Review of the Molecular Structure and Aggregation of Asphaltenes and Petroleomics

Summary Tremendous strides have been made recently in asphaltene science. Many advanced analytical techniques have been applied recently to asphaltenes, elucidating many asphaltene properties. The inability of certain techniques to provide correct asphaltene parameters has also been clarified. Longstanding controversies have been resolved. For example, molecular structural issues of asphaltenes have been resolved; in particular, asphaltene molecular weight is now known. The primary aggregation threshold has recently been established by a variety of techniques. Characterization of asphaltene interfacial activity has advanced considerably. The hierarchy of asphaltene aggregation has emerged into a fairly comprehensive picture, essentially in accord with the Yen model with the additional inclusion of certain constraints. Crude oil and asphaltene science is now poised to develop proper structure-function relations that are the defining objective of the new field: petroleomics. The purpose of this paper is to review these developments in order to present a more clear and accessible picture of asphaltenes, especially considering that the asphaltene literature is a bit opaque. Introduction The asphaltenes are a very important class of compounds in crude oils (Chilingarian and Yen 1978; Bunger and Li 1981; Sheu and Mullins 1995; Mullins and Sheu 1998; Mullins et al. 2007c). The asphaltenes represent a complex mixture of compounds and are defined by their solubility characteristics, not by a specific chemical classification. A common (laboratory) definition of asphaltenes is that they are toluene soluble, n-heptane insoluble. Other light alkanes are sometimes used to isolate asphaltenes. This solubility classification is very useful for crude oils because it captures the most aromatic portion of crude oil. As we will see, this solubility defintion also captures those molecular components of asphaltene that aggregate. Other carbonaceous materials such as coal do possess an asphaltene fraction, but that often will not correspond to the most aromatic fraction. Petroleum asphaltenes, the subject of this paper, can undergo phase transitions that are an impediment in the production of crude oil. Fig. 1 shows a picture of an asphaltene deposit in a pipeline; obviously, asphaltene deposition is detrimental to the production of oil. Immediately it becomes evident that different operational definitions apply for the term asphaltene in the field vs. the lab. Indeed, the field deposit is very enriched in n-heptane-insoluble, toluene-soluble materials, but this field asphaltene deposit is not identically the standard laboratory solubility class. It is common knowledge that a pressure drop on certain live crude oils (containing dissolved gas) can cause asphaltene flocculation, the first step in creating deposits that are seen in Fig. 1. Highly compressible, very undersaturated crude oils are most susceptible to asphaltene deposition problems with a pressure drop (de Boer et al. 1995). In depressurization flocculation, the character of the asphaltene flocs is dependent on the extent of pressure drop, suggesting some variations in the corresponding chemical composition (Hammami et al. 2000; Joshi et al. 2001). Comingling different oils can result in asphaltene precipitation that can resemble solvent precipitation. Asphaltenes are hydrogen-deficient compared to alkanes; thus, either hydrogen must be added or coke removed in crude oil refining to generate transportation fuels. Thus, asphaltene content lowers the economic value of crude oil. Increasing asphaltene content is associated with dramatically increasing viscosity, especially at room temperature; again, this is of operational concern. The strong temperature dependence of viscosity of asphaltic materials is one of their important properties that make them useful for paving and coating; application of asphaltic materials is facile at moderately high temperatures, while desired rheological properties are obtained at ambient temperatures.