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Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices

Marko Dokic (UGent) , Nenad Ristic (UGent) , Natália Olahová (UGent) , Guy Marin (UGent) and Kevin Van Geem (UGent)
(2017) JOURNAL OF CHROMATOGRAPHY A. 1509. p.102-113
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Abstract
An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC × GC) equipped with two capillary columns (Rtx® -1 PONA × SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC × GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H2S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC × GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefinrich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC × GCFID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75% of the sulfur contained in the feed is converted to hydrogen sulfide, 13% to alkyl homologues of thiophene while the remaining 12% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen evolution, bio-waste pyrolysis, supercritical water treatment, etc
Keywords
2-DIMENSIONAL GAS-CHROMATOGRAPHY, GC X GC, CHEMILUMINESCENCE DETECTOR, MASS-SPECTROMETRY, INTERCOMPARISON EXPERIMENT, STEAM CRACKING, OIL, PYROLYSIS, MIXTURES, SEPARATION

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Chicago
Dokic, Marko, Nenad Ristic, Natália Olahová, Guy Marin, and Kevin Van Geem. 2017. “Quantitative On-line Analysis of Sulfur Compounds in Complex Hydrocarbon Matrices.” Journal of Chromatography A 1509: 102–113.
APA
Dokic, M., Ristic, N., Olahová, N., Marin, G., & Van Geem, K. (2017). Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices. JOURNAL OF CHROMATOGRAPHY A, 1509, 102–113.
Vancouver
1.
Dokic M, Ristic N, Olahová N, Marin G, Van Geem K. Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices. JOURNAL OF CHROMATOGRAPHY A. 2017;1509:102–13.
MLA
Dokic, Marko, Nenad Ristic, Natália Olahová, et al. “Quantitative On-line Analysis of Sulfur Compounds in Complex Hydrocarbon Matrices.” JOURNAL OF CHROMATOGRAPHY A 1509 (2017): 102–113. Print.
@article{8536609,
  abstract     = {An improved method for on-line measurement of sulfur containing compounds in complex matrices is presented. The on-line system consists of a specifically designed sampling system connected to a comprehensive two-dimensional gas chromatograph (GC {\texttimes} GC) equipped with two capillary columns (Rtx{\textregistered} -1 PONA {\texttimes} SGE BPX50), a flame ionization detector (FID) and a sulfur chemiluminescence detector (SCD). The result is an unprecedented sensitivity down to ppm level (1 ppm-w) for various sulfur containing compounds in very complex hydrocarbon matrices. In addition to the GC {\texttimes} GC-SCD, the low molecular weight sulfur containing compounds such as hydrogen sulfide (H2S) and carbonyl sulfide (COS) can be analyzed using a thermal conductivity detector of a so-called refinery gas analyzer (RGA). The methodology was extensively tested on a continuous flow pilot plant for steam cracking, in which quantification of sulfur containing compounds in the reactor effluent was carried out using 3-chlorothiophene as internal standard. The GC {\texttimes} GC-FID/-SCD settings were optimized for ppm analysis of sulfur compounds in olefinrich (ethylene- and propylene-rich) hydrocarbon matrices produced by steam cracking of petroleum feedstocks. Besides that is primarily used for analysis of the hydrocarbon matrix, FID of the GC {\texttimes} GCFID/-SCD set-up serves to double check the amount of added sulfur internal standard which is crucial for a proper quantification of sulfur compounds. When vacuum gas oil containing 780 ppm-w of elemental sulfur in the form of benzothiophenes and dibenzothiophenes is subjected to steam cracking, the sulfur balance was closed, with 75\% of the sulfur contained in the feed is converted to hydrogen sulfide, 13\% to alkyl homologues of thiophene while the remaining 12\% is present in the form of alkyl homologues of benzothiophenes. The methodology can be applied for many other conversion processes which use sulfur containing feeds such as hydrocracking, catalytic cracking, kerogen evolution, bio-waste pyrolysis, supercritical water treatment, etc},
  author       = {Dokic, Marko and Ristic, Nenad and Olahov{\'a}, Nat{\'a}lia and Marin, Guy and Van Geem, Kevin},
  issn         = {0021-9673 },
  journal      = {JOURNAL OF CHROMATOGRAPHY A},
  keyword      = {2-DIMENSIONAL GAS-CHROMATOGRAPHY,GC X GC,CHEMILUMINESCENCE DETECTOR,MASS-SPECTROMETRY,INTERCOMPARISON EXPERIMENT,STEAM CRACKING,OIL,PYROLYSIS,MIXTURES,SEPARATION},
  language     = {eng},
  pages        = {102--113},
  title        = {Quantitative on-line analysis of sulfur compounds in complex hydrocarbon matrices},
  url          = {http://dx.doi.org/10.1016/j.chroma.2017.06.006},
  volume       = {1509},
  year         = {2017},
}

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