Comprehensive two-dimensional GC for the analysis of low-molecular-weight oxygenates in three different matrices from a petrochemical pilot plant using a single calibration.

A method using comprehensive (2) DGC with flame ionisation detection was developed to quantify 17 low-molecular-weight oxygenates in three different matrices, namely water, oil and gas, using a single calibration. The method was required for the pilot-plant experiments of a chemical process unit. From an analytical perspective, the first task was to find a suitable analytical method with sufficient selectivity and sensitivity to analyse the selected oxygenates at low levels in the presence of high levels of hydrocarbons. The second was the accurate quantitation of oxygenates in the water, oil and gas fractions, using the same instrument and calibration. Both these requirements were met by using comprehensive (2) DGC in the inverse configuration and calibrating the detector with the number of moles injected versus response. The method was successfully applied for the characterisation of the reactor product stream of the chemical process unit and made it possible to determine the fate of the selected oxygenates after passing through the reactor. The development of the method and some of the results are described in this paper.

Comprehensive two-dimensional gas chromatography for the analysis of synthetic and crude-derived jet fuels.

Fully synthetic jet fuel (FSJF) produced via Fischer-Tropsch (FT) technology was recently approved by the international aviation fuel authorities. To receive approval, comparison of FSJF and crude-derived fuel and blends on their qualitative and quantitative hydrocarbon composition was of utmost importance. This was performed by comprehensive two-dimensional gas chromatography (GC×GC) in the reversed phase mode. The hydrocarbon composition of synthetic and crude-derived jet fuels is very similar and all compounds detected in the synthetic product are also present in crude-derived fuels. Quantitatively, the synthetic fuel consists of a higher degree of aliphatic branching with less than half the aromatic content of the crude-derived fuel. GC×GC analyses also indicated the presence of trace levels of hetero-atomic impurities in the crude-derived product that were absent in the synthetic product. While clay-treatment removed some of the impurities and improved the fuel stability, the crude-derived product still contained traces of cyclic and aromatic S-containing compounds afterwards. Lower level of aromatics and the absence of sulphur are some of the factors that contribute to the better fuel stability and environmental properties of the synthetic fuel. GC×GC was further applied for the analysis of products during Jet Fuel Thermal Oxidation Testing (JFTOT), which measures deposit formation of a fuel under simulated engine conditions. JFTOT showed the synthetic fuel to be much more stable than the crude-derived fuel.

Fractionation by liquid chromatography combined with comprehensive two-dimensional gas chromatography-mass spectrometry for analysis of cyclics in oligomerisation products of Fischer-Tropsch derived light alkenes.

In oligomerisation products of High Temperature Fischer-Tropsch (HTFT) derived light alkenes using a solid phosphoric acid (SPA) catalyst, the presence of cyclics was presumed although their occurrence could not be explained by the generally accepted oligomerisation mechanism. Notwithstanding the use of GC×GC-TOFMS, the cyclic alkanes could not be differentiated from the alkenes. On the one hand, compounds co-eluted in GC×GC and, on the other hand, MS cannot distinguish between these classes because of identical molecular masses and very similar mass fragmentation patterns. An LC pre-fractionation procedure utilising a silver-modified column was developed to separate the saturates from the unsaturates. Using this approach we were able, for the first time, to confirm the presence of cyclics, probably resulting from secondary reactions, in HTFT oligomerisation products. The occurrence of cyclics can be an indication of the beginning of carbonaceous deposit formation that could eventually lead to catalyst deactivation.

Comprehensive two-dimensional gas chromatography for the analysis of Fischer-Tropsch oil products.

The Fischer-Tropsch (FT) process involves a series of catalysed reactions of carbon monoxide and hydrogen, originating from coal, natural gas or biomass, leading to a variety of synthetic chemicals and fuels. The benefits of comprehensive two-dimensional gas chromatography (GC×GC) compared to one-dimensional GC (1D-GC) for the detailed investigation of the oil products of low and high temperature FT processes are presented. GC×GC provides more accurate quantitative data to construct Anderson-Schultz-Flory (ASF) selectivity models that correlate the FT product distribution with reaction variables. On the other hand, the high peak capacity and sensitivity of GC×GC allow the detailed study of components present at trace level. Analyses of the aromatic and oxygenated fractions of a high temperature FT (HT-FT) process are presented. GC×GC data have been used to optimise or tune the HT-FT process by using a lab-scale micro-FT-reactor.

The use of GC x GC with time-of-flight mass spectrometry to investigate dienes and Diels-Alder polymerisation products in high-temperature Fischer-Tropsch-based fuels.

Comprehensive GC in the reversed polarity mode i.e. a polar main column and an apolar secondary column have been used to differentiate cyclic olefins, dienes and cyclic dienes in high temperature Fischer-Tropsch (FT)-based fuels. The elucidation of the blobs in the contour plot was based on spectral data obtained by TOF-MS. The effectiveness of selective catalytic hydrogenation in transforming dienes into olefins could be studied. Dienes are prone to polymerisation by Diels-Alder reactions and dimers and trimers were detected in the 2-D plot by operating the MS in the ion extraction mode. Polymerisation is thought to be partially responsible for gum formation in high temperature FT-derived products.