Fabrice Bertoncini

Using comprehensive two-dimensional gas chromatography for the analysis of oxygenates in middle distillates I. Determination of the nature of biodiesels blend in diesel fuel.

In the current energetic context (increasing consumption of vehicle fuels, greenhouse gas emission etc.) government policies lead to mandatory introduction in fossil fuels of fuels resulting from renewable sources of energy such as biomass. Blending of fatty acid alkyl esters from vegetable oils (also known as biodiesel) with conventional diesel fuel is one of the solutions technologically available; B5 blends (up to 5%w/w esters in fossil fuel) are marketed over Europe. Therefore, for quality control as well as for forensic reasons, it is of major importance to monitor the biodiesel origin (i.e. the fatty acid ester distribution) and its content when it is blend with petroleum diesel. This paper reports a comprehensive two-dimensional gas chromatography (GC x GC) method that was developed for the individual quantitation of fatty acid esters in middle distillates matrices. Several first and the second dimension columns have been investigated and their performances to achieve (i) a group type separation of hydrocarbons and (ii) individual identification and quantitation of fatty acid ester blend with diesel are reported and discussed. Finally, comparison of quantitative GC x GC results with reference methods demonstrates the benefits of GC x GC approach which enables fast and reliable individual quantitation of fatty acid esters in one single run. Results show that under developed chromatographic conditions, quantitative group type analysis of hydrocarbons is also possible, meaning that simultaneous quantification of hydrocarbons and fatty acid esters can be achieved in one single run.

High-temperature two-dimensional gas chromatography of hydrocarbons up to nC60 for analysis of vacuum gas oils

In a tense energetic context, the characterization of heavy petroleum fractions becomes essential. Conventional comprehensive two-dimensional gas chromatography (2D-GC or GCxGC) is widely used for middle distillates analysis, but only a few applications are devoted to these heavier fractions. In this paper, it is shown how the optimization of GCxGC separation allowed the determination of suitable high-temperature (HT) conditions, adjusting column properties and operating conditions. 2D separations were evaluated using 2D separation criteria and a new concept of 2D asymmetry (As(2D)). New HT conditions allowed the extension of GCxGC range of applications to heavier hydrocarbons, up to nC(60). A first application of high-temperature two-dimensional gas chromatography (HT-2D-GC) to a full vacuum gas oil (VGO) feed stock is described. Comparisons with other standardized methods illustrate the high potential of HT-2D-GC for heavy fractions analysis.

Supercritical fluid chromatography hyphenated with twin comprehensive two-dimensional gas chromatography for ultimate analysis of middle distillates

This paper reports the conditions of online hyphenation of supercritical fluid chromatography (SFC) with twin comprehensive two-dimensional gas chromatography (twin-GCxGC) for detailed characterization of middle distillates; this is essential for a better understanding of reactions involved in refining processes. In this configuration, saturated and unsaturated compounds that have been fractionated by SFC are transferred on two different GC x GC columns sets (twin-GCxGC) placed in the same GC oven. Cryogenic focusing is used for transfer of fractions into the first dimension columns before simultaneous GCxGC analysis of both saturated and unsaturated fractions. The benefits of SFC-twin-GC x GC are demonstrated for the extended alkane, iso-alkane, alkene, naphthenes and aromatics analysis (so-called PIONA analysis) of diesel samples which can be achieved in one single injection. For that purpose, saturated and unsaturated compounds have been separated by SFC using a silver loaded silica column prior to GC x GC analysis. Alkenes and naphthenes are quantitatively recovered in the unsaturated and saturated fractions, respectively, allowing their identification in various diesel samples. Thus, resolution between each class of compounds is significantly improved compared to a single GCxGC run, and for the first time, an extended PIONA analysis of diesel samples is presented.

Characterisation of biodegradation capacities of environmental microflorae for diesel oil by comprehensive two-dimensional gas chromatography

In contaminated soils, efficiency of natural attenuation or engineered bioremediation largely depends on biodegradation capacities of the local microflorae. In the present study, the biodegradation capacities of various microflorae towards diesel oil were determined in laboratory conditions. Microflorae were collected from 9 contaminated and 10 uncontaminated soil samples and were compared to urban wastewater activated sludge. The recalcitrance of hydrocarbons in tests was characterised using both gas chromatography (GC) and comprehensive two-dimensional gas chromatography (GC×GC). The microflorae from contaminated soils were found to exhibit higher degradation capacities than those from uncontaminated soil and activated sludge. In cultures inoculated by contaminated-soil microflorae, 80% of diesel oil on an average was consumed over 4-week incubation compared to only 64% in uncontaminated soil and 60% in activated sludge cultures. As shown by GC, n-alkanes of diesel oil were totally utilised by each microflora but differentiated degradation extents were observed for cyclic and branched hydrocarbons. The enhanced degradation capacities of impacted-soil microflorae resulted probably from an adaptation to the hydrocarbon contaminants but a similar adaptation was noted in uncontaminated soils when conifer trees might have released natural hydrocarbons. GC×GC showed that a contaminated-soil microflora removed all aromatics and all branched alkanes containing less than C15. The most recalcitrant compounds were the branched and cyclic alkanes with 15–23 atoms of carbon.

Extended characterization of a vacuum gas oil by offline LC‐high‐temperature comprehensive two‐dimensional gas chromatography

In a context of environmental preservation, purification and conversion of heavy petroleum cuts into high-quality fuel becomes essential. The interest for the characterization of those very complex matrices becomes a trendy analytical challenge, when it comes to get molecular information for the optimization of industrial processes. Among new analytical techniques, high-temperature 2-D GC has recently proved its applicability to heavy petroleum matrices, but lacks in selectivity to separate all chemical groups. To gain resolution, heart cutting is demonstrated for LC separation of saturated, aromatic and polar compounds prior to high-temperature 2-D GC. Therefore, an extended global resolution was obtained, especially by a better distinction of saturated compounds. This includes iso-paraffins and biomarker polynaphthenic structures, which are impossible to quantify with MS methods. This new way to analyze heavy petroleum fractions gives innovative opportunities for the construction of global weight distributions by carbon atoms number and by chemical families. This can right now be employed for quantitative analysis of heavy petroleum fractions and for studying conversion processes.

Aplicación de la Cromatografía de Gases Bidimensional en el Análisis de Derivados Azufrados y Nitrogenados en Gasolina

The comprehensive two-dimensional gas chromatography (GC×GC) is used as a powerful tool for an improved characterization in sulphur and nitrogen speciation in gasoline. There are shown the results obtained of the connection between GC×GC and a specific detector, sulphur (SCD) and Nitrogen (NCD). This technique is based on the separation of two orthogonal dimensions, achieved by two chromatographic capillary columns with different polarity. The final chromatogram obtained was structured according to the volatility and polarity of hydrocarbons which facilitates its identification. The results are a very promising alternative in the characterization of these types of compounds in middle distillates. This work illustrates the high resolution power of the GC×GC in combination with a selective detection of sulphur or nitrogen compounds in gasoline when a specific detector is used.