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677
I. Introduction
Asphaltenes occupy a central, if often hindering, role
in the utilization of hydrocarbon resources.1-6 The
increase in viscosity in crude oil which accompanies
increased asphaltene content coupled with the tendency
of asphaltenes to phase separate creates significant
difficulties in the production and transportation of crude
oil. The coating tendencies of asphaltenes along with
their heavy metal content interfere with catalytic
processing of crude oils. Other applications of asphaltic
materials such as for paving materials7 or coating
materials8 are strongly affected by the asphaltene
content. Despite the impact of asphaltenes in very
important economic spheres, some of their most fundamental properties have remained unresolved.
The molecular weight of asphaltenes has been a
matter of considerable controversy for 20 years. Various
measurements have yielded values which differ by as
much as a factor of 10 or more. For instance, field
ionization mass spectroscopy results have indicated a
molecular weight in the range of 700 amu,9 while vapor
pressure osmometry (VPO) has produced much larger
molecular weights for the same asphaltenes, e.g., 4000
amu.9 The large molecular weights obtained by VPO
were explained by evident aggregation of asphaltenes
* Corresponding author.
(1) Bitumens, Asphalts, and Tar Sands; Chilingarian, G. V., Yen,
T. F., Eds.; Elsevier Scientific Publishing Co.: New York, 1978.
(2) Speight, J. G. The Chemistry and Technology of Petroleum;
Marcel Dekker: New York, 1980.
(3) Tissot, B. P.; Welte, D. H. Petroleum Formation and Occurrence;
Springer-Verlag: Berlin, 1984.
(4) Chemistry of Asphaltenes; Bunger, J. W.; Li, N. C., Eds.;
American Chemical Society: Washington DC, 1984.
(5) Asphaltenes, Fundamentals and Applications; Sheu, E. Y.;
Mullins, O. C., Eds.; Plenum Press: New York, 1995.
(6) Structures and Dynamics of Asphaltenes; Mullins, O. C., Sheu,
E. Y., Eds.; Plenum Press: New York, 1998.
(7) Lin, M. S.; Lunsford, K. M.; Glover, C. J.; Davidson, R. R.; Bullin,
J. A. Chapter 5, ref 5.
(8) Lian, H.; Yen, T. F. Chapter 6, ref 5.
(9) Boduszynski, M. W. Chapter 7, ref 4.
at requisite concentrations. Size exclusion chromatography has yielded average molecular weights as high
as 10 000 amu.10 Recent laser desorption mass spectroscopic11 results have given asphaltene molecular
weights of 400 amu (with a range of roughly 200-600
amu) in rough agreement with the FIMS work.9 Rough
agreement here means that there is less than a factor
of 2 difference in the average molecular weight as
opposed to the one-to-two orders of magnitude difference
found among different measurements. The factor of 2
difference may be due in part to different samples.
Other laser desorption mass spectral measurements
yield a range of 250-1200 amu with a mean of about
500 amu for vacuum resid petroleum asphaltenes.12
Nevertheless, a widely quoted recently proposed
structure of an asphaltene molecule incorporated a
molecule weight in excess of 6000 amu.13 Apparently a
consensus has not been reached. Those supporting large
molecular weights claim that at least mass spectral
measurements suffer from fragmentation and do not
volatilize the heaviest ends. There is general agreement
that colligative methods such as VPO suffer from
aggregate formation; thereby yielding aggregate molecular weights. In addition, chromatographic methods
such as gel permeation chromatography have the additional problem of the lack of good standards. However,
there is not general agreement as to how debilitating
these problems are.
The number of rings in a single asphaltene fused ring
system has been another area of uncertainty with early
estimates ranging from a few rings to 20. However, a
concurrence of results from many different techniques
indicate that on average asphaltene ring systems have
(10) Anderson, S. I. Fuel Sci. Technol. Int. 1994, 12, 51.
(11) Miller, J. T.; Fisher, R. B.; Thiyagarajan, P.; Winans, R. E.;
Hunt, J. E. Energy Fuels 1998, 12, 1290.
(12) Yang, M.-G.; Eser, S. ACS Reprints, ACS New Orleans Meeting,
768, 1999.
(13) Strausz, O. P.; Mojelsky, T. W.; Lown, E. M. Fuel 1992, 71,
1355.
678
III. Theory
In the following we will assume a spherical molecule
rotating in a viscous medium subject to a sticking
boundary condition. The following definitions are used:23
Figure 1. Structures of dye compounds used for comparison
with asphaltene molecules.
(1)
(2)
and
r(t) )
D(t)
S(t)
(3)
W(,,t)
) D2W(,,t)
t
(4)
W(,,t) )
1
[1 + 2e-6DtP2(cos)]
4
(5)
2
r(t) ) e-6Dt
5
(6)
680
r/r,sph
2
4
1.41
2.25
6D )
kT
V
(7)
kT
V
(8)
aromatic
hydrocarbon
number
of rings
HO-LU
excitation [nm]
emission
maximum [nm]
benzene
naphthalene
anthracene
tetracene
pentacene
1
2
3
4
5
265
300
380
475
580
280
320
390
485
590
682
Table 3. Wavelengths, Anisotropies, and Derived Diameters Assuming a Sphere and an Oblate Spheroid of Aspect
Ratio ) 2
ex
em
ST1 [ns]
UG8 [ns]
AniST1
AniUG8
DiamST1 []
DiamUG8 []
major
axisST1 []
major
axisUG8 []
365
406
440
480
530
595
410
450
480
520
570
635
0.270
0.430
0.518
0.674
0.909
1.19
0.134
0.311
0.356
0.546
0.751
1.06
0.62
0.43
0.79
0.28
0.35
0.37
0.51
0.34
0.34
0.26
0.27
0.30
15.2
17.8
18.9
20.7
22.8
25.0
12.1
16.0
16.7
19.3
21.4
24.1
17.1
20.0
21.3
23.2
25.7
28.1
13.6
18.0
18.8
21.6
24.1
27.1
em
UG8
ST1
CAL
coal
resin
365
406
440
480
530
595
410
450
480
520
570
635
13.6
18.0
18.8
21.6
24.1
27.1
17.1
20.0
21.3
23.2
25.7
28.1
11.3
15.7
16.5
19.6
22.7
25.6
10.3
11.4
10.5
13.7
17.3
20.4
12.8
15.3
16.8
18.8
22.2
25.5
OEP
solar dye
13.0
22.1
Table 3 lists for ST1 and UG8, the rotational correlation time, anisotropy and diameters (assuming the
spherical model and an oblate spheroid with an aspect
ratio of 1/2).
Table 4 lists the derived molecular major axis diameters presuming an oblate spheroid with an aspect ratio
of 2 for asphaltenes ST1, UG8, Cal, Coal, and for UG8
resin. The two dyes are also listed for comparison. These
sizes are rather small implying small asphaltene molecular weights. The large variation of molecular size
with chromophore size shows that each molecule has
only one or perhaps two chromophores.
The petroleum asphaltene with the smallest rotational correlation times is Cal. Thus for a given spectral
range, Cal molecular sizes tend to be toward the smaller
end of the (narrow) range of sizes probed by a given
excitation and emission wavelength pair. In addition,
Cal asphaltene also has the shortest wavelength fluorescence maximum, also indicating that the Cal ring
systems are on average smaller than for the other
asphaltenes. X-ray absorption near edge structure studies on asphaltenes show that Cal asphaltene is anomalously high in its sulfoxide content. 44% of the sulfur in
Cal is in the sulfoxide group, while typically asphaltenes
possess only a few percent sulfoxide.30 (Cal asphaltene
is 3.75% S by mass.) Sulfoxide is a very polar group and
as such limits the solubility of sulfoxide-containing
molecules. It is known from a variety of studies that it
is sulfide sulfur, not thiophene sulfur which oxidizes to
the sulfoxide group30,31 (perhaps for Cal via biodegradation or contact with meteoric water). The implication is
that Cal ring systems are smaller because molecules
with large rings and sulfoxide groups would become
insoluble in toluene and thus be removed from the
asphaltene fraction. These Cal asphaltene molecules are
bidentate, the aromatic ring system and the aliphatic
sulfoxide group both produce strong intermolecular
interaction.
The coal asphaltene exhibits some fundamental differences from the petroleum asphaltenes. The fluores(30) Waldo, G. S.; Mullins, O. C.; Penner-Hahn, J. E.; Cramer, S.
P. Fuel 1992, 71, 53.
(31) Kelemen, S. R.; George, G. N.; Gorbaty, M. L. Fuel 1990, 69,
939.
asphaltene
V [ppm]
Ni [ppm]
ST1
BG5
Cal
2.6
438
141
8.5
141
632
684