Journal of Analytical Science and Technology (Sep 2020)
Quantitative carbon distribution analysis of hydrocarbons, alcohols and carboxylic acids in a Fischer-Tropsch product from a Co/TiO2 catalyst during gas phase pilot plant operation
Abstract
Abstract Comprehensive two-dimensional gas chromatography (GCxGC) analysis for 1-alcohols and gas chromatography–mass spectrometry (GC-MS) analysis for carboxylic acids, derivatised as their methyl esters, have been applied to liquid and wax Fischer-Tropsch (FT) hydrocarbon products. These methods in combination with conventional one-dimensional gas chromatography (GC) analysis of the aqueous, gaseous, liquid hydrocarbon and wax products plus conventional high-performance liquid chromatography (HPLC) analysis of the aqueous phase has allowed a quantitative distribution analysis of FT hydrocarbon and oxygenated products to be demonstrated for a Co/TiO2 catalyst operating in a fixed bed gas phase pilot plant utilising CANSTM catalyst carrier devices. The GC-MS method used is, to the best of our knowledge, the first application of this derivatisation route for the quantification of individual carboxylic acids in FT hydrocarbon product streams. Whilst the hydrocarbons and oxygenates that were identified are known compounds formed during the low temperature, Co catalysed, FT process the combination of the multiple analysis techniques used has allowed a level of detail to be gained on the product composition that is seldom reported. Additionally, 1H nuclear magnetic resonance spectroscopy (NMR) and 13C NMR analyses were used to quantify the average concentration of 1-olefin, cis- and trans-2-olefins, 1-alcohol and aldehyde as appropriate for the technique used. Comparison of GCxGC versus 1H NMR and GC-MS versus a KOH titration confirmed the applicability of the chromatographic methods for the quantitative analysis of FT oxygenated compounds. Long-chain 1-alcohols and carboxylic acids, ≥ C3, were found to be present at levels of 1/10th and 1/1000th that of hydrocarbons of equivalent carbon chain length respectively. The 1-olefin:n-paraffin ratio in the hydrocarbon liquid and wax products was found to decrease significantly with increasing carbon chain length and much more so than those of the 2-olefin or 1-alcohol.
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