Petroleum analysis by atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry

To meet the more stringent environmental regulations, refineries are facing major challenges. Chapter 1 is a brief discussion of basic Ion Cyclotron Resonance (ICR) principles, Atmospheric Pressure PhotoIonization (APPI) pathways, instrumentation and data analysis.; In Chapter 2, I describe an APPI source coupled to the in-house-built 9.4 Tesla Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer at the National High Magnetic Field Laboratory (NHMFL) in Tallahassee, Florida. This chapter highlights the complexity of crude oil analysis with an APPI source. This report establishes the highest number of resolved (and assigned elemental formulas) spectral peaks (>12,000 peaks in a single mass spectrum and up to 63 peaks of the same nominal mass) in one mass spectrum.; In Chapter 3, I compare ESI and APPI data from the same crude oil and also pyridinic and pyrrolic nitrogen model compounds. The chapter defines instrument parameters which can cause fragmentation (loss of H2) and parameters which do not. ESI and APPI crude oil spectra yield the same elemental species, providing evidence that APPI can produce an ion population without fragmentation.; In Chapter 4, I investigate the proton transfer reaction for a Canadian bitumen petroleum in deuterated toluene (C7D8). Nitrogen class compounds are also analyzed in deuterated toluene. The dopant percent contribution to the even-electron ions (protonated and deuterated compounds) of the petroleum is ∼5%. The nitrogen model compounds exhibited a similar trend.; Petrochemical analysis commonly employs the saturates-aromatic-resins-asphaltenes (SARA) separation method. In Chapter 5, the sulfur containing compounds of a Middle East crude oil are speciated.; In Chapter 6, the derivatized and non-derivatized samples of a petroleum vacuum bottom residue (the highest boiling point fraction of petroleum and hence, the most complex heteroatom content) are analyzed by ESI and APPI. Significant differences in the double bond equivalent values between the ESI and APPI analyzed sulfur species are identified. Furthermore, this report provides data that probes APPI ionization efficiency.; Chapter 7 is a synopsis of the APPI technology applied to petroleum analysis. The chapter presents molecular speciation from intermediate stages of a hydroconversion process; a first step in hydroconversion catalytic technology improvement.; Appendix A describes the ongoing construction and adaptation of an ion cluster source to an existing FT-ICR mass spectrometer. The primary investigator is Professor Harry Kroto, Nobel prize laureate for the discovery of fullerenes. The research focuses on the formation of C28 by laser vaporization and gas phase reaction products in the ICR cell.; In appendix B, the reaction products of C60 and hydrogen at high temperature and pressure are resolved and identified. The product species formed at elevated temperature and hydrogen pressure are characterized by APPI FT-ICR mass spectrometry. Only the APPI analysis (and Field Desorption, FD) were accomplished at Florida State University and the first report (of three published reports) is presented. (Abstract shortened by UMI.)...