The organic matter in five oil shales (three from the Kimmeridge Clay sequence, one from the Oxford Clay sequence and one from the Julia Creek deposits in Australia) has been isolated by acid demineralisation, separated into kerogens and bitumens by solvent extraction and then characterised in some detail by chromatographic, spectroscopic and degradative techniques.
Kerogens cannot be characterised as easily as bitumens because of their insolubility, and hence before any detailed molecular information can be obtained from them they must be degraded into lower molecular weight, more soluble components. Unfortunately, the determination of kerogen structures has all too often involved degradations that were far too harsh and which lead to destruction of much of the structural information. For this reason a number of milder more selective degradative procedures have been tested and used to probe the structure of kerogens. These are:
1. Lithium aluminium hydride reduction. - This procedure is commonly used to remove pyrite from kerogens and it may also increase their solubility by reduction of labile functional groups. Although reduction of the kerogens was confirmed, increases in solubility were correlated with pyrite content and not kerogen reduction.
2. O-methylation in the presence of a phase transfer catalyst. - By the removal of
hydrogen bond interactions via O-methylation, it was possible to determine the
contribution of such secondary interactions to the insolubility of the kerogens. Problems were encountered with the use of the phase transfer catalyst.
3. Stepwise alkaline potassium permanganate oxidation. - Significant kerogen
dissolution was achieved using this procedure but uncontrolled oxidation of initial
oxidation products proved to be a problem. A comparison with the peroxytrifluoroaceticacid oxidation of these kerogens was made.
4. Peroxytrifluoroacetic acid oxidation. - This was used because it preferentially
degrades aromatic rings whilst leaving any benzylic positions intact. Considerable
conversion of the kerogens into soluble products was achieved with this procedure.
At all stages of degradation the products were fully characterised where possible
using a variety of techniques including elemental analysis, solution state 1H and 13C nuclear magnetic resonance, solid state 13C nuclear magnetic resonance, gel-permeationchromatography, gas chromatography-mass spectroscopy, fourier transform infra-red spectroscopy and some ultra violet-visible spectroscopy.
|Date of Award||Dec 1987|
- oil shales
- structural analysis
Student thesis: Doctoral Thesis › Doctor of Philosophy