On-line liquid chromatography/mass spectrometry for heavy hydrocarbon characterization

Hsu, Chang Samuel; McLean, Matt; Qian, Kuangnan; Aczel, T.; Blum, S. C.; Olmstead, William N.; Kaplan, L. H.; Robbins, Winston K.; Schulz, W.

doi:10.1021/ef00027a007

Cited by 47 publications

(26 citation statements)

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“…However, various MS applications that employ some partial chromatographic separation of the naphthenic acids have been used successfully for the structural elucidation of classes of naphthenic acids, including useful approaches such as: GC-MS (Green et al, 1985;Dzidic et al, 1988;St. John et al, 1998), 2D GC-MS and liquid chromatography MS (LC-MS) (Hsu et al, 1991). Detection has employed, in general, low-resolution triplequadrupole MS and ion trap technology; along with medium mass resolution time-of-flight MS (TOF-MS).…”

Section: Gas and Liquid Chromatography Mass Spectrometrymentioning

confidence: 99%

Mass spectrometric characterization of naphthenic acids in environmental samples: A review

Headley

Peru

Barrow

2008

Mass Spectrometry Reviews

151

124

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There is a growing need to develop mass spectrometric methods for the characterization of oil sands naphthenic acids (structural formulae described by C(n)H(2n+z)O(2) where n is the number of carbon atoms and "z" is referred to as the "hydrogen deficiency" and is equal to zero, or is a negative, even integer) present in environmental samples. This interest stems from the need to better understand their contribution to the total acid number of oil sands acids; along with assessing their toxicity in aquatic environments. Negative-ion electrospray ionization has emerged as the analytical technique of choice. For infusion samples, matrix effects are particularly evident for quantification in the presence of salts and co-elutants. However, such effects can be minimized for methods that employ chromatographic separation prior to mass spectrometry (MS) detection. There have been several advances for accurate identification of classes of naphthenic acid components that employ a range of MS hyphenated techniques. General trends measured for degradation of the NAs in the environment appear to be similar to those obtained with either low- or high-resolution MS. Future MS research will likely focus on (i) development of more reliable quantitative methods that use chromatography and internal standards, (ii) the utility of representative model naphthenic acids as surrogates for the complex NA mixtures, and (iii) development of congener-specific analysis of the principal toxic components.

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Section: Gas and Liquid Chromatography Mass Spectrometrymentioning

confidence: 99%

Mass spectrometric characterization of naphthenic acids in environmental samples: A review

Headley

Peru

Barrow

2008

Mass Spectrometry Reviews

151

124

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“…In regard to aromatic ring composition, comprehensive 2-dimensional gas chromatography (GC × GC) may be used to separate compounds by aromaticity; however, it is limited to only the most volatile/low-boiling fractions of crude oil . HPLC methods that utilize a single stationary phase were developed on alumina, amine, and charge-transfer stationary phases that extend the accessible boiling range; however, these methods were often unable to resolve saturated hydrocarbons from monoaromatics. − ,, As a result, two-column approaches were developed to address the comprehensive separation of hydrocarbon compounds, including saturates, by aromaticity. Robbins previously developed an online two-column approach, termed HPLC-2, which used a dinitroanilinopropyl silica gel column (DNAP) to separate mono-, di-, tri-, and tetra-aromatic and polar compounds and a propylaminocyano (PAC) column to separate saturated hydrocarbons from monoaromatics .…”

Section: Introductionmentioning

confidence: 99%

Dual-Column Aromatic Ring Class Separation with Improved Universal Detection across Mobile-Phase Gradients via Eluate Dilution

et al. 2017

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The herein described High Performance Liquid Chromatography (HPLC) platform (termed HPLC-3) combines a complex solvent gradient with two electron acceptor columns to provide aromatic ring class (ARC) separation for heavy oils. The separation yields seven major fractions: saturates, monoaromatics (1 ring), diaromatics (2 rings), triaromatics (3 rings), tetra-aromatics (4 rings), polyaromatics and polars (5+ polars), and aliphatic sulfides. The system utilizes a photodiode array detector (PDA) for online measurements of aromaticity in series with an evaporative light scattering detector (ELSD) to provide improved quantitative mass determination across the entire solvent gradient. A new postcolumn dilution strategy was successfully utilized to compensate for solvent effects on the ELSD signal. The method allows for calibration across the entire HPLC-3 solvent gradient and simultaneously diverts ∼90% of the sample effluent for fraction collection and further characterization. In addition to the major ARC fractions, the retention characteristics of various heteroatomic functional groups were studied to demonstrate the HPLC-3 system’s ability to further separate polar compounds on the basis of hydrogen bonding.

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“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Qian

Diehl

Dechert

et al. 2004

Eur J Mass Spectrom (Chichester)

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We report the first coupling of supercritical fluid chromatography (SFC) with field ionization time-of-flight high-resolution mass spectrometry (FI-ToF HRMS), in parallel with ultraviolet (UV) detection and flame ionization detection (FID), for rapid and quantitative analysis of petroleum middle distillates. SFC separates petroleum middle distillates into saturates and 1- to 3-ring aromatics. FI generates molecular ions for hydrocarbon species eluted from the SFC. The high resolution and exact mass measurements by ToF mass spectrometry provide elemental compositions of the molecules in the petroleum product. The amounts of saturates and aromatic ring types were quantified using the parallel SFC-FID assisted by SFC-UV. With a proper carbon-number calibration, the detailed composition of the petroleum middle distillate was rapidly determined.

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On-line liquid chromatography/mass spectrometry for heavy hydrocarbon characterization

Cited by 47 publications

References 0 publications

Mass spectrometric characterization of naphthenic acids in environmental samples: A review

Mass spectrometric characterization of naphthenic acids in environmental samples: A review

Dual-Column Aromatic Ring Class Separation with Improved Universal Detection across Mobile-Phase Gradients via Eluate Dilution

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

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