A Unified Approach for the Measurement of Individual or Total Volatile Organic Sulfur Compounds in Hydrocarbon Matrices by Dual-Plasma Chemiluminescence Detector and Low Thermal Mass Gas Chromatography

Abstract

A novel gas chromatographic technique has been developed, offering dual-analytical capability of either speciation or rapid measurement of total volatile sulfur compounds in hydrocarbon matrices using the same hardware. The technique employs a pressurized liquid injection system for the delivery of volatile liquid hydrocarbons, low thermal mass gas chromatography, and a dual-plasma sulfur chemiluminescence detector to enable this dual capability with a high degree of sensitivity and selectivity towards sulfur-containing compounds. Using the technique described, a detection limit in the range of 20 ppb sulfur and less than 30 s analysis is attained. Response is linear over five orders of magnitude, with a high degree of repeatability.

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes

“…Equimolar response of a detector refers to its ability to yield a constant response per mole of S regardless of the type of sulfur compounds involved. The equimolar response of SCD has been established in previous report and has become widely accepted . In this study, standards of individual sulfur compounds were analyzed using GC as a sample introduction device with a short piece of uncoated deactivated fused‐silica tubing connecting the inlet and the SCD.…”

“…semivolatile sulfur-containing compounds in various matrices. A number of selective detectors, such as flame photometric detector (FPD) and its variants, sulfur chemiluminescence detector (SCD), atomic emission detector, and mass spectrometry detector have been applied successfully for the selective determination of sulfur compounds [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. As sulfur selective detectors, both SCD and FPD utilize the chemiluminescent reactions of sulfur compounds in a hydrogen/air flame to achieve selective and sensitive detection of these specific compounds.…”

“…FPD has its constraints including the lack of linearity in response due to formation of diatomic species S 2 and quenching or suppression of sulfur signal by coeluted hydrocarbons. Compared to FPD, SCD favorably produces a linear response, offers very high selectivity, and is far less susceptible to hydrocarbon interferences [6,10,11,[18][19][20][21][22].…”

“…SCD is proved to be an excellent tool for sulfur compound analysis in hydrocarbon matrices. By combining the separation power of an analytical column in capillary GC with this highly sensitive and selective detector, detailed speciation analysis of individual sulfur compounds can be achieved . Speciation is desirable but not always necessary.…”

“…As sample matrices become more complex and the needs for ultratrace analysis intensify, a reliable, rapid, low‐maintenance, and cost‐effective technique for total sulfur analysis is highly demanded in nearly all segments of the petroleum and chemical industry. SCD offers capability of rapid measurement of total sulfur without chromatographic separation, which has been showcased in the literature . The burner employed in this model, 8355 SCD is a redesigned and upgraded version of the original 2004 dual‐plasma design with substantial mechanical improvements, which render a platform that is more robust and reliable, easy to operate and maintain, and offers better sensitivity and selectivity .…”