Group-type fractionation of petroleum and alternative fuels by column liquid chromatography

The present paper introduces an instrumental procedure based on column liquid chromatography for the total analysis of petroleum heavy ends and similar samples. The procedure avoids the precipitation of asphaltenes and asphaltols. One sequence of eluents fractionates the sample into 8 fractions: 5 non-polar (hydrocarbons), one intermediate (resins), and 2 polar fractions (asphaltenes and asphaltols). Quantitative results from gravimetric measurements and UV-Vis and FTIR spectra of fractions obtained from petroleum heavy ends are presented, as well as those from GC/MS data obtained from one fraction obtained from liquefaction of biomass. The method presented is easy to set up and operate, requires minimum operator attention, is reliable (no precipitation), reproducible, and inexpensive.     

Multi micro high performance liquid chromatography

Summary The purpose of the study was to develop a micro HPLC system with physically changeable selectivity. This was done using two series-coupled beds of chemically differing stationary phases in a packed fused silica column. The selectivity change, in fine repeatable steps, was possible by the stepwise moving of a tube oven, covering only 50% of this tandem column. Each step of selectivity started with a position change of the oven, thus heating up a fresh position of the more polar and the non-polar column bed. As the chromatogram is thus repeated under these new selectivity conditions, multiple chromatograms result. For this reason we call the technique Multi Micro HPLC. This very simple mode of operation provides an analytical tool for developing separation conditions and which allows optimizing for a given special sample and checking for one of the most critical problems in HPLC: unidentified peak overlapping. The selectivity changes are nonlinearly correlated with the oven position with regards to temperature field distribution and are greater than is possible by simple change of column temperature. Micropacked columns are ideal for quick temperature changes. Elevated temperatures in HPLC help to shorten analysis time. The concepts discussed above provide an explanation of how a normal, formerly chemically homogeneous, column can become very temperature sensitive after detoriation at the inlet. In fact the column has become an unintentional tandem column and peak positions tend to move erratically as its selectivity changes drastically by inhomogeneous temperature changes along the separation path.     

The determination of serum retinol by high performance liquid chromatography

A method for the quantitation of retinol in serum by normal phase high performance liquid chromatography is described. The mobile phase consists of a hexane/diethylether/methanol mixture with spectrophotometric detection. The sample preparation is similar to that described by other authors and involves protein precipitation followed by extraction and direct injection onto the chromatograph. Adequate sensitivity is achieved using 200 μl samples. The internal standard chosen is α-naphthol because of its spectral similarities to retinol and its greater stability than the commonly used retinyl esters. The method has been successfully applied to the clinical evaluation of a number of malabsorption syndromes for which it is preferred to the measurement of total carotenoids.     

Investigation of the low temperature effect in normal phase micro high performance liquid chromatography

The low temperature effect has been investigated on a set of three different silica-gel micro columns with FC-78 as eluent. An open tubular micro glass capillary, a packed micro glass capillary, and a packed micro teflon column were examined. Temperature dependences of separation factors and theoretical plate numbers were determined. It appears that a decrease in column temperature improves chromatographic selectivity while column efficiency decreases. The compensation temperatures were determined for these systems. The results suggest that the retention mechanism operative in the low temperature range is almost the same as that in the normal temperature range. However, the mechanism differs from that of reversed phase systems.     

Investigation of the low temperature effect in reversed phase micro high performance liquid chromatography

The low temperature effect has been investigated in reversed phase micro high performance liquid chromatography with various aqueous mobile phase systems by an approach based on enthalpy-entropy compensation. The compensation temperatures, Tc , were determined for these systems, and the results show that the retention mechanism in a lower temperature column is similar to that in a normal temperature column in the reversed phase mode at mobile phase water contents above 9.8%. At lower water contents, the separation mechanism is different from that in the reversed phase mode, but otherwise very similar to that in the normal phase mode.     

Identification of compounds in gasoline range mixtures using combined group-type and capillary GC separations

Summary A procedure is described to improve the identification of the hydrocarbon isomers separated on a single capillary column. Group-type PNA separation was combined with capillary GC analysis. Different paraffin and naphthene groups separated by carbon number on the 13X column of a PNA-analyzer were heart-cut and analysed off-line by capillary GC. Capillary GC chromatograms of the trapped groups compared to that of the original sample helped to identify the peaks (at least by group-type), to clear up mixed peaks and to find out the ratio of the compounds co-eluting in that particular peak. Results were used to create identification tables for different types of naphthas. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Endcapping of high performance liquid chromatography packings derived from silica gel

The effect of endcapping a reversed phase chromatographic packing material derived from silica gel depends on the degree of derivatization of the phase. The effect can be dramatic for phases with low loading. Whether an octadecylated silica gel has been endcapped or not can be ascertained by chromatographing the pair naphthalene/1-nitronaphthalene with a water/methanol eluent producing at least k' ≈ 10 for naphthalene. The ratio of the two k' values is 1.4 or higher for an endcapped material, while it is only 1.1 -1.2 for a non-endcapped phase. A similar approach fails to give conclusions of similar utility for octylated silica gels.     

Detailed hydrocarbon analysis of gasoline by GC-MS (SI-PIONA)

A gas chromatographic – mass spectrometric (GC-MS) method has been developed for detailed analysis of the hydrocarbon content of gasoline. The method is equipped with special software and includes the analysis of oxygenated compounds in a single run. The technique utilizes three basic components: the separating power of high resolution capillary gas chromatography, a mass spectrometer with a controllable ion source and ion fragmentation ratios, and unique software for data handling and preparation of reports. The C₄ to C₁₂ range of hydrocarbons in gasoline is covered by the method. A sample of unleaded gasoline from a gas station was analyzed without sample preparation. The results are discussed.     

Quantitative determination of low concentrations of DHETX m. s. in human plasma by high performance liquid chromatography with fluorescence detection

A method is described for separation of low amounts of DHETX m. s. from human plasma, based on extraction and determination by high performance liquid chromatography with fluorimetric detection.