Composition asphaltene

Relationship between kerogens and asphaltenes have taken on new meaning in the last few years especially for relatively low maturity oils. Asphaltene composition can give inferences about the source kerogen composition when kerogen data are unavailable (53.58-59). Asphaltenes are defined as materials soluble or peptized in oil or bitumen that precipitate when... 

The basic structural changes in asphaltene composition during visbreaking are as follows ... 

Regarding feed characterization, there is a need to characterize the residue from commonly available information without losing its essential characteristics. Typical feed analysis consists of distillation curve, kinematic viscosity, specific gravity, and sulfur, asphaltenes, and CCR residue contents. To develop more detailed kinetic models, advanced characterization is necessary for instance, SARA (saturates, aromatics, resins, asphaltenes) composition and analysis of each component would improve the prediction capability of kinetic models. 

An important industrial example of W/O emulsions arises in water-in-crude-oil emulsions that form during production. These emulsions must be broken to aid transportation and refining [43]. These suspensions have been extensively studied by Sjoblom and co-workers [10, 13, 14] and Wasan and co-workers [44]. Stabilization arises from combinations of surface-active components, asphaltenes, polymers, and particles the composition depends on the source of the crude oil. Certain copolymers can mimic the emulsion stabilizing fractions of crude oil and have been studied in terms of their pressure-area behavior [45]. 

Gas oil fractions (204—565°C) from coal Hquefaction show even greater differences in composition compared to petroleum-derived counterparts than do the naphtha fractions (128). The coal-gas oils consist mostly of aromatics (60%), polar heteroaromatics (25%), asphaltenes (8—15%), and saturated... 

However, for the past 30 years fractional separation has been the basis for most asphalt composition analysis (Fig. 10). The separation methods that have been used divide asphalt into operationally defined fractions. Four types of asphalt separation procedures are now in use ( /) chemical precipitation in which / -pentane separation of asphaltenes is foUowed by chemical precipitation of other fractions with sulfuric acid of increasing concentration (ASTM D2006) (2) solvent fractionation separation of an "asphaltene" fraction by the use of 1-butanol foUowed by dissolution of the 1-butanol solubles in... 

Asphaltenes seem to be relatively constant in composition in residual asphalts, despite the source, as deterrnined by elemental analysis (6). Deterrnination of asphaltenes is relatively standard, and the fractions are termed / -pentane, / -hexane, / -heptane, or naphtha-insoluble, depending upon the precipitant used (5,6,49). After the asphaltenes are removed, resinous fractions are removed from the maltenes-petrolenes usually by adsorption on activated gels or clays. Recovery of the resin fraction by desorbtion is usually nearly quantitative. 

Colloidal State. The principal outcome of many of the composition studies has been the delineation of the asphalt system as a colloidal system at ambient or normal service conditions. This particular concept was proposed in 1924 and described the system as an oil medium in which the asphaltene fraction was dispersed. The transition from a coUoid to a Newtonian Hquid is dependent on temperature, hardness, shear rate, chemical nature, etc. At normal service temperatures asphalt is viscoelastic, and viscous at higher temperatures. The disperse phase is a micelle composed of the molecular species that make up the asphaltenes and the higher molecular weight aromatic components of the petrolenes or the maltenes (ie, the nonasphaltene components). Complete peptization of the micelle seems probable if the system contains sufficient aromatic constituents, in relation to the concentration of asphaltenes, to allow the asphaltenes to remain in the dispersed phase. 

Many investigations of relationships between composition and properties take into account only the concentration of the asphaltenes, independendy of any quality criterion. However, a distinction should be made between the asphaltenes which occur in straight mn asphalts and those which occur in blown asphalts. Remembering that asphaltenes are a solubiUty class rather than a distinct chemical class means that vast differences occur in the make-up of this fraction when it is produced by different processes. 

Surface Active Composition for Conditioning a Gas Containing Entrained Asphaltenes... 

Each oil-dispersant combination shows a unique threshold or onset of dispersion [589]. A statistic analysis showed that the principal factors involved are the oil composition, dispersant formulation, sea surface turbulence, and dispersant quantity [588]. The composition of the oil is very important. The effectiveness of the dispersant formulation correlates strongly with the amount of the saturate components in the oil. The other components of the oil (i.e., asphaltenes, resins, or polar substances and aromatic fractions) show a negative correlation with the dispersant effectiveness. The viscosity of the oil is determined by the composition of the oil. Therefore viscosity and composition are responsible for the effectiveness of a dispersant. The dispersant composition is significant and interacts with the oil composition. Sea turbulence strongly affects dispersant effectiveness. The effectiveness rises with increasing turbulence to a maximal value. The effectiveness for commercial dispersants is a Gaussian distribution around a certain salinity value. 

The effect of water temperature variation is logarithmically correlated with dispersant effectiveness [585]. Dispersant/oil ratios greater than approximately 1 40 or 1 60 result in a low dispersant effectiveness. Dispersion experiments were conducted to investigate the effects of oil composition. The effectiveness is positively and strongly correlated with the saturate concentration in the oil and is negatively correlated with the contents of aromatic, asphaltene, and polar compounds in the oil. The effectiveness is weakly correlated with the viscosity of the oil. The dispersant effectiveness is limited primarily by the oil composition. 

S. D. Dzhanakhmedova, E. I. Pryanikov, S. A. Sulejmanova, K. K. Mamedov, E. G. Dubrovina, N. M. Indyukov, and A. B. Sulejmanov. Composition for preventing asphaltene-resin-paraffin deposits—contains waste from production of synthetic glycerine, in mixture with polyacrylamide. Patent SU 1761772-A, 1992. 

A. L. Mendoza. Surface active composition for conditioning a gas containing entrained asphaltenes. Patent GB 2279964,1995. 

For crude oils C and D, some lighter hydrocarbons are formed during the cracking reactions but the composition of the 210 fraction is hardly modified. In particular, it can be noticed that the asphaltene contents of both of the recovered oils remain high. 

In part II of the present report the nature and molecular characteristics of asphaltene and wax deposits from petroleum crudes are discussed. The field experiences with asphaltene and wax deposition and their related problems are discussed in part III. In order to predict the phenomena of asphaltene deposition one has to consider the use of the molecular thermodynamics of fluid phase equilibria and the theory of colloidal suspensions. In part IV of this report predictive approaches of the behavior of reservoir fluids and asphaltene depositions are reviewed from a fundamental point of view. This includes correlation and prediction of the effects of temperature, pressure, composition and flow characteristics of the miscible gas and crude on (i) Onset of asphaltene deposition (ii) Mechanism of asphaltene flocculation. The in situ precipitation and flocculation of asphaltene is expected to be quite different from the controlled laboratory experiments. This is primarily due to the multiphase flow through the reservoir porous media, streaming potential effects in pipes and conduits, and the interactions of the precipitates and the other in situ material presnet. In part V of the present report the conclusions are stated and the requirements for the development of successful predictive models for the asphaltene deposition and flocculation are discussed. 

In modern terms, asphaltene is conceptually defined as the normal-pentane-insoluble and benzene-soluble fraction whether it is derived from coal or from petroleum. The generalized concept has been extended to fractions derived from other carbonaceous sources, such as coal and oil shale (8,9). With this extension there has been much effort to define asphaltenes in terms of chemical structure and elemental analysis as well as by the carbonaceous source. It was demonstrated that the elemental compositions of asphaltene fractions precipitated by different solvents from various sources of petroleum vary considerably (see Table I). Figure 1 presents hypothetical structures for asphaltenes derived from oils produced in different regions of the world. Other investigators (10,11) based on a number of analytical methods, such as NMR, GPC, etc., have suggested the hypothetical structure shown in Figure 2. 

Table I. Elemental compositions of asphaltenes precipitated by different flocculants from various sources (16)...

A most striking result from the work described above is that the composition of the bottoms product and residues from the dissolution reaction did not depend on the chemical structure of the original coal material only their relative quantities differed. This supports the view of a mechanism involving the stabilisation of reactive fragments rather than an asphaltene-intermediate mechanism. The formation of a carbon-rich condensed material as a residue of the reaction and the fact that hydrogen transfer occurred largely to specific parts of the coal further supports this view. 

Mansuy et al. [97] investigated the use of GC-C-IRMS as a complimentary correlation technique to GC and GC-MS, particularly for spilled crude oils and hydrocarbon samples that have undergone extensive weathering. In their study, a variety of oils and refined hydrocarbon products, weathered both artificially and naturally, were analyzed by GC, GC-MS, and GC-C-IRMS. The authors reported that in case of samples which have lost their more volatile n-alkanes as a result of weathering, the isotopic compositions of the individual compounds were not found to be extensively affected. Hence, GC-C-IRMS was shown to be useful for correlation of refined products dominated by n-alkanes in the C10-C20 region and containing none of the biomarkers more commonly used for source correlation purposes. For extensively weathered crude oils which have lost all of their n-alkanes,it has been demonstrated that isolation and pyrolysis of the asphaltenes followed by GC-C-IRMS of the individual pyrolysis products can be used for correlation purposes with their unaltered counterparts [97]. 

In addition, a method of petroleum classification based on other properties as well as the density of selective fractions has been developed. The method consists of a preliminary examination of the aromatic content of the fraction boiling up to 145°C (295°F), as well as that of the asphaltene content, followed by a more detailed examination of the chemical composition of the naphtha (bp < 200°C < 390°F). For this examination a graph is nsed that is a composite of cnrves expressing the relation among the percentage distillate from the naphtha. 

Petroleum is typically described in terms of its physical properties (such as density and pour point) and chemical composition (such as percent composition of various petroleum hydrocarbons, asphaltenes, and sulfur). Although very complex in makeup, crude can be broken down into four basic classes of petroleum hydrocarbons. Each class is distinguished on the basis of molecular composition. In addition, properties important for characterizing the behavior of petroleum and petroleum products when spilled into waterways or onto land and/or released into the air include flash point, density (read specific gravity and/or API gravity), viscosity, emulsion formation in waterways, and adhesion to soil. 

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