Determination of sulfur components in light petroleum streams by high-resolution gas chromatography with chemiluminescence detection

Chawla, B.; Sanzo, Frank Di

doi:10.1016/0021-9673(92)80032-p

Cited by 76 publications

(25 citation statements)

References 16 publications

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“…With the three standards (thiophene, BT and DBT), it was first established that the peaks areas per S were statistically the same for these three molecules. Thus, the total concentration of sulfur compounds was taken to be proportional to the sum of the peaks sulfur concentration values (a similar approach was used by Chawla and Di Sanzo, 1992). This was acceptable for conditions where complete sample elution was achieved after injection and upon correction for noise data.…”

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confidence: 99%

New sorbents for desulfurization of diesel fuels via π‐complexation

2004

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Desulfurization of a commercial diesel fuel by different adsorbents was studied in a fixed-bed adsorber operated at ambient temperature and pressure. In general, the adsorbents tested for total sulfur adsorption capacity at breakthrough followed the order: AC/Cu(I)-Y Ͼ Cu(I)-Y Ͼ Selexsorb CDX (alumina) Ͼ CuCl/␥-Al 2 O 3 Ͼ activated carbon Ͼ Cu(I)-ZSM-5. The best adsorbent, AC/Cu(I)-Y (layered bed of 15 wt % activated carbon followed by Cu(I)Y), is capable of producing 30 cm 3 of diesel fuel per gram of adsorbent with a weighted average content of 0.15 ppmw-S, and about 20 cm 3 of diesel fuel per gram of adsorbent with a weighted average content of 0.06 ppmw-S. These low-sulfur fuels are suitable for fuel cell applications. The added layer of carbon not only delayed the sulfur breakthrough significantly but also sharpened the sulfur wavefronts. GC-FPD results showed that the -complexation sorbents selectively adsorbed highly substituted thiophenes, benzothiophenes, and dibenzothiophenes from diesel, which is not possible with conventional hydrodesulfurization (HDS) reactors. The high sulfur selectivity and high sulfur capacity of Cu(I)Y were because of -complexation. © 2004 AmericanInstitute of Chemical Engineers AIChE J, 50: [791][792][793][794][795][796][797][798][799][800][801] 2004 Keywords: desulfurization of liquid fuels, -complexation sorbent, desulfurization by adsorption, desulfurization of diesel, 4-methyl-dibenzothiophene adsorption, 4, 6-dimethyl- dibenzothiophene adsorption IntroductionThe federal government mandates a reduction in gasoline and diesel sulfur levels to 30 and 15 ppm, respectively, from the current levels of 300 -500 ppmw, to be implemented by 2006(Krause, 2000. This makes refiners consider eliminating production of onboard transportation fuels because of the high costs that will arise from compliance with such regulations (Parkinson, 2001). For fuel cell applications with gasoline as the feed, the sulfur content should be below 1 ppmw. For automotive fuel cells, liquid hydrocarbons are ideal fuels because of their higher energy density, availability, and safety for transportation and storage. However, the water-gas shift catalysts as well as fuel-cell electrode catalysts are poisoned by sulfur, and the sulfur content in the liquid fuel needs to be preferably less than 0.1 ppmw.Hydrodesulfurization (HDS) is very effective in removing thiols and sulfides, but it is not effective for the removal of thiophenic compounds. For example, the H 2 S produced during reaction of some thiophene derivatives is one of the main inhibitors for deep HDS of unreactive species (Ma et al., 1994;Knudsen et al., 1999). Among the unreacted refractory species are 4-methyl-dibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4, 6-DMDBT). These molecules are common in diesel fuels. The methyl groups in these species create a steric effect that hinders the capacity of HDS catalysts to chemisorb the sulfur atoms as depicted in Figure 1a. Such steric hindrance is not present for adsorption by -complexatio...

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New sorbents for desulfurization of diesel fuels via π‐complexation

2004

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“…For petrochemical and petroleum related samples, SCD results generally agree with other accepted test procedures and equipment, such as X-ray fluorescence, to within 10% [12][13][14]. Coupled with chromatography, however, the SCD possesses the ability to speciate sulfur compounds of interest, while strictly elemental techniques cannot.…”

Section: Introductionmentioning

confidence: 80%

Simultaneous Measurement of Hydrocarbons and Sulfur Compounds using Flame Ionization and Sulfur Chemiluminescence Detection for Sulfur Simulated Distillation

Shearer¹,

Meyer²

1999

J. High Resol. Chromatogr.

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“…However, GC with SCD is an outstanding combination for selective detection of trace concentration of sulphur-containing compounds in different kinds of samples. The SCD possesses advantages over other sulphur selective detectors and it is finding widespread application in the analysis of petrochemical products [40 -42], natural gases [43], foods and beverages [44,45], environmental samples [46], perfume, fragrances etc. The SCD was first developed as an analyser for the determination of sulphur compounds in air [47], and later it was commercialised as a GC detector utilising an FID-style arrangement operated under hydrogen-rich conditions to generate sulphur monoxide (SO) as the basis of chemiluminescence [48].…”

Section: Sulphur Chemiluminescence Detector (Scd)mentioning

confidence: 99%

Detector technologies for comprehensive two‐dimensional gas chromatography

Mühlen

Khummueng

Zini

et al. 2006

J of Separation Science

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The detector is an integral and important part of any chromatographic system. The chromatographic peak profiles (i.e. peak separation) should, ideally, be unaffected by the detector--it should only provide the sensing capacity required at the end of a column separation process. The relatively new technique of comprehensive 2-D GC (GC x GC) extends the performance of GC manyfold, but comes at a price--existing GC systems may not be adequately designed with the requirements of GC x GC in mind. This is primarily the need for precise measurement of very fast peaks entering the detector (e.g. as fast as 50 ms basewidth in some instances). The capacity of the detector to closely track a rapidly changing chromatographic peak profile depends on a number of factors, such as design of flow paths and make-up gas introduction, type of detector response mechanism, and the chemistry of the response. These factors are discussed here as a means to appreciate the technical demands of detection in GC x GC. The MS detector will not be included in this review.

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Determination of sulfur components in light petroleum streams by high-resolution gas chromatography with chemiluminescence detection

Cited by 76 publications

References 16 publications

New sorbents for desulfurization of diesel fuels via π‐complexation

New sorbents for desulfurization of diesel fuels via π‐complexation

Simultaneous Measurement of Hydrocarbons and Sulfur Compounds using Flame Ionization and Sulfur Chemiluminescence Detection for Sulfur Simulated Distillation

Detector technologies for comprehensive two‐dimensional gas chromatography

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