Diesel Fuel Analysis by GC-FIMS:  Normal Paraffins, Isoparaffins, and Cycloparaffins

Abstract

A reliable and convenient characterization method that provides a detailed hydrocarbon composition profile for transportation fuels is an important part of process optimization directed at reducing regulated emissions. In our previous study (Briker, Y.; Ring, Z.; Iacchelli, A.; McLean, N.; Rahimi P. M.; Fairbridge, C.; Malhotra, R.; Coggiola, M. A.; Young, S. E. Energy Fuels 2001, 15 (1), 23-37) we described the development of a modified gas chromatography, field ionization mass spectrometry method for detailed hydrocarbon type characterization of diesel fuel. The method proved to be an invaluable technique for rapid analysis of diesel fuel. It was less timeconsuming and more informative than the existing mass spectrometry methods, from a characterization point of view, and it was user-friendly and did not require any major modification to an existing commercial instrument, from an instrumentation point of view. This method correlated well with the other methods for total aromatic and saturate groups, and the data for aromatic subgroups were verified against the data obtained from other mass spectrometric and nonmass spectrometric techniques. This paper describes a continuing effort to verify the new GC-FIMS method and produce correlations for the saturate groups. The purpose of this study was to validate GC-FIMS measurements of various saturate types using samples of physically separated fractions, enriched in the individual types by various LC methods described in the literature. In this study, the non-normal paraffinic portion of the saturate fraction of the selected diesel cut was separated into iso-and cycloparaffins. The normal paraffins were quantitatively removed by molecular sieve and additionally determined by high-resolution gas chromatography of the saturate fraction. The contents of iso-and cycloparaffins were calculated gravimetrically in each separated fraction and also analyzed by mass spectrometry methods. The results obtained for the saturate types by different methods were all in good agreement, which demonstrates the applicability of the GC-FIMS method for saturates analysis.

Development of an Experimental Database and Kinetic Models for Surrogate Diesel Fuels

“…Commercial diesel fuels are complex blends of several hundreds of individual species [2][3][4]. The primary chemical and physical property ranges of North American (U.S. and Canada) diesel fuels are given in Table 1 [5,6].…”

The Coupling of Supercritical Fluid Chromatography and Field Ionization Time-of-Flight High-Resolution Mass Spectrometry for Rapid and Quantitative Analysis of Petroleum Middle Distillates

“…Characterization of petroleum feeds and products at molecular level are key to the molecule management of refining processes. 1,2 There have been continuous efforts in developing and improving mass spectrometric tools for hydrocarbon analysis of various boiling ranges, including gasoline, diesel, 3,4 gas oil and vacuum gas oil, [5][6][7][8] polar hydrocarbons [9][10][11][12][13] and coke. 14,15 Molecular compositions of petroleum middle distillates, such as diesels, kerosenes and jet fuels, are traditionally characterized in terms of group types (for example, saturates, 1-to 3-ring aromatics) by a variety of chromatographic, mass spectrometric and combined chromatography/mass spectrometry methods.…”

Core Structure Analysis of Heavy Oil Components with Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

“…It is essential to understand the reactivities and physical properties of feedstocks in process development. Regarding atmospheric distillates, such as naphtha, kerosene, and diesel, component data have been obtained through conventional analyses, e.g., gas chromatographymass spectrometry (GC-MS) 1) , GC-field ionization mass spectrometry (GC-FIMS) 2) , and two-dimensional GC (2DGC) 3), 4) . High temperature 2DGC 5) and a combination of multidimensional liquid chromatographic separation and high-resolution mass spectrometry 6), 7) has been used for the characterization of vacuum gas oil.…”