Asphaltenes structures

Asphaltenes and resins are dark substances (from dark red to brown). They are soluble in aromatic solvents but insoluble in paraffin solvents [3]. Asphaltenes have various types of heteroatoms present in crude oil in their structure. Asphaltenes are the most complicated known compounds in crude oil. 

The classic definition of asphaltenes is based on the solution properties of petroleum residuum in various solvents. Broadly speaking, asphaltenes are insoluble in paraffin solvents but soluble in aromatic solvents. Structurally, asphaltenes... 

Structurally, asphaltene contains flat sheets of condensed aromatic systems that may be interconnected by sulfide, ether, aliphatic chains or naphthenic ring linkages. Gaps and holes appear as defect centers in the aromatic systems with heterocyclic atoms coordinated to transition metals such as vanadium and nickel, most likely caused by free radicals. Due to the complexity and the large size of asphaltene molecules, asphaltene particles conveniently faU within the colloidal range. The stmcture of asphaltene has been determined previously by the x-ray diffraction method and is shown as Figure 2. 

Bouquet, M. and A. Bailleul (1986), Routine method for quantitative carbon 13 NMR spectra editing and providing structural patterns. Application to every kind of petroleum fraction including residues and asphaltenes . Fuel, Vol. 65, p. 1240. 

Thus, based on material applications, the following polymers are important natural rubber, coal, asphaltenes (bitumens), cellulose, chitin, starch, lignin, humus, shellac, amber, and certain proteins. Figure 4 shows the primary structures of some of the above polymers. For detailed information on their occurrence, conventional utilization, etc., refer to the references cited previously. 

Binuclear aromatic hydrocarbons are found in heavier fractions than naphtha. Trinuclear and polynuclear aromatic hydrocarbons, in combination with heterocyclic compounds, are major constituents of heavy crudes and crude residues. Asphaltenes are a complex mixture of aromatic and heterocyclic compounds. The nature and structure of some of these compounds have been investigated. The following are representative examples of some aromatic compounds found in crude oils ... 

The heptane insoluble (ASTM D-3279) method is commonly used to measure the asphaltene content of the feed. Asphaltenes are clusters of polynuclear aromatic sheets, but no one has a clear understanding of their molecular structure. They are insoluble in C3 to paraffins. The amount of asphaltenes that precipitate varies from one solvent to another, so it is important that the reported asphaltene values be identified with the appropriate solvent. Both normal heptane and... 

Yen, T. F. Structural Differences Between Asphaltenes Isolated from Petroleum and from Coal Liquid, Chemistry of Asphaltenes-, Bunger, J. W. Li, N. C., Eds. Advances in Chemistry Series No. 195 American Chemical Society Washington, D.C., 1981, p 39. 

In this zone, the quantity of extracted oil is generally sufficient to obtain the distribution of the different structural groups (SARA analysis) except for oil A (Fig. 6 to 9) For oil B (Fig. 6), for the first two samples, the amount of extracted products is too low and the analysis is uncertain. It can only be noticed that the asphaltene content is null. On the contrary, just beyond the coke zone (samples III-IV), the asphaltene content respectively reaches 12.9 and 5 4 whereas the asphaltene content of the initial oil is only 0.3. This effect is also observed for oil C (10 versus 6.3%) (Fig. 7), D 24% versus 13.8 ) (Fig. 8), E (24 4 versus 8.1 ) (Fig. 9) For all the oils, the amount of resins+asphaltenes generally remains constant and the amount of saturates increases... 

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. 

Figure 1. An example of a hypotetical structure of asphaltene, among the many suggested, showing their aromatic character.

Figure 2. Asphaltene structure deduced from microscopic and macroscopic analysis, showing their micro- and macro-molecular bonding. T. F. Yen, 1972, first suggested this type of structure.

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. 

In this paper we have looked firstly at the effect that the catalyst concentration, secondly at the effect that the reactor temperature and finally at the effect that the residence time at temperature have on the chemical structure of the oils (hexane soluble product) produced on hydropyrolysis (dry hydrogenation) of a high volatile bituminous coal. Generally, the hydropyrolysis conditions used in this study resulted in oil yields that were considerably higher than the asphaltene yields and this study has been limited to the effects that the three reaction conditions have on the chemical nature of the oils produced. 

Figure 8. Distribution of structural parameters of asphaltene from Shin-Yubari coal hydrogenation at 450°C (O), H2 100kg/cm2 ( ), H2 75 + CHh 25 ( ),...

Figure 9. Structural parameters of asphaltene from Soya-Koishi coal by CO + H,0 and Ht reduction at 400° C...

In the resid, the largest molecular weight belongs to the asphaltenes, whose molecular structure is not known, until now. Asphaltenes are not defined in chemical or physical terms, but rather in an operational manner as a crude oil fraction that is insoluble in light... 

The effect of conversion on the structure of an asphaltene molecule has been reported to depend on the operating conditions and on the presence or not of a catalyst. The effect of thermal processing reaction of a vacuum residue resulted in the selective cracking of the aliphatic or naphthenic side chains of the molecule, leaving the highly condensed aromatic core structure almost intact (see Fig. 16) [116]. 

Figure 16. Effect of thermal processing on asphaltene structures of a VR [116].

However, for the heavier resides, zeolite pore structure may preclude their use in HCK. We have introduce the effect of the pore size and distribution on the conversion and coke formation of asphaltene containing feeds (Section 5.2.1), but we should also point out that they also affect the dispersion of the hydrogenation metals on the catalyst surface. A poor dispersion will also lead to poor hydrogenation and indirectly favor coke formation. 

Leon, O. Rogel, E. Espidel, J., and Torres, G., Asphaltenes Structural Characterization, Self-Association, and Stability Behavior. Energy Fuels, 2000. 14 pp. 6-10. 

Siskin, M. Kelemen, S. R. Eppig, C. P., et al., Asphaltene Molecular Structure and Chemical Influences on the Morphology of Coke Produced in Delayed Coking. Energy Fuels Published on Web Nov. 4th, 2006, pp. 1-8. 

Michael, G. Al-Siri, M. Khan, Z. H., and Ah, F. A., Differences in Average Chemical Structures of Asphaltene Fractions Separated From Feed and Product Oils of a Mild Thermal Processing Reaction. Energy Fuels, 2005. 19 pp. 1598-1605. 

Figure 36. Proposed structural models of asphaltene molecules.

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