8
VUV, D1319 (FIA), D5186 (SFC), and D6379 (HPLC-UV). While both the SFC and HPLC methods biased high on every sample for total aromatics, GC-VUV was evenly distributed on either side of the D1319 results, with four results slightly higher than, four slightly lower than, and two equal to reported D1319 data, and an average difference of only 0.4% volume (Figure 5). For the di- aromatic values, nine of the ten samples showed good correlation with D1840, and while the sample with the highest expected di-aromatic concentration reported high for GC-VUV, both SFC and HPLC reported a similar result (Figure 6).
In a world where time is money, the data gained from an analysis must be worth the time devoted to acquiring that data, and effi ciency is king. As the VUV technology matures, the effi ciency of its applications will only continue to grow as it is able to provide more accurate and detailed information in shorter analysis times.
References
1. Kanaujia, P., Gas Chromatography: Petroleum and Petrochemical Applications, in Encyclopedia of Analytical Science (Third Edition. 2019, Elsevier Ltd. p. 217-231.
2. Beens, J. and U. Brinkman, The role of gas chromatography in compositional analyses in the petroleum industry. Trends in Analytical Chemistry, 2000. 19(4).
3. Kosal, N., A. Bhairi, and M.A. Ali, Determination of hydrocarbon types in naphthas, gasolines and kerosenes: a review and comparative study of different analytical procedures. 1990, Fuel. p. 1012-1019.
4. International, A., D6730-01 Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography. 2016.
5. Dunkle, M.N., et al., Quantifi cation of the composition of liquid hydrocarbon streams: Comparing the GC-VUV to DHA and GCxGC. J Chromatogr A, 2019. 1587: p. 239-246.
Figure 6. A comparison of measured total di-aromatics content for 10 jet fuel samples. GC-VUV correlates well with both the referee method (D1840) and the alternative methods.
This method operates with a similarly high level of precision as D8071. Six jet fuel profi ciency samples were run 8 times each and analysed. All %RSD values are below 0.1% for total saturates, below 0.5% for total aromatics, and below 3.5% for total di- aromatics (Table 4).
Table 4. Precision of GC-VUV jet fuel analysis run on six jet samples, with 8 runs per sample. All %RSD values are below 3.5%, and most are below 1%.
6. International, A., D6839-18 Standard Test Method for Hydrocarbon Types, Oxygenated Compounds, and Benzene in Spark Ignition Engine Fuels by Gas Chromatography. 2018.
7. International, A., D1319-14 Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption. 2014.
8. International, A., D1840-07 Standard Test Method for Naphthalene Hydrocarbons in Aviation Turbine Fuels by Ultraviolet Spectrophotometry. 2017.
9. International, A., UOP326-17 Diene Value by Maleic Anhydride Addition Reaction. 2017.
10. de Andrade, D.F., D.R. Fernandes, and J.L. Miranda, Methods for the determination of conjugated dienes in petroleum products: A review. Fuel, 2010. 89: p. 1796-1805.
11. Schug, K.A., et al., Vacuum ultraviolet detector for gas chromatography. Anal Chem, 2014. 86(16): p. 8329-35.
12. Bai, L., et al., Permanent gas analysis using gas chromatography with vacuum ultraviolet detection. J Chromatogr A, 2015. 1388: p. 244-50.
13. International, A., D8071-17 Standard Test Method for Determination of Hydrocarbon Group Types and Select Hydrocarbon and Oxygenate Compounds in Automotive Spark-Ignition Engine Fuel using Gas Chromatography with Vacuum Ultraviolet Absorption Spectroscopy Detection (GC-VUV). 2017.
5. Conclusions
GC-VUV has quickly become a reputed methodology for analysis of fuels [16]. Applications for both gasoline and jet fuels display good correlation to existing methods with high levels of precision, while reducing run times by up to 80%. Future applications for both lighter (e.g., liquefi ed petroleum gas) and heavier (e.g., diesel, crude oils) distillation cuts are sure to follow in the wake of the technology’s current successes.
14. Walsh, P., M. Garbalena, and K.A. Schug, Rapid Analysis and Time Interval Deconvolution for Comprehensive Fuel Compound Group Classifi cation and Speciation Using Gas Chromatography-Vacuum Ultraviolet Spectroscopy. Anal Chem, 2016. 88(22): p. 11130-11138.
15. Liu, H., et al., Is vacuum ultraviolet detector a concentration or a mass dependent detector? J Chromatogr A, 2017. 1530: p. 171-175.
16. Santos, I.C. and K.A. Schug, Recent advances and applications of gas chromatography vacuum ultraviolet spectroscopy. J Sep Sci, 2017. 40(1): p. 138-151.
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