Comparison of cryogenic and differential flow (forward and reverse fill/flush) modulators and applications to the analysis of heavy petroleum cuts by high-temperature comprehensive gas chromatography

Duhamel, Chloé; Cardinaël, Pascal; Peulon-Agasse, Valérie; Firor, Roger L.; Pascaud, Laurent; Semard-Jousset, Gaëlle; Giusti, Pierre; Livadaris, Vincent

doi:10.1016/j.chroma.2015.01.095

Cited by 47 publications

(25 citation statements)

References 22 publications

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“…effective re-injection bands thanks to the geometry of the CFT plate and of the re-injection dynamics (e.g., RFF). These values are in perfect agreement with those reported by Duhamel et al [23] that studied the effectiveness of FFF and RFF dynamics for the analysis of vacuum distilled mineral oils. The net separation measure (S GC×GC ) was assumed as quantitative descriptor of the system separation ability, under the experimental conditions applied.…”

Section: Systems Performance Evaluationsupporting

confidence: 93%

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Potential of the reversed-inject differential flow modulator for comprehensive two-dimensional gas chromatography in the quantitative profiling and fingerprinting of essential oils of different complexity

Cordero

Rubiolo

Cobelli³

et al. 2015

Journal of Chromatography A

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Section: Systems Performance Evaluationsupporting

confidence: 93%

“…Advantages include: (a) higher efficiency of band re-injection with improved 2 D peak-widths and symmetry, (b) adjustable collection channel volume, (c) better handling of the overloading phenomenon without dramatic loss of separation power and resolution [22,23].…”

Section: Regionmentioning

confidence: 99%

Potential of the reversed-inject differential flow modulator for comprehensive two-dimensional gas chromatography in the quantitative profiling and fingerprinting of essential oils of different complexity

Cordero

Rubiolo

Cobelli³

et al. 2015

Journal of Chromatography A

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“…The use of pulsed flow modulation two‐dimensional comprehensive GC in combination with MS with an SMB interface can be investigated in the future to improve the GC separation of oxidised heavy paraffinic samples to allow identification of oxygenated compounds without the use of offline pre‐separation techniques, such as SPE. The use of pulsed flow modulation in combination with cold‐EI is also preferred to cryogenic modulation and standard EI to reduce peak tailing of high boiling compounds . The column sets for the optimum HT‐GC × GC separation of oxygenates in oxidised heavy paraffinic fractions were reported previously, and hydrocarbons up to a carbon number of C60 could be eluted with a reversed column configuration.…”

Section: Resultsmentioning

confidence: 99%

“…The use of pulsed flow modulation in combination with cold-EI is also preferred to cryogenic modulation and standard EI to reduce peak tailing of high boiling compounds. 45 The column sets for the optimum HT-GC × GC separation of oxygenates in oxidised heavy paraffinic fractions were reported previously, 15 and hydrocarbons up to a carbon number of C60 could be eluted with a reversed column configuration.…”

Section: Figure 13mentioning

confidence: 99%

The pre‐separation of oxygen containing compounds in oxidised heavy paraffinic fractions and their identification by GC‐MS with supersonic molecular beams.

et al. 2019

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The heavy petroleum fractions produced during refining processes need to be upgraded to useable products to increase their value. Hydrogenated heavy paraffinic fractions can be oxidised to produce high value products that contain a variety of oxygenates. These heavy oxygenated paraffinic fractions need to be characterised to enable the control of oxidation processes and to understand product properties. The accurate identification of the oxygenates present in these fractions by electron ionisation (EI) mass spectrometry is challenging due to the complexity of these heavy fractions. Adding to this challenge is the limited applicability of EI mass spectral libraries due to the absence of molecular ions from the EI mass spectra of many oxygenates. The separation of oxygenates from the complex hydrocarbon matrix prior to high temperature GC‐MS (HT‐GC‐MS) analysis reduces the complexity of these fractions and assists in the accurate identification of these oxygenates. Solid phase extraction (SPE) and supercritical fluid chromatography (SFC) were employed as prefractionation techniques. GC‐MS with supersonic molecular beams (SMBs) (also named GC‐MS with cold‐EI) utilises a SMB interface with which EI is done with vibrationally cold sample compounds in a fly‐through ion source (cold‐EI) resulting in a substantial increase in the molecular ion signal intensity in the mass spectrum. This greatly enhances the accurate identification of the oxygenates in these fractions. This study investigated the ionisation behaviour of oxygenated compounds using cold‐EI. The prefractionation by SPE and SFC and the subsequent analysis with GC‐MS with cold‐EI were applied to an oxygenated heavy paraffinic fraction.

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“…Examples include the congeners of polychlorinated biphenyls and other polyhalogenated aromatic compounds [1,2], pesticide residues [3,4], hydrocarbon fractions in crude oil [5,6], fatty-acid methyl esters in biodiesel blends [7], and trace-level VOC biomarkers of disease or metabolism in breath and urine [8,9].…”

Section: Introductionmentioning

confidence: 99%

Comprehensive two-dimensional gas chromatographic separations with a temperature programmed microfabricated thermal modulator

Collin

Nuñovero

Paul

et al. 2016

Journal of Chromatography A

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Comprehensive two-dimensional gas chromatography (GC×GC) with a temperature-programmed microfabricated thermal modulator (μTM) is demonstrated. The 0.78 cm(2), 2-stage μTM chip with integrated heaters and a PDMS coated microchannel was placed in thermal contact with a solid-state thermoelectric cooler and mounted on top of a bench scale GC. It was fluidically coupled through heated interconnects to an upstream first-dimension ((1)D) PDMS-coated capillary column and a downstream uncoated capillary or second-dimension ((2)D) PEG-coated capillary. A mixture of n-alkanes C6-C10 was separated isothermally and the full-width-at-half-maximum (fwhm) values of the modulated peaks were assessed as a function of the computer-controlled minimum and maximum stage temperatures of μTM, Tmin and Tmax, respectively. With Tmin and Tmax fixed at -25 and 100°C, respectively, modulated peaks of C6 and C7 had fwhm values<53 ms while the modulated peaks of C10 had a fwhm value of 1.3s, due to inefficient re-mobilization. With Tmin and Tmax fixed at 0 and 210°C, respectively, the fwhm value for the modulated C10 peaks decreased to 67 ms, but C6 and C7 exhibited massive breakthrough. By programming Tmin from -25 to 0°C and Tmax from 100 to 220°C, the C6 and C7 peaks had fwhm values≤50 ms, and the fwhm for C10 peaks remained<95 ms. Using the latter conditions for the GC×GC separation of a sample of unleaded gasoline yielded resolution similar to that reported with a commercial thermal modulator. Replacing the PDMS phase in the μTM with a trigonal-tricationic room temperature ionic liquid eliminated the bleed observed with the PDMS, but also reduced the capacity for several test compounds. Regardless, the demonstrated capability to independently temperature program this low resource μTM enhances its versatility and its promise for use in bench-scale GC×GC systems.

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Comparison of cryogenic and differential flow (forward and reverse fill/flush) modulators and applications to the analysis of heavy petroleum cuts by high-temperature comprehensive gas chromatography

Cited by 47 publications

References 22 publications

Potential of the reversed-inject differential flow modulator for comprehensive two-dimensional gas chromatography in the quantitative profiling and fingerprinting of essential oils of different complexity

Potential of the reversed-inject differential flow modulator for comprehensive two-dimensional gas chromatography in the quantitative profiling and fingerprinting of essential oils of different complexity

The pre‐separation of oxygen containing compounds in oxidised heavy paraffinic fractions and their identification by GC‐MS with supersonic molecular beams.

Comprehensive two-dimensional gas chromatographic separations with a temperature programmed microfabricated thermal modulator

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