Heat-Exchanger Deposits in an Inverted Steam-Assisted Gravity Drainage Operation. Part 2. Organic Acid Analysis by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Abstract

As a complement to the bulk analyses presented in part 1 (Jennings, D. W.; Shaikh, A. Energy Fuels 2007, 21, 176-184), we report detailed compositional analysis of the organic acids from heat-exchanger deposits and produced water from an inverted steam-assisted gravity drainage (SAGD) bitumen production process. The current analyses were performed by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [(-) ESI FT-ICR MS] and reveal distributions of molecular weight, heteroatom content, aromaticity, and carbon number for several thousand organic acids in each sample. High mass accuracy combined with Kendrick mass defect analysis allows for assignment of a unique elemental composition, C c H h N n O o S s , to each mass spectral peak. Three-dimensional mass spectral images generated from the molecular formulas reveal compositional differences that may be rationalized on the basis of sample processing. In particular, we report lower overall heteroatom content, higher average carbon number, and lower aromaticity for early stage deposits and the produced bitumen compared to later stage samples that show increased water solubility. Little was previously known about those species other than the presence of organic acid/acid salt functionality. Moreover, we report the first in Vacuo isolation and tandem mass spectrometry of individual components of petroleum mixtures. Tandem mass spectrometry by infrared multiphoton dissociation of trapped ions indicates dicarboxylic acid structures for predominant C c H h O 4 and dicarboxylic acid structures with thiophenic sulfur for predominant C c H h SO 4 species. In this manner, we provide a highly detailed landscape for the organic acid content of inverted SAGD heat-exchanger deposits, to further illuminate the nature of fouling in those systems.

Dissolved organic compounds in reused process water for steam-assisted gravity drainage oil sands extraction

“…The application of high-resolution MS to such a study can provide more insights on the structure of components in environmental samples. Recently, a wide range of other chemical species containing oxygen, sulfur, and/or nitrogen atoms in their structures, like humic substances, have been detected in water samples from oil sands production using high-resolution MS methods (Headley et al, 2011;Schaub et al, 2007), along with tricyclic diamondoid and steroidal aromatic NAs (Rowland et al, 2011b(Rowland et al, , 2012. However, there is no universal method for the study of complex NA mixtures in environmental samples to date.…”

“…There are currently two methods for recovering bitumen. The first is surface mining of oil sands ores with subsequent separation of bitumen from the other constituents by an alkaline hot water extraction process (Schramm et al, 2000). The second method is an in situ thermal process for extracting bitumen from oil sands that are too deep to mine (Butler, 2001).…”

Characterization of Heavy Oil by FT-ICR MS Coupled with Various Ionization Techniques

“…FT ICR MS can be used in tandem mass spectrometry for isomer analysis, but the amount of ions with certain m/z in the ICR cell is not sufficient to detect the product ion spectrum. Isolation by quadrupole before MS/MS in the ICR cell is one of the potential solutions for isomer analysis 56) . MS/MS measurement is not enough for complete characterization of the isomers since about 50 fragment peaks are detected from a single precursor peak.…”

Application of Clustering Methods for Interpretation of Petroleum Spectra from Negative-Mode ESI FT-ICR MS

“…1 FT-ICR MS was shown to be effective for identifying the molecular composition of crude oils. [2][3][4][5][6][7][8][9][10][11][12] One of the most important goals of petroleomics is to predict the reactivities and properties of crude oils based on molecular information, which is obtained using high-resolution mass spectroscopy. Interpretation of high-resolution mass spectra can cause difficulties because of the large amounts of information contained in each spectrum.…”