Adnan Al-Hajji

Evaluation of Quantitative Sulfur Speciation in Gas Oils by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: Validation by Comprehensive Two-Dimensional Gas Chromatography

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been applied for the quantitative speciation of sulfur containing compounds in gas oil (GO). For this purpose, ionization and mass spectrometric parameters have been studied and optimized with a set of standard compounds and GO samples. Comprehensive two-dimensional gas chromatography (GCxGC) was used as the reference method. To allow a quantitative comparison between FT-ICR MS and GCxGC results for GO samples, FT-ICR MS parameters were optimized and data obtained by both techniques were standardized. Response factors were established for two ionization modes: atmospheric pressure photo ionization (APPI) and electrospray after selective derivatization of sulfur compounds (MeESI). To test the validity of the developed MS methods, a third GO was analyzed and response factors were applied. Comparison with GCxGC results showed good agreement for sulfur families (deviation within 5% and 15% for MeESI and APPI data, respectively). Abundances of individual isomer groups match within 40% in most cases. These results principally demonstrate the suitability of FT-ICR MS for a quantitative analysis of sulfur compounds (by DBE and carbon number distribution pattern) in petroleum middle distillates. This approach has the potential to be extended to higher- and non-boiling petroleum fractions where quantitative speciation is presently not available.

Controls on hydrocarbon properties in a Paleozoic petroleum system in Saudi Arabia: Exploration and development implications

The unpredicted discovery of downdip oil in Permian–Carboniferous Unayzah sandstone reservoirs along the southern flank of the predominantly gas condensate Ghazal field in Saudi Arabia highlighted the need for a thorough assessment of controls on hydrocarbon properties, with the aim to improve prediction and reduce uncertainty. Primary controls on hydrocarbon property variations (condensate-to-gas ratio) here appear to be compartmentalization, multiple charging, presumably from a Lower Silurian Qusaiba kitchen to the south and east within the late-oil to wet-gas generation window, and dysmigration to the north and west. Gas on production represents mostly unmixed thermogenic accumulations of variable maturities, with no sign of biodegradation or thermal cracking. Light oil (1.06–1.21% calculated vitrinite reflectance [Rc]) in the southern part of the field represent late-mature accumulations that apparently escaped flushing by subsequent gas condensate charges generated near the wet-gas generation window (1.41–1.55% Rc) and currently occupying the field to the north. Constant maturity variations for both gasoline range and heavier components in each sample testify to a lack of mixing between the hydrocarbon phases. Petroleum inclusions similarly comprise either light oil or gas condensate that coexist with significantly overlapping homogenization temperatures, suggesting considerable overlap in their trapping history (135–35 Ma). Less mature petroleum has not been identified in the field, possibly because of a lack of trap closure or migration focus prior to the inferred Late Jurassic filling or because of displacement to updip structures, thereby high grading the probability of undiscovered oil west and northwest of Ghazal. If thermal generation instead of retrograde condensation or phase separation controls this petroleum system, then the potential for deeper oil accumulations is limited.

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Abstract Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, 13C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The 13C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.

Ligand exchange chromatography: a vital dimension for the reliable characterization of heterocycles in crude oils and refined products

In the present study, we established a statistical distribution pattern of indigenous sulfur, nitrogen, and oxygen species in Arabian Heavy crude oil and its distilled fractions: naphtha, gas oil, and vacuum gas oil (VGO) using chemical derivatization with methyl iodide and subsequent characterization by positive electrospray Fourier transform mass spectrometry. It was observed that sulfur species for naphtha and gas oil were accumulated at lower double bond equivalent values and at lower carbon numbers compared to VGO, whereas crude oil encompassed a complete range of the sulfur species detected in all distilled fractions. Moreover, the use of alumina column chromatography and ligand exchange chromatography (LEC) on a palladium-bonded silica stationary phase revealed additional structural features of sulfur heterocycles in terms of condensed and non-condensed thiophenes. During LEC separation, in addition to sulfur heterocycles, interesting results were obtained for oxygen-containing compounds. Ortho-substituted alkyl phenols were separated from meta- and para-substituted alkyl phenols on a palladium-bonded silica stationary phase.

Methods of analysis modified size exchange chromatography method for analysis of heavy oil residues

A modified size exchange chromatography method is used to obtain molecular weight distributions, average molecular weight, and other characteristics of heavy oil residues: coal asphalt, petroleum asphalt, vacuum residue oil, and ethylene residue oil. This method can be applied for developing and studying processes involved in hydrogenation of heavy oil residues, road asphalt production, and coal liquefaction.