Shale chromatographic analysis

Also important is the use of the modem chromatographic methods to separate and identify individual components in commercial cmde shale oil. The use of efficient gas chromatographic columns coupled with ancillary techniques such as mass spectrometry and vapor-phase IR spectroscopy allows the identification of individual shale oil components. A principal part of this study is the comparison of diflFerent types of open tubular columns for the separation of the alkane-alkene fraction of shale oil WCOT, SCOT, and PLOT columns are examined. Gas chromatographic separation of shale oil acids and bases also is performed allowing the identification of these components. The potential utility of subtractive pre-columns in HPLC analysis is illustrated also. 

On considering the optimal chromatographic conditions for analysis of the more polar constituents of shale oil it becomes apparent that both packed columns and PLOT columns have useful features. An example involves the acid-component fraction of shale oil obtained by sodium hydroxide extraction, removal of nonpolar species with benzene, methyl-... 

The classical silica gel chromatographic method for determination of percent olefins in shale oils was studied and found wanting, mainly because of cross-contamination from high levels of olefins and heteroatom-containing compounds. This paper describes a new hydroboration/oxidation procedure for olefins, and reports its use in hydrocarbon-type analysis of both whole shale oils and distillate fractions. Percent composition values for three whole oils ranged as follows saturates, 13-26 olefins, 16-20 aromatics, 5-14 polar compounds, 41S2. A discussion of IR analysis for relative amounts of specific olefin types such as terminal, internal trans, and methylene structures is included. 

Other major shale constituents such as C, H, N, and S are determined by thermal decomposition and instrumental detection methods. Oxygen is determined by 14 MeV neutron activation analysis. Parr or Leco BTU bomb combustion and subsequent ion chromatographic determination is used for halogens, sulfate and nitrate. Ion chromatography is also suitable for anionic characterization of shale process waters. Two analytical procedures for oil shales should be used with caution. Kjeldahl nitrogen procedure has been found to give reproducible but considerably low results for certain oil... 

The use of thermogravimetric analysis (TGA) apparatus to obtain kinetic data involves a series of trade-offs. Since we chose to employ a unit which is significantly larger than commercially available instruments (in order to obtain accurate chromatographic data), it was difficult to achieve time invariant O2 concentrations for runs with relatively rapid combustion rates. The reactor closely approximated ideal back-mixing conditions and consequently a dynamic mathematical model was used to describe the time-varying O2 concentration, temperature excursions on the shale surface and the simultaneous reaction rate. Kinetic information was extracted from the model by matching the computational predictions to the measured experimental data. 

Another promising spectroscopic method for the infrared analysis of samples which do not lend themselves readily to normal preparation techniques is that of photoacoustic detection 4,12,17,18) Examples of the application to catalyst, poiymer, chromatographic sections or spots, and coals, tar sands and shale oils, have been discussed (F5-7,9,10,13,16) most novel applications of infrared photo-... 

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