Studies of the saturate and aromatic hydrocarbon unresolved complex mixtures in petroleum
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This thesis reports the results of investigations carried out into the composition of the saturate and aromatic unresolved complex mixtures (UCMs) in crude oils. It is divided into two sections. Section A reports on studies of the saturate UCM and Section B reports on studies of the aromatic UCM. UCMs are mixtures of very large numbers of compounds of low individual abundances, hence structural information on individual components is difficult or impossible to obtain using conventional GC or GC-MS techniques. The investigations reported in this thesis used a combination of GC-MS techniques (Section A) and oxidations of UCMs followed by GC-MS characterisation of the oxidation products (Section B) to develop a more detailed picture of the structures of components of the saturate and aromatic UCMs. UCMs are present in all crude oils, and may account for the vast majority of the material present in heavily weathered or biodegraded oils. An understanding of the types of compounds present may have a bearing on the refining processes an oil is subjected to, as well as assessing its potential environmental and toxicological effects.Single branched C(subscript)18 isomers were prepared to establish the chromatographic behaviour and mass spectral fragmentation patterns of open chain compounds with ethyl-, propyl-, butyl- and pentyl- substituents. All open chain structural isomers with a single n-alkyl branch larger than methyl in the range C(subscript)10 to C(subscript)20 were identified at each carbon number in a series of crude oils of varying ages, source types and depositional environments. Also, C(subscript)21 to C(subscript)25 structural isomers containing an ethyl branch were identified in all of these samples. This represents a total of 163 compounds. These monoalkylalkanes comprise approximately 3 % of the alkanes in these oils, with the n-alkanes (35-60 %) and methylalkanes (10 %) being the most abundant compound classes present. Isoprenoids, alkylcyclohexanes and other branched and/or cyclic alkanes make up the remainder of the material.Rock samples from a sedimentary sequence of Late Cretaceous age were analysed for ethylalkanes using GC-MS techniques. In the less mature samples, 3- and 5-ethylalkanes were in higher abundance relative to the other isomers at odd carbon numbers from C(subscript)17 to C(subscript)23. In the more mature samples, this odd preference was no longer apparent. Several other low maturity sediment samples were analysed and found to have a similar ethylalkane distribution to the shallow sample from the sedimentary sequence. A mature crude oil which was also analysed exhibited a distribution similar to the deeper sample from the sedimentary sequence. Tetralin pyrolysis of a low maturity lignite sample yielded only the 3- and 5-substituted ethylalkanes, providing supporting evidence that the initial odd preference is the result of defunctionalisation of specific natural product precursors containing a 3- or 5-ethylalkyl structural moiety. With increasing maturity this preference is diluted by input of ethylalkanes without preference. A mechanism involving acid-catalysed rearrangement of n-alkenes to form monoalkylalkanes is proposed to account for the loss of preference in ethylalkane relative abundances.Investigations into the composition of aromatic unresolved complex mixtures were conducted by oxidising the total aromatic fraction of a moderately biodegraded crude oil (biodegradation level 4) using potassium permanganate. This reagent cleaves the alkyl substituents attached to aromatic rings between the alpha and beta carbons and oxidises the alpha carbon to a carboxylate group. A biodegraded crude oil was chosen because the majority of the resolved components have been removed by biodegradation, leaving a complex mixture of compounds almost completely unresolved by gas chromatography. The oxidation product was separated into dichloromethane-soluble monocarboxylic acids (both aliphatic and aromatic) and water-soluble polycarboxylic acids (aromatic only). GC-MS analysis of these oxidation products gave the proportions of monosubstituted:disubstituted:trisubstituted:tetrasubstituted monoaromatic rings as 29:59:12:0.1, of which from one to three substituents were carboxylic acid groups with the remainder of the substituents being unoxidised methyl groups. Of the disubstituted monoaromatic oxidation products, 53 % were dicarboxylic acids with the most sterically hindered 1,2-substitution pattern. This observation was interpreted as evidence for the presence of significant amounts of naphthenoaromatic systems such as tetralins and indanes in the crude oil aromatic fraction. Analysis of the permanganate oxidation products also enabled a quantitative measure of the proportion of methyl substituents to be made. It was found that methyl groups accounted for a significant proportion of the alkyl substituents attached to aromatic systems. Of the disubstituted monoaromatic oxidation products, 59 % had a methyl group as one of the substituents, while of trisubstituted monoaromatic systems, 41% had one methyl and 37 % had two methyls. Compounds containing a biphenyl carbon skeleton comprised 3 % of the aromatic oxidation products, with isomers containing from one to four substituents of which one was a carboxylic acid group and the remainder were unoxidised methyls. This indicates that biphenyls containing more than one alkyl (>C(subscript)1) substituent were not present. Of the monosubstituted biphenylcarboxylic acids, the ratio of ortho:meta:para substituted isomers was 0:65:35, which correlates well with literature reports of the relative abundances of methylbiphenyl isomers, and suggests that the overall distribution of all monosubstituted biphenyls has not been significantly affected by biodegradation to level 4.The monoaromatic, diaromatic and triaromatic fractions of the same biodegraded crude oil (level 4) were separately treated with ruthenium tetroxide, which cleaves aromatic rings so that the ring carbon bearing the substituent is oxidised to become the carbonyl carbon of a carboxylic acid. These oxidation products represent the alkyl moieties that were attached to aromatic rings in the initial crude oil aromatic fractions. Identification of these alkyl side chains provides an insight into the nature of the components of the aromatic crude oil UCM. The oxidation products were separated into dichloromethane-soluble monocarboxylic acids, which were subsequently reduced to monodeuterated hydrocarbons for characterisation using gas chromatography-mass spectrometry (GC-MS) techniques, and water-soluble dicarboxylic acids which were analysed as dimethyl esters. n-Alkanes, methylalkanes, alkylalkanes, alkylcyclohexands, methylalkylcyclohexanes, isoprenoids and bicyclic alkanes were identified in the monodeuterated hydrocarbon samples derived from all three aromatic fractions. Most of these compounds had carbon skeletons strikingly similar to those observed in the saturate fractions of unbiodegraded crude oils, with the only differences being the addition of a carbon from the aromatic ring, and the presence of a deuterium atom attached to that carbon. Because the electron-withdrawing nature of carboxylic acid groups prevents further aromatic ring oxidation, numerous aromatic monocarboxylic acids were also identified in the acidic products of the oxidation of the crude oil diaromatic and triaromatic fractions. These included C(subscript)1 to C(subscript)3 alkyl-substituted benzoic acids derived from compounds containing a biphenyl or phenylnaphthalene structural moiety, as well as omega-phenylalkanoic acids with chain lengths up to C(subscript)11, derived from compounds in which two aromatic systems are connected by an alkyl chain. The main components of the dicarboxylic acid oxidation products of all three aromatic fractions were alpha, omega-dicarboxylic acids and alkylcyclopentane-dicarboxylic acids and alkylcyclohexane-dicarboxylic acids, with phthalic acids also present in the oxidation products of the diaromatic and triaromatic fractions. The observation that 1,5-pentanedicarboxylic acids and 1,6-hexanedicarboxylic acids were the only alpha, omega-dicarboxylic acids in the oxidation products of the crude oil monoaromatic fraction, and were present in high abundance relative to other alpha, omega-dicarboxylic acids in the oxidation products of the diaromatic and triaromatic fractions indicated that substituted indanes and/or tetralins were quantitatively important constituents of the overall crude oil aromatic fraction. This finding is supported by the results of the analysis of the mass spectra of the crude oil aromatic fractions.These studies of aromatic UCMs have provided new insights into the origins of the aromatic components of petroleum. The presence of a pronounced odd-over-even predominance in the C(subscript)25, C(subscript)27, and C(subscript)29 monodeuterated n-alkanes (CPI = 1.07), which corresponds to the odd-over-even predominance observed in the n-alkane components of unbiodegraded crude oils from the same basin, suggests that the n-alkyl side chains and the n-alkanes have a common source. Evidence is presented to support the hypothesis that the n-alkylaromatics are formed in part by geosynthetic processes involving alkylation of aromatic systems by electrophilic species such as carbocations and acylium ions formed from carboxylic acids. This hypothesis is then extended to explain the formation of other groups of compounds, including aromatic systems with isoprenoidal-, methylalkyl- and monoalkyl-branched side chains. Because isoprenoids, methylalkanes and alkylalkanes are well-known components of petroleum, these results suggest that these alkylaromatic components of petroleum may share a common source with the corresponding alkane components. It is suggested that aromatic unresolved complex mixtures arise due to the very large number of structurally related compounds present, which are formed by geosynthetic processes such as alkylation of aromatic rings.
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