Molecular Characterisation of Fluidised Catalytic Cracker Feedstocks using Ruthenium Tetroxide Oxidation: a Study of Model Hydrocarbons
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The world's proven reserves of crude oil will be depleted in 42 years at the current rate of consumption. Oil refiners are under considerable economic and environmental pressure to improve the efficiency of refining and the quality and definition of products. Statistical and fundamental models are extensively used to more accurately model the important refinery processes such as Fluidised Catalytic Cracking (FCC). A major problem with the fundamental approach is that FCC feedstocks are by definition heavy petroleum fractions, and as such constitute highly complex mixtures of aromatic and aliphatic hydrocarbons. Gas chromatography (GC) analysis of heavy petroleum fractions reveals a broad 'hump' of unresolved compounds termed an Unresolved Complex Mixture (UCM) of hydrocarbons. Conventional instrumental techniques alone are unable to elucidate the composition of UCMs, they are simply too complex. Oxidative degradation of UCMs has already been used with some success to selectively oxidise aliphatic and aromatic UCMs to reveal some of the structures incorporated in UCMs from various natural and anthropogenic sources. Ruthenium tetroxide (RUO4) attacks aromatic rings at the ipso-carbon of aromatic moieties. Unsubstituted aromatic carbon is oxidised to CO2 whereas substituents are preserved as carboxylic acids. "Retro-structural analysis" involves reconstruction of the products of oxidation to reveal the original molecule or 'average' molecule. However, previous studies have highlighted problems with the recovery of products from die oxidation of hydroaromatic compounds. Hydroaromatic compounds contain an alicyclic ring attached to an aromatic ring e.g. tetralin. This study presents evidence that (theoretically) data from RUO4 oxidation FCC feedstocks can make a significant improvement to the accuracy of FCC modelling at BP Amoco. RUO4 oxidation and work-up procedures were developed further in an attempt to overcome problems with 'losses' of oxidation products from hydroaromatic compounds, including an improved carbon dioxide trap. Several novel hydroaromatic compounds and a diaromatic compound proposed in a previous study as being 'average' UCM components were synthesised and fully characterised by GC, GCMS, FTIR and NMR spectroscopy. The compounds synthesised were 6-cyclohexyltetralin, l-(3'- methylbutyl)7-cyclohexyltetralin, 1-n-nonyl-7-cyclohexyltetralin and 1-/n-nonyl-7- cyclohexylnaphthalene. RUO4 oxidation of the synthetic compounds and commercial tetralin revealed that while losses of between 70 and 50% of the expected water soluble dicarboxylic acids are observed, these losses can be at least partially accounted for by the 'over oxidation' of carboxylic acids to produce smaller carboxylic acids. For example, the RUO4 oxidation of tetralin produces 1,6-hexanedioic acid as a major product but significant amounts of 1,5-pentanedioic acid is observed along with trace amounts of 1,4- butanedioic acid. Smaller acids are likely to be undetected or lost as butyl esters during the work-up. Where 2-n-nonyl-1,6-hexanedioic acid was produced, decanoic and nonanoic acid as well as 1,5- pentanedioic acid and 1,4-butanedioic acid were observed corresponding to oxidation of the 2- position on the dicarboxylic acid. The three major products from RUO4 oxidation of ln-nonyl-7-cyclohexylnaphthalene were partially oxidised compounds including 2-(l-oxo-n-decane)-4-cyclohexylbenzoic acid, showing that the oxidation of diaromatic compounds in UCMs gives more complex oxidation products. This is consistent with previous studies where diaromatic UCMs were oxidised to give a more complex 'oxidised UCM' rather than simple carboxylic acids. The observation of monocarboxylic acids in oxidation products from the alicyclic portion of a hydroaromatic compound has not previously been reported. This represents a new source of monocarboxylic acids in the RUO4 oxidation products of UCMs and should be taken into account when oxidising UCMs likely to contain a significant proportion of hydroaromatic structures, such as hydrotreated FCC feedstocks. The synthesis and oxidation of di-substituted teiralins has increased the understanding of RuG4 oxidation products from UCMs and consequently furthered the use of RUO4 as a potentially useftjl tool in the elucidation of FCC feedstock compositions and other aromatic UCMs.
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