With biomass feedstock supply not readily available in quantities required by refineries and most biomass conversion technologies still being developed and scaled up, mixing renewable carbon from biomass with fossil carbon by co-processing or post-catalytic upgrading blending are considered promising paths to incorporate biogenic carbon into the existing liquid transportation fuel infrastructure. These approaches require the accurate determination of the amount of biogenic carbon present in a blend of fossil-based and biomass-based transportation liquid, both for determining product quality as well as assigning the appropriate amount of renewable carbon credits. Carbon-14 (14C) is ideal in tracking the amount of biogenic carbon due to the absence of 14C in much older petroleum liquids. In this presentation, we describe a method using liquid scintillation counter (LSC) to analyze and quantify biogenic carbon concentrations as low as 1 wt% in two non-biogenic matrices: toluene and refinery petroleum diesel cut. Compared to the more sensitive accelerator mass spectroscopy (AMS), LSC has the advantages of simple sample preparation, smaller footprint, lower cost and relatively short analysis time, making the latter instrument more suited in an industrial setting. Quenching effects, which results when the energy emitted by the radioisotope is not completely received by the detector, affect the accuracy of the measurement, were considered. Quench curve, external standard and spiked internal standard methods for quench determination were compared. Two types of LSC instruments, Perkin Elmer’s Quantulus and TriCarb, were used to develop the method and analyze the samples. Lastly, a series of samples with low concentration of upgraded pyrolysis bio-oil cuts were analyzed using both AMS and LSC, showing comparable values.

Quantification of biogenic carbon in petroleum-renewable carbon mixture through 14C determination by liquid scintillation counter (LSC) detector

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ACS Fall 2022

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