Hypernated supercritical fluid chromatography: potential application for car lubricant analysis.

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. In previous papers related to this purpose, it was demonstrated that SFC allows the elution of common low molecular weight additives. Since their total resolution could not be achieved owing to the limited peak capacity of packed columns, the hyphenation of selective and informative detectors, atomic emission and mass spectrometry, were also carried out for identification. This paper describes the final implementation of a packed column SFC/FID-UV-AED-FTIR-MS system to contribute to the characterisation of both the base stock, mineral or semi-synthetic, and the low molecular weight additives. SFC/FID-UV-FTIR ensures the easy confirmation of the presence of esters in the base stock. Reference additives are used to demonstrate the performances of the multi hyphenated system prior to its implementation for their identification in packages and in formulated lubricants. Identification and partial structure elucidation of additives and families of additives in package and formulated car lubricants are presented: using combined information obtained from AED traces and FTIR chemigrams, chemical families of additives can be deduced. Then, the mass spectra can be interpreted in the elution zone of interest in order to go further in the determination of the additive molecular structure. The hypernated SFC system was also employed to follow the ageing of car lubricants.

Supercritical fluid chromatography hyphenated to bidimensional gas chromatography in comprehensive and heart-cutting mode: design of the instrumentation.

A new multidimensional chromatographic instrument has been developed to perform both SFC-GC×GC and SFC×GC×GC, in response to the challenge of complex matrices characterization. The design of this online system is fully described and enriched by theoretical and practical discussions. A new interface has been investigated: this interface allows the temporary storage of SFC fractions inside sampling loops before their quantitative transfer toward the GC×GC. This innovative design allows flexible and automatic hyphenated approaches such as single, multiple, total heart-cutting and comprehensive modes. An overview of the interfacing experimental conditions is also presented. Thanks to all the hyphenation possibilities of the three dimensions, this instrument opens up new prospects for the quantitative analysis of very complex matrices.

Global approach for the selection of high temperature comprehensive two-dimensional gas chromatography experimental conditions and quantitative analysis in regards to sulfur-containing compounds in heavy petroleum cuts.

Extending the knowledge on sulfur-containing compounds is crucial for the petroleum industry because they contribute to atmospheric pollution by combustion. Most of them are concentrated in heavy petroleum cuts, such as vacuum gas oils (VGOs). However, the resolution of the existing analytical methods does not allow a quantitative speciation of S-compounds contained in VGOs. Therefore, a high temperature GC×GC chromatograph hyphenated to a SCD was implemented in this study to obtain a quantitative S-compounds speciation. Firstly, various thermally stable stationary phases, in particular the new ionic liquid IL59 and Mega Wax-HT, were investigated in 1D-GC as a way to reduce the number of columns sets to be used in GC×GC. Consequently, several normal and reversed configurations of these columns were selected and tested in GC×GC. Then, a decision method was applied to facilitate the choice of the best combination of columns. Finally, the most adapted methods led to an innovative group type quantification and to a quantitative distribution of heavy sulfur species contained in a VGO sample. These results represent a major step towards the study of S-compounds in heavy petroleum cuts.

Challenge in the speciation of nitrogen-containing compounds in heavy petroleum fractions by high temperature comprehensive two-dimensional gas chromatography.

Extending the knowledge related to nitrogen-containing compounds presents an important interest for the petroleum industry due to their implication in atmosphere pollution as well as their inhibitive or refractive behaviour towards hydroprocessing. Most of the nitrogenated species are concentrated in heavy petroleum cuts. As no analytical method is resolutive enough for these heavy cuts, particularly regarding nitrogen-containing compounds, a new approach is needed. For this reason, this study focuses on the development of a GC×GC technique, through the hyphenation of a specific NCD detector with a GC×GC system at high temperature. The performances of highly polar thermally stable stationary phases, in particular those composed of promising ionic liquids, were monitored in normal and reversed configurations. Subsequently, after the extraction of neutral or basic compounds by adsorption on an ion-exchange resin, a first quantitative determination was attempted for a straight-run and a direct coal liquefaction vacuum gas oils. This study led to a better understanding of the behaviour of highly aromatic N-compounds by 2D-GC including an ionic liquid phase as well as a deeper N-characterization of heavy petroleum fractions.

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.

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.

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.

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.

Comprehensive two-dimensional gas chromatography for enhanced analysis of naphthas: new column combination involving permethylated cyclodextrin in the second dimension.

A new column association using comprehensive two-dimensional gas chromatography for the detailed molecular analysis of hydrocarbon mixtures is reported in this paper. In order to compare the impact of two different secondary columns, a novel column combination relying on a GC x 2GC system was used. This system is based on a non-polar first column (PONA) combined with both a permethylated beta-cyclodextrin (beta-Dex 120) stationary phase and a polysilphenylensiloxane (BPX 50) in the second dimension. Compared to BPX 50 stationary phase, the implementation of beta-cyclodextrin columns as the second dimension was found to improve the resolution between paraffins and naphthenes in the naphtha range but not in the middle distillate range. Attempts to improve the results and to understand the interaction mechanism remained unsuccessful. Therefore, the benefits of the beta-Dex 120-column are only demonstrated on heavy naphtha cut for the quantitation of hydrocarbons.

Towards comprehensive hydrocarbons analysis of middle distillates by LC-GCxGC.

The detailed characterization of middle distillates is essential for a better understanding of reactions involved in refining processes. Owing to a higher resolution power and an enhanced sensitivity, but especially to a group-type ordering in the chromatographic plane, comprehensive two-dimensional gas chromatography (GCxGC) offers unsurpassed characterization possibilities for petroleum samples. However, GCxGC fails to totally discriminate naphthenes from unsaturates occurring in hydrotreated diesel samples. This article aims at promoting the implementation of LC-GCxGC for the quantitative determination of hydrocarbon distribution in middle distillates, including naphthenes. In this configuration, liquid chromatography (LC) enables the separation of hydrocarbons into two fractions (viz., saturated and unsaturated) before the subsequent analysis of each fraction by GCxGC. In this paper, the choice of GCxGC conditions in order to achieve the separation and identification of hydrocarbons by chemical class is discussed; under these conditions, naphthenes are separated according to the number of saturated rings. For the first time, the presence of di-, tri-, and tetra-naphthenes resulting from the hydroconversion of aromatics can clearly be evidenced. A quantitative procedure for the determination of the distribution of hydrocarbons, including the distribution of naphthenes according to the number of saturated rings, is also proposed and discussed in detail. LC-GCxGC is found to provide an unequalled degree of information that will widely contribute to a better understanding of hydroconversion processes.

Supercritical fluid chromatography and two-dimensional supercritical fluid chromatography of polar car lubricant additives with neat CO(2) as mobile phase.

Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors.

New benchmark for basic and neutral nitrogen compounds speciation in middle distillates using comprehensive two-dimensional gas chromatography.

This paper reports an analytical method for the comprehensive two-dimensional gas chromatography (GC x GC) separation and identification of nitrogen compounds (N-compounds) in middle distillates according to their types (basicity). For the evaluation of the best chromatographic conditions, a non-polar x polar approach was chosen. The impact of the second dimension (stationary phase and column length) on the separation of basic and neutral N-compounds was evaluated by mean of two-dimensional resolution. This study revealed that the implementation of polar secondary column having free electron pairs improves drastically the separation of N-compounds. Indeed, the presence of permanent dipole-permanent dipole interactions between neutral N-compounds and the stationary phase was enlightened. The comparison of two different nitrogen chemiluminescence detectors (NCD) was also evaluated for GC x GC selective monitoring of N-compounds. Owing to higher resolution power and enhanced sensitivity achieved using developed chromatographic and detection conditions, it was possible to identify univocally and to quantitate N-compounds (i) by class of compounds and (ii), within a class, by carbon number. Finally, quantitative comparison of GC x GC-NCD with conventional gas chromatography illustrates the benefits of GC x GC leading to an excellent correlation with results obtained by American Society for Testing Materials (ASTM) methods for the determination of basic/neutral nitrogen ratio in diesel samples.

Comparison of comprehensive two-dimensional gas chromatography coupled with sulfur-chemiluminescence detector to standard methods for speciation of sulfur-containing compounds in middle distillates.

The monitoring of total sulfur content and speciation of individual sulfur-containing compounds in middle distillates is required for efficient catalyst selection and for a better understanding of the kinetics of the reactions involved in hydrotreament processes. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GCxGC) hyphenated to sulfur chemiluminescence detection (SCD) has recently evolved as a powerful tool for improving characterization and identification of sulfur compounds. The aim of this paper is to compare quantitatively GCxGC-SCD and various other methods commonly employed in the petroleum industry, such as X-ray fluorescence, conventional GC-SCD, and high-resolution mass spectrometry, for total sulfur content determination and speciation analysis. Different samples of middle distillates have been analyzed to demonstrate the high potential and important advantages of GCxGC-SCD for innovative and quantitative analysis of sulfur-containing compounds. More accurate and detailed results for benzothiophenes and dibenzothiophenes are presented, showing that GCxGC-SCD should become, in the future, an essential tool for sulfur speciation analysis.

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 (GCxGC). 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. GCxGC showed that a contaminated-soil microflora removed all aromatics and all branched alkanes containing less than C(15). The most recalcitrant compounds were the branched and cyclic alkanes with 15-23 atoms of carbon.

Multidimensional gas chromatography for the detailed PIONA analysis of heavy naphtha: hyphenation of an olefin trap to comprehensive two-dimensional gas chromatography.

A multidimensional method providing the composition of a heavy naphtha in paraffins, isoparaffins, olefins, naphthenes, and aromatics (PIONA) in the C8-C14 range is presented. The analytical set-up consists in a silver modified silica olefin trap on-line coupled to comprehensive two-dimensional gas chromatography (GC x GC). In this configuration, hydrocarbons are separated, in gaseous state, in two fractions, saturate and unsaturate, each fraction being subsequently analysed by GC or by GC x GC. The resolution between saturates and olefins was found to be improved compared to a single GC x GC run. The characterisation of the olefin trap highlights the benefits and the limits related to the use of that stationary phase as a double bond selective fractionation medium.

Characterisation of middle-distillates by comprehensive two-dimensional gas chromatography (GC x GC): A powerful alternative for performing various standard analysis of middle-distillates.

The detailed characterisation of middle distillates is essential for a better understanding of reactions involved in refining process. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GC x GC) is a powerful tool for improving characterisation of petroleum samples. The aim of this paper is to compare GC x GC and various ASTM methods -- gas chromatography (GC), liquid chromatography (LC) and mass spectrometry (MS) -- for group type separation and detailed hydrocarbon analysis. Best features of GC x GC are demonstrated and compared to these techniques in terms of cost, time consumption and accuracy. In particular, a new approach of simulated distillation (SimDis-GC x GC) is proposed: compared to the standard method ASTM D2887 it gives unequal information for better understanding of conversion process.

Evaluation of a retention model in comprehensive two-dimensional gas chromatography.

Modeling the retention in comprehensive two-dimensional gas chromatography (GC x GC) was achieved using retention indices obtained in conventional GC. Predicted results were compared with experimental data obtained in the two-dimensional separation of a synthetic hydrocarbon mixture. This proved to be helpful in optimizing the operating conditions of GC x GC separation of a complex petroleum sample and in identifying chemical families.

Comparison of conventional gas chromatography and comprehensive two-dimensional gas chromatography for the detailed analysis of petrochemical samples.

Comprehensive two-dimensional gas chromatography (GC x GC) has been investigated for the characterization of high valuable petrochemical samples from dehydrogenation of n-paraffins, Fischer-Tropsch and oligomerization processes. GC x GC separations, performed using a dual-jets CO2 modulator, were optimized using a test mixture representative of the hydrocarbons found in petrochemicals. For complex samples, a comparison of GC x GC qualitative and quantitative results with conventional gas chromatography (1D-GC) has demonstrated an improved resolution power of major importance for the processes: the group type separation has permitted the detection of aromatic compounds in the products from dehydrogenation of n-paraffins and from oligomerization, and the separation of alcohols from other hydrocarbons in Fischer-Tropsch products.