Development of on-line comprehensive two-dimensional liquid chromatography method for the separation of biomass compounds.

Comprehensive on-line two-dimensional liquid chromatography (on-line LC × LC) was used for the characterization of bio-oils obtained by fast pyrolysis of lignocellulosic biomass. The resulting bio-oil contains a large number of oxygenated chemical families and must therefore be upgraded before being used as drop-in transportation biofuels. The good knowledge of its complex composition is essential for optimizing the mandatory bio-oil upgrading process to biofuels, thereby requiring powerful separation techniques designed to be hyphenated to mass spectrometry detection (LC × LC-MS). In this study, reversed phase conditions were optimized in both dimensions for the RPLC × RPLC separation of the aqueous fraction of bio-oils. The first step of method development consisted in searching for a suitable set of RP-conditions via the screening of a large number of RP-systems (made up of different stationary phases and/or mobile phases and/or temperature). The practical peak capacity and the degree of orthogonality were calculated for a sample of 38 representative compounds, both descriptors having been considered as selection criterion. Two different couplings were chosen and evaluated for the RPLC × RPLC separation of the 38 representative compounds. The best of both, in terms of real practical peak capacity, was further successfully applied to the separation of the aqueous phase of a partially dehydroxygenated bio-oil.

Complete elution of vacuum gas oil resins by comprehensive high-temperature two-dimensional gas chromatography.

The development of efficient conversion processes requires extended knowledge on vacuum gas oils (VGOs). Among these processes, hydrocracking is certainly one of the best suited to meet the increasing demand on high quality diesel fuels. Most of refractory and inhibiting compounds towards hydrocracking and especially nitrogen containing compounds are contained in a fraction of the VGO called the resin fraction, which corresponds to the most polar fraction of a VGO obtained by liquid chromatography (LC) fractionation on a silica column. However, the lack of resolution observed through existing analytical methods does not allow a detailed characterization of these fractions. A recent study showed that comprehensive high temperature two-dimensional gas chromatography (HT-GC×GC) methods could be optimized in order to elute heavy compounds. This method was implemented for the analysis of VGO resin fractions and complete elution was reached. Firstly, the method was validated through repeatability, accuracy, linearity and response factors calculations. Four VGO resin fractions were analyzed and their HT-GC×GC simulated distillation curves were compared to their GC simulated distillation (GC-SimDist) curves. This comparison showed that the method allows complete elution of most of the analyzed VGO resin fractions. However, a detailed characterization of these fractions is not yet obtained due to the very large number of heteroatomic and aromatic species that a flame ionization detector can detect. Current work aims at increasing the selectivity of GC×GC by using heteroatom selective detectors in order to improve the characterization of such products.

Development of heart-cutting multidimensional gas chromatography coupled to time of flight mass spectrometry for silicon speciation at trace levels in gasoline samples.

To improve the understanding of hydrotreatment (HDT) catalyst poisoning by silicon species, these molecules must be characterized in petroleum products using powerful analytical systems. Heart-cutting gas chromatography coupled to time of flight mass spectrometry (GC-GC/TOFMS) method equipped with a Deans switch (DS) system was developed for the direct characterization of target silicon compounds at trace level (µg kg(-1)) in gasoline samples. This method was performed to identify silicon compounds never characterized before. After the selection of the second dimension column using GC-GC-FID, GC-GC/TOFMS was performed. The calibration curves obtained by the GC-GC/TOFMS method were linear up to 1,000 µg kg(-1). Limits of detection (LOD) were ranging from 5 to 33 µg kg(-1) in spiked gasoline. The method provided sufficient selectivity and sensitivity to characterize known silicon compounds thanks to their specific ions and their retention times. The analysis of a naphtha sample by GC-GC/TOFMS has shown the presence of cyclic siloxanes (D(n)) as major compounds of PDMS thermal degradation with the occurrence of linear siloxanes, especially hexamethyldisiloxane (L(2)), which was never characterized in petroleum products but already known as severe poison for catalyst.

Combining Fourier transform-ion cyclotron resonance/mass spectrometry analysis and Kendrick plots for silicon speciation and molecular characterization in petroleum products at trace levels.

A new method combining FT-ICR/MS analysis and Kendrick plots for the characterization of silicon species at trace levels in light petroleum products is presented. The method provides efficient instrumental detection limits ranging from 80 ng/kg to 5 µg/kg and reliable mass accuracy lower than 0.50 ppm for model silicon molecules in spiked gasoline. More than 3000 peaks could be detected in the m/z 50-500 range depending on the nature of the gasoline sample analyzed. An in-house software program was used to calculate Kendrick plots. Then, an algorithm searched, selected, and represented silicon species classes (O(2)Si, O(3)Si, and O(4)Si classes) in Kendrick plots by incorporating model molecules' information (i.e., exact mass and intensity). This procedure allowed the complete characterization of more than 50 new silicon species with different degrees of unsaturation in petroleum products.

Overcoming the high-temperature two-dimensional gas chromatography limits to elute heavy compounds.

Overcoming high-temperature (HT) two-dimensional gas chromatography (GC × GC) limits is critical for the analysis of heavy hydrocarbons, particularly those contained in heavy petroleum fractions. To reach this goal, HT-GC × GC analysis was adapted from HT-GC Simulated Distillation (HT-GC SimDist) operating conditions as this analysis embraces compounds whose boiling point ranges from 35 °C to 700 °C and from a previous study that enabled the elution of linear alkane nC(60) and tetraaromatic compounds by HT-GC × GC. This paper shows that HT-GC × GC analysis using CO(2) cryogenic modulator and short wide bore columns with a thin film of stationary phase allows the elution of linear alkanes up to nC(68) (641 °C) as well as of highly aromatic hydrocarbons like coronene. Furthermore, compared to previous studies, an on-column injector was used to reduce discrimination of high boiling point compounds.

Using gas chromatography to characterize a direct coal liquefaction naphtha.

Speciation of oxygenated compounds in direct coal liquefaction naphthas is essential considering their important roles in coal conversion reactions. This study attempts to characterize them as fully as possible using gas chromatographic systems. Firstly, GC-MS was deployed allowing the identification of a few ketones, alcohols, and phenols. This conventional analysis was complemented by the application of GC-GC-FID aiming to overcome the coelutions highlighted when using one-dimensional gas chromatography. Heart-cutting and comprehensive two-dimensional gas chromatography were used and the comprehensive system led to better performances as expected considering the complexity of the matrix. In fact, it allowed the identification of more than a hundred of oxygenated compounds belonging to five chemical families: alcohols, ketones, furans, acids and phenols. Average response factors of each of these families were determined by GC×GC-FID using calibration curves and vary from 1 (hydrocarbons) to 2.50 (carboxylic acids). Thanks to a breakthrough columns set involving a trifluoropropyl stationary phase, alcohols and phenols which represent around 14% of the sample were fully identified. A detailed quantification of these species was carried out for the first time in such matrices using the determined response factors. It was concluded that 90% (w/w) of the alcohols are aromatic (phenols), 5% (w/w) are cyclic and 5% (w/w) are linear. A quantification of hydrocarbon families was also achieved and shows that the matrix is mostly naphthenic (56%, w/w), but also contains aromatics (22%, w/w) and paraffins (8%, w/w). This detailed characterization leads to a better understanding of coal conversion processes and is essential to convert them into synthetic fuels.

Silicon speciation by gas chromatography coupled to mass spectrometry in gasolines.

A method for the speciation of silicon compounds in petroleum products was developed using gas chromatography coupled to mass spectrometry (GC-MS). Prior to analysis, several precautions about storage and conservation were applied for all samples. In spiked gasoline samples, limits of detection between 24 and 69 µg kg(-1) for cyclic siloxanes (D(4)-D(6)) and between 1 and 7 µg kg(-1) for other species were obtained. In this study, cyclic siloxanes (D(n)) and one ethoxysilane were quantified for the first time in petroleum products by a specific method based on response factor calculation to an internal standard. This method was applied to four samples of naphthas and gasolines obtained from a steam cracking process. Cyclic siloxanes were predominant in four investigated samples with concentrations ranging between 101 and 2204 µg kg(-1). Cyclic siloxane content decreased with an increase in their degree of polymerization. During a steam cracking process, silicon concentrations determined by GC-MS SIM (single ion monitoring) significantly increase. This trend was confirmed by ICP-OES (inductively coupled plasma optical emission spectroscopy) measurements but a difference on the total silicon content was observed, certainly highlighting the presence of unknown silicon species. GC-MS SIM method gives access to the chemical nature of the silicon species, which is crucial for the understanding of hydrotreatment catalyst poisoning in the oil and gas industry.

Considerations on orthogonality duality in comprehensive two-dimensional gas chromatography.

The term "orthogonal" in comprehensive two-dimensional gas chromatography (GC × GC) has a double sided meaning as it stands for a separation resulting from the combination of two independent retention mechanisms (Giddings, J. C. J. High Resolut. Chromatogr. 1987, 10, 319) but also for a 2D separation where the components are evenly distributed over the entire 2D space. It is shown in the present study that a nonorthogonal GC × GC system associating a polar stationary phase in the first dimension (poly(ethylene glycol)) to a nonpolar one in the second dimension (poly(dimethyl siloxane)) leads to a structured chromatogram, a high peak capacity, and a great 2D space occupation. This idea is demonstrated through the characterization of oxygenated compounds in a coal-derived middle distillate. Results show a clear separation between oxygenated species and hydrocarbons which are classified into linear alkanes, cyclic alkanes, and aromatics. A breakthrough configuration combining a polar poly(ethylene glycol) first dimension and a trifluoropropyl methyl stationary phase in the second dimension enabled a unique identification and quantification of linear, cyclic, and aromatic alcohols. This configuration which could be considered as nonorthogonal still involves two different retention mechanisms: polarity and boiling point in the first dimension and electronic interactions in the second dimension. It is selective toward electronegative poles of alcohols and phenols. The contributions of these two configurations compared to a conventional orthogonal system as well as their roles for oxygenated compounds speciation are highlighted. This contribution is measured through three 2D space occupation factors. It appears through these two examples that orthogonality is intimately linked to analyte properties, and a general concept of dimensionality must be considered.