The Application Notebook
F. Adam,1 F. Bertoncini,1 D. Thiébaut,2 M.-C. Hennion,2 N. Lahoutifard3 and A. Addinall,4
1IFP, Vernaison, France, 2ESPCI, Laboratoire Environnement et Chimie Analytique, 10 rue Vauquelin, Paris, France,
3SGE EUROPE, 12 avenue du Québec, Courtaboeuf, France, 4SGE Analytical Science, 7 Argent Place, Ringwood, Victoria, Australia.
The detailed molecular characterization of feedstocks and resulting products is a critical issue to better understand and improve hydroconversion processes.1 Neutral (indole, carbazole) and basic (aniline, quinoline and acridine) nitrogen containing hydrocarbons present in middle distillates at concentrations as low as 0.1–2.0% w/w poison catalysts used for hydrodesulphurization (HDS).2 They are also refractory to hydrotreatment processes preventing the efficient upgrade of middle distillates to transportation fuels.3 Conventional molecular analysis techniques fail to provide a detailed characterization of nitrogen compounds. As investigated here, comprehensive two-dimensional gas chromatography (GC×GC) appears to be a promising technique for overcoming these limitations.
Table 1: GCÃGC-NCD set-up.
A diesel cut was provided by IFP-Lyon, from cokefaction (diesel B, density: 0.880; total N: 1328 ppm; total basic N: 501 ppm; bp: 200–423 °C). A synthetic mixture of 14 relevant N-compounds (N-Mix) obtained from Chiron (Villeurbanne, France), Sigma-Aldrich (Lyon, France) and Acros (Noisy le grand, France) was prepared for GC×GC separation evaluation.
Figure 1
Several secondary columns have been investigated for the separation of some reference nitrogen compounds occurring in middle distillates.1 Results are presented in Figure 1 and demonstrate that the combination of a polar and longer SolgelWax as the second dimension column to a first non polar BPX5 column allows the total separation when hyphenated.
Figure 2
Diesel B was then analysed using this column combination. The resulting GC×GC chromatogram is shown in Figure 2.
The results clearly show that GC×GC allows the comprehensive separation and precise quantitative analysis of nitrogen compounds by chemical class in middle distillates.
The enhanced peak capacity and sensitivity of comprehensive two-dimensional gas chromatography provided unequalled separation and identification of nitrogen compounds in diesel samples.
The proposed GC×GC method allows the accurate determination of basic to neutral nitrogen ratio. For the first time, the comprehensive determination of nitrogen compounds by family can also be reported.
1. F. Adam et al., J Chromatogr. A, 1148, 55 (2007).
2. Y. Briker et al., Fuel, 82, 1621 (2003).
3. G.W. Mushrush et al., Fuel Process. Technol., 61, 197 (1999).
4. J. Beens et al., J. Chromatogr. A, 919, 127 (2001).
SGE Analytical Science Pty Ltd
7 Argent Place, Ringwood, Victoria 3134, Australia
tel. +61 3 9837 4200 fax +61 3 9874 5672
E-mail: support@sge.com Website: www.sge.com
Inside the Laboratory: The Gionfriddo Group at the University at Buffalo
March 28th 2024In this edition of “Inside the Laboratory,” Emanuela Gionfriddo, PhD, an associate professor of chemistry at the University at Buffalo, discusses her group’s current research endeavors, including using solid-phase microextraction (SPME) coupled to liquid chromatography (LC) and gas chromatography (GC) to further understand the chemical relationship between environmental exposure and disease and elucidate micropollutants fate in the environment and biological systems.
High-Throughput Analysis of Volatile Compounds in Air, Water, and Soil Using SIFT-MS (Apr 2024)
March 27th 2024This study demonstrates high-throughput analysis of BTEX compounds from several matrices (air, water and soil). Detection limits in the single-digit part-per-billion concentration range (by volume) are readily achievable within seconds using SIFT-MS, because sample analysis is achieved without chromatography, pre-concentration, or drying. We also present a calibration approach that enables speciation of ethylbenzene from the xylenes in real time.
Adoption of SIFT-MS for VOC Pollution Monitoring in South Korea
March 27th 2024This publication reviews VOC pollutant monitoring applications of SIFT-MS in South Korea. SIFT-MS has been applied to emission source characterization, fenceline monitoring, ambient monitoring, pollution mapping, and incident response (including the use of drone-based sampling) for hazardous air pollutants (HAPs), odor nuisance species, and compounds that have high ozone formation potential (OFP) and/or contribute to secondary aerosol (SOA) formation.