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The development of new analytical methods and expensive. The secondsand more importantsreason is
microscopy and molecular simulation techniques has that the asphaltene content is a poor prediction of
generated considerable interest in the classic problem performance in catalytic cracking and coking. In these
of asphaltene chemistry. The most contentious issues processes, the Conradson carbon residue (CCR) or
are the true molecular weight of the asphaltenes1 and microcarbon residue (MCR) is a more useful predictor
the presence (or absence) of various sizes of aromatic of the coke-forming tendency. This point is illustrated
groups and bridges.2-4 The complexity of both the in the residue phase diagram proposed by Wiehe.5 As
chemistry of these materials and their solution and illustrated in Figure 1, the asphaltenes cluster in a
colligative properties require that effective models for particular region of molecular weight and hydrogen
asphaltene chemical structure include data from a content. The upper axis shows that the CCR content of
variety of sources.2 Although asphaltenes are a major the asphaltenes can be in the range of 40-85 wt %,
concern in production operations, because of their role based on the sample set of Wiehe.5 If we add additional
in emulsion stabilization and fouling, this fraction of data from studies that incorporate a wider range of
crude oil is also important in the conversion of vacuum heptane-insoluble asphaltenes,6,7 the domain of asphalt-
residues by processes such as coking, catalytic cracking, enes in the diagram then is extended and the range of
and hydroconversion. The purpose of this paper is to CCR or MCR contents for asphaltenes becomes even
set boundaries on proposed models for the asphaltene wider. Given that the CCR or MCR content correlates
chemical structure, using data from studies of residue well with some refinery processes, Figure 1 illustrates
conversion chemistry. Cracking and pyrolysis are not why these measures are used frequently instead of the
preferred analytical methods for defining chemical asphaltene content.
structure; however, any model for the asphaltene chemi- A simple reason for the wide range of MCR content
cal structure must be consistent with the observed in heptane-insoluble material is that the liquid-phase
reaction characteristics in regard to upgrading the solubility in a solvent at low temperature is a poor
processes. predictor of high-temperature behavior. Neither solubil-
Although thousands of metric tons of asphaltenes are ity nor reactivity at temperatures of >300 °C are
cracked, coked, or hydrogenated in refineries each day, predicted by the solubility in heptane at 20 °C. Variables
relatively few studies have considered the conversion that affect asphaltene precipitation include aromaticity
of asphaltenes under normal processing conditions. Most (and, indirectly, the H/C ratio and hydrogen content1,5),
studies have examined entire residues, for two excellent molecular weight, and polar functional groups.2,9 The
reasons. The first reason is that the separation of role of hydrogen bonding, because of the acids and
heptane-insoluble asphaltenes from residues or crude hydroxyl groups, is diminished significantly at 100 °C10
oil for subsequent processing studies is difficult and and would be insignificant at refinery processing tem-
(5) Wiehe, I. A. Ind. Eng. Chem. Res. 1992, 31, 530-536.
* Author to whom correspondence should be addressed. E-mail: (6) Calemma, V.; Rausa, R. J. Anal. Appl. Pyrolsis 1997, 40-41,
murray.gray@ualberta.ca. 569-584.
(1) Groenzin, H.; Mullins, O. C. Energy Fuels 2000, 14, 677-684. (7) Rahmani, S.; McCaffrey, W. C.; Dettman, H. D.; Gray, M. R.
(2) Speight, J. G. The Chemistry and Technology of Petroleum, 2nd Energy Fuels 2003, 17, 1048-1056.
ed.; Marcel Dekker: New York, 1991. (8) Rogel, E. Energy Fuels 1997, 11, 920-925.
(3) Murgich, J.; Abanero, J. A.; Strausz, O. P. Energy Fuels 1999, (9) McLean, J. D.; Kilpatrick, P. K. Energy Fuels 1997, 11, 570-
13, 278-286. 585.
(4) Ralston, C. Y.; Mitra-Kirtley, S.; Mullins, O. C. Energy Fuels (10) Pauling, L. The Chemical Bond: A Brief Introduction to Modern
1996, 10, 623-630. Structural Chemistry; Cornell University Press: Ithaca, NY, 1967.
Figure 1. Residue phase diagram, following Wiehe.5 Curve a represents the boundary for heptane solubles (from Wiehe5), and
curve b represents the revised boundary based on expanded data set. Legend for the data from Wiehe5 is as follows: ([) toluene
insolubles, (0) asphaltenes, and (O) heptane-soluble resins. Legend for the data from Rogel8 is as follows: (9) asphaltenes and
(3) heptane-soluble resins. Legend for other asphaltene data is as follows: (2) from Calemma and Rausa6 and (b) from Rahmani
et al.7
Figure 3. Proposed asphaltene structural models: (a) condensed aromatic cluster model14 and (b) bridged aromatic model.3
Yen,14 assumes extensive condensation of the aromatic this chemical structure, Wiehe13 depicted maltenes and
rings into large sheets. These sheets are assumed to be asphaltenes in residue schematically as aromatic cores
soluble, because of the saturated rings and side chains that are linked by reactive bridges and substituted with
around the molecular periphery (Figure 3a). This type side chains. Under coking conditions, the larger core
of structure, with lower molecular weight, has been aromatic groups would accumulate in the liquid phase
proposed by Groenzin and Mullins,1 on the basis of and contribute to coke formation, whereas sufficiently
spectroscopic studies. A very different structural orga- small fragments would form the observed liquid prod-
nization, illustrated in Figure 3b, was proposed by ucts. In a complex mixture, structures such as Figure
Speight2 and by Strausz and co-workers (e.g., Murgich 3a cannot be ruled out, particularly when the fraction
et al.3), on the basis of pyrolytic and selective oxidation of aromatic carbon approaches 70%, as in the extremum
studies to determine the building blocks of asphaltenes. in Figure 2; however, such a chemical structure cannot
A molecule of the type shown in Figure 3a cannot give account for the average amount of volatile product
significant mass yields of volatile product in a pyrolysis evolution under the pyrolysis conditions from a range
experiment. The side chains would crack off readily, and of asphaltenes.
the naphthenic rings then would undergo a combination Data on the nature of products from the cracking of
of dehydrogenation (to form aromatics) and cracking (to asphaltenes give further support to the diversity of
give mainly light ends). In contrast, a structure of the asphaltenes from different crude oils and indicate that
type in Figure 3b can easily give a wide range of product the chemical structures in asphaltenes must be consis-
sizes, from methane to toluene-insoluble carbon residue,
tent with the evolution of a significant yield of volatile
depending on the balance between cracking, product
products during pyrolysis. The data of Figure 4 show
release, and molecular rearrangements. Consistent with
simulated distillation curves from cracked products from
(14) Yen, T. F. Prepr.sAm. Chem. Soc., Div. Pet. Chem. 1972, 17, asphaltenes prepared by the supercritical fluid extrac-
(4), F102. tion of Athabasca bitumen.15 The asphaltenes were
Consistency of Asphaltene Structures Energy & Fuels, Vol. 17, No. 6, 2003 1569