) 2012-05, Vol.84 (10), p.4544-4551
• Main Authors: Qian, Kuangnan, Edwards, Kathleen E, Mennito, Anthony S, Freund, Howard, Saeger, Roland B, Hickey, Karl J, Francisco, Manny A, Yung, Cathleen, Chawla, Birbal, Wu, Chunping, Kushnerick, J. Douglas, Olmstead, William N
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Biological and medical sciences; Chemical reactions; Chemical synthesis; Chemistry; Classical genetics, quantitative genetics, hybrids; Exact sciences and technology; Fundamental and applied biological sciences. Psychology; Genetics of eukaryotes. Biological and molecular evolution; Methods, theories and miscellaneous; Molecular chemistry; Molecular weight; Petroleum
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac300544s

Collision-induced dissociation Fourier Transform ion cyclotron resonance mass spectrometry (CID-FTICR MS) was developed to determine structural building blocks in heavy petroleum systems. Model compounds with both single core and multicore configurations were synthesized to study the fragmentation pattern and response factors in the CID reactions. Dealkylation is found to be the most prevalent reaction pathway in the CID. Single core molecules exhibit primarily molecular weight reduction with no change in the total unsaturation of the molecule (or Z-number as in chemical formula C c H2c+Z N n S s O o VNi). On the other hand, molecules containing more than one aromatic core will decompose into the constituting single cores and consequently exhibit both molecular weight reduction and change in Z-numbers. Biaryl linkage, C1 linkage, and aromatic sulfide linkage cannot be broken down by CID with lab collision energy up to 50 eV while C2+ alkyl linkages can be easily broken. Naphthenic ring-openings were observed in CID, leading to formation of olefinic structures. Heavy petroleum systems, such as vacuum resid (VR) fractions, were characterized by the CID technology. Both single-core and multicore structures were found in VR. The latter is more prevalent in higher aromatic ring classes.