Investigation of different chemical modifiers based on the Pd/Mg mixture for the determination of sulfur in shale oil by high-resolution continuum source graphite furnace molecular absorption spectrometry

摘要

This study investigated different combinations of Pd/Mg, as chemical modifier, for sulfur determination, via CS molecule, in shale oil samples by high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS GF MAS). It was evaluated the mixture Pd/Mg in aqueous solution, Pd/Mg in propan-1-ol and the Pd/Mg in propan-1-ol plus Ru as a permanent modifier. The best sensitivity was achieved with Pd/Mg mixture in propan-1-ol. The high solubility of the samples in propan-1-ol promotes a better interaction with the modifier and, consequently, a more efficient thermal stability of the CS molecules. Due to the high sulfur content in the samples, the analytical line at 258.288 nm was used. Only a minimum sample preparation was required, i.e., a dilution in propan-l-ol by a factor of 1:10 (w/w). Temperatures of 800 degrees C and 2200 degrees C were the optimized conditions for pyrolysis and vaporization, respectively. The calibration curve was constructed with c-cysteine aqueous standard solutions. The characteristic mass was 27 ng; detection and quantification limits were 0.012% (w/w) and 0.039% (w/w), respectively. The accuracy of the proposed method was confirmed by the statistical agreement (Student's and Welch's t-test at 95% confidence level) using the certified reference material CRM NIST 1084a and an OTE oil sample whose sulfur content was previously determined by the standard method ASTM D4294. The method was successfully applied in three shale oil samples. The sulfur content in the investigated samples ranged from 1.0% (w/w) to 1.3% (w/w).