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Preliminary Results on Molecular Modeling of


Asphaltenes Using Structure Elucidation
Programs in Conjunction with Molecular
Simulation Programs

ARTICLE in ENERGY & FUELS · JANUARY 1996


Impact Factor: 2.73 · DOI: 10.1021/ef950106t

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Energy & Fuels 1996, 10, 97-107 97

Preliminary Results on Molecular Modeling of


Asphaltenes Using Structure Elucidation Programs in
Conjunction with Molecular Simulation Programs
I. Kowalewski,*,† M. Vandenbroucke, and A. Y. Huc
Division Géologie-Géochimie, Institut Français du Pétrole, 1-4 Avenue de Bois Préau,
Rueil-Malmaison, 92506 Cedex, France

M. J. Taylor
TACIT, Postfach 1250, D-61186 Rosbach v.d.H, Germany

J. L. Faulon
Sandia National Laboratories, Albuquerque, New Mexico 87185

Received June 9, 1995. Revised Manuscript Received August 8, 1995X

Molecular modeling using structure elucidation programs in conjunction with molecular


simulation programs has been performed on asphaltene molecules, the heaviest fraction of crude
oil, in order to obtain a chemical model allowing us to tentatively study their physicochemical
properties. We have analyzed Boscan asphaltenes (Venezuela) derived from a marine source
rock. The different steps of this molecular modeling are described. First, a 3-D chemical
representation of Boscan asphaltene is defined from an analytical data set. Second, the results
of molecular dynamic simulations indicate that only a few stable conformations are possible due
to the high reticulation of the model of the asphaltene unit obtained.

Introduction carrying alkyl or naphthenic substituents with hetero-


atoms (especially N, S, O) interspersed within the
During this last decade, asphaltene fractions of system.2-5 The resin fraction of petroleum, containing
petroleum have been the focus of much attention due smaller and more polar molecules, could play an im-
to the potential production problems during exploitation portant role in the dispersion of the asphaltenes in the
of fields caused by the viscous and flocculating nature crude oil. Some authors consider that asphaltenes form
of these products. In the extreme limit, one implication colloids which are solubilized by resins.6-9
of asphaltene precipitation can be the nonproduction of Different asphaltene models have been already pro-
oil due to a global reduction of reservoir permeability. posed. A classical model developed by Yen et al.10,11
But, since asphaltenes are poorly characterized on a describes aggregation of asphaltene “units”. These
molecular basis,1 the causes of precipitation are not well authors have proposed a three-dimensional structure for
understood. asphaltene characterized by the stacking of more or less
In order to better understand the physicochemical polycondensed aromatic sheets linked by Π-Π bonds,
behavior of asphaltenes, it is of interest to know more hydrogen bonds, or sulfur and oxygen bridges.12 Several
about their chemical structure in terms of macro- of these units are associated and form micellar ag-
molecular groups (primary bonding structure) and intra- gregates. This model has been defined using data
and intermolecular bonds (secondary bonding struc- collected from solid phase compounds. Other models,
ture). In addition, another essential parameter is the
determination of the average molecular weight in their (2) Yen, T. F. Prepr.sAm. Chem. Soc. Div. Pet. Chem. 1972, 17(4),
natural environment, the other constituents of oils, and F.102-F.114.
in an isolated state. Asphaltenes consist of a macro- (3) Yen, T. F. Prepr.sAm. Chem. Soc. Div. Pet. Chem. 1979, 24(4),
901-909.
structure made up of an aggregation of asphaltene (4) Tissot, B. Rev. Inst. Fr. Pet. 1981, 36(4), 429-446.
“units” comprising Π and hydrogen bonds. They can (5) Tissot, B.; Welte D. H. Petroleum Formation and Occurrence;
2nd ed.; Springer: Verlag, Berlin, 1984; p 538.
be viewed as geomacromolecules including heteroge- (6) Pfeiffer, J. P.; Saal, R. N. J. J. Phys. Chem. 1940, 44, 139-149.
neous units randomly connected by covalent bonds (7) Speight, J. G.; Moschopedis, S. E. Prepr.sAm. Chem. Soc. Div.
(primary bonding structure); because of their mobility Pet. Chem. 1979, 24, 910-923.
(8) Moschopedis, S. E.; Fryer, J. F.; Speight, J. G. Fuel 1976, 55,
their secondary bonding structure is probably in an 187-192.
energy-minimized configuration. These units are con- (9) Pelet, R.; Behar, F.; Monin, J. C. Org. Geochem. 1986, 10, 839-
stituted of more or less condensed aromatic rings 846.
(10) Yen, T. F.; Erdmann, J. G.; Pollack, S. S. Anal. Chem. 1961,
33(11), 1587-1594.
* To whom correspondence should be addressed. (11) Sadeghi, M. A.; Chilingarian, G. V.; Yen, T. F. Energy Sources
† E-mail: Kowalew@irsil32.ifp.fr. 1986, 8, 99-123.
X Abstract published in Advance ACS Abstracts, October 15, 1995. (12) Ignasiak, T. M.; Bimer, J.; Samman, N.; Montgomery, O. P.;
(1) Speight, J. G. Prepr.sAm. Chem. Soc. Div. Pet. Chem. 1989, Strausz, D. S. Prepr.sAm. Chem. Soc. Div. Pet. Chem. 1979, 24(4),
321-328. 1001.

0887-0624/96/2510-0097$12.00/0 © 1996 American Chemical Society


98 Energy & Fuels, Vol. 10, No. 1, 1996 Kowalewski et al.

published in the literature13-15 and developed from Table 1. Elemental Analysis, Liquid 13C NMR, and
asphaltenes in solution, lead to a bidimensional planar Density for BOSCAN Asphaltenes
organization (disks). More recently, Ravey et al.16-18 elemental analysis
have investigated the macrostructure of asphaltene SIGNATURE
particles in solution using small angle X-ray scattering parameters
wt % (atomic ratios) 13C NMR (C %) density
(SAXS) and small angle neutron scattering (SANS) and
seem to confirm a bidimensional model for asphaltenes C 79.66 faa 39.6 1.24
when dispersed in an efficient solvent. Their results H 7.76 (h 116.9)d Caro.-H 11.3
suggest the existence of a colloidal and micellar nature O 1.79 (o 1.685)d subst. Caro. 13.9
N 1.73 (np 1.86)d cond. Caro. 14.4
for the asphaltene dispersion involving reversible as- S 6.83 (s 3.215)d degree of 4.5
sociation of asphaltene units. With flocculating agents, condensation
the association between these large primary particles ashes 2.23 degree of 0.551
would lead to the formation of a three-dimensional substitution
dipolar 28.5
network. dephasingb
To investigate the physicochemical behavior of as- CH 5.5
phaltenes, molecular modeling offers new insights into CH2 + CQc 42.6
the chemical structure of asphaltenes by taking into CH3 12.8
account the contribution of molecular groups and the a f × 100: carbon aromaticity %. b Caro.-H/f . c CQ: quaternary
a a
bonds which are involved. This method seems to be of carbon. d INSIGHT II/DISCOVER nomenclature (see Glossary).
interest for studying their chemical structure and
behavior, and for following the physicochemical rela- Torr). The liquid 13C NMR data were obtained on a MSL 400
tionships that exist between them and the other con- Bruker spectrometer using a solution of 100 mg of asphaltenes in
stituents of the oil. 2 mL of CDCl3 with 15 mg of iron acetylacetonate as relaxation
agent. To calculate aromaticity, “one-pulse” sequences were used
The aim of this paper is to present the pertinence of
with proton inversed gated decoupling. Pulse time was 5 µs
molecular modeling for the understanding of asphaltene
corresponding to a 60° angle with a time delay (D0) of 7 s. Other
molecules by combining structure elucidation programs averaged structural parameters were determined using spin echo
(XMOL and SIGNATURE software) and molecular and attached proton test sequences with echo time (τ) of 8 and
simulation programs (INSIGHT II/DISCOVER soft- 3.125 ms, respectively, for saturated and aromatic carbons. 5000
ware). XMOL (developed by IFP) and SIGNATURE acquisitions were accumulated. The results of atomic analysis are
(developed by J. L. Faulon) allow a 3-D graphic repre- summarized in Table 1.
sentation of the asphaltene “molecule” generated from Care must be taken when determining asphaltene molecular
a consistent quantitative analytical data set. Then, this weights because the analysis is complicated by the tendency
molecular model was used as an input for INSIGHT II/ of asphaltene molecules to associate with each other and with
DISCOVER software provided by Biosym Technologies. other surrounding constituents. It is known that according
Starting from the final structure obtained by SIGNA- to the techniques which are involved (viscosity, vapor pressure
osmometry, ultracentrifugation, small angle neutron scatter-
TURE, INSIGHT II (a graphic molecular modeling
ing, ...), the molecular weight varies within a large range.8,19-23
program) allows the building and the modification of the We have calculated the average molecular weight in THF
molecular system. DISCOVER (molecular simulation solution using gel permeation chromatography (GPC). Our
program), used in conjunction with INSIGHT II, calcu- analyses have been carried out using a HPLC pump (P2000
lates the minimum energy of the most stable conforma- Spectra Physics) operating at a flow rate of 1 mL/min on two
tion(s). consecutive PLgel columns (1000 and 100 Å pore size) following
a PLgel guard column. THF was chosen first because it is a
Experimental Section good solvent for asphaltenes and second because it has a
relatively high dipolar moment and provides relatively low
Sample. To perform this study, we have isolated and molecular masses due to low association phenomena; the GPC
analyzed the asphaltene fraction of Boscan crude oil (type II, chromatograms obtained for asphaltenes show a better defined
Venezuela). This crude oil contains a high amount of asphalt- profile distribution when compared to those obtained with
enes (13%) and does not present any asphaltene precipitation other solvents (CH2Cl2, benzene, ...).23 In addition, and in
during production operation. order to minimize as far as possible intermolecular interac-
Analytical Procedure. The asphaltene fraction was pre- tions, the asphaltene solution was very diluted. Using these
pared from the topped crude oil (fraction boiling above 210 experimental conditions, the measured molecular masses are
°C) using n-heptane precipitation. The asphaltenes were then assimilated to those of individual covalent “units” of asphalt-
characterized by two types of analyses: ene. The detection was done in absorbance mode monitoring
Atomic Analyses and Molecular Weight. These analyses at 260 nm (UV2000 Spectra-Physics). This wavelength is
(elemental analysis, density, 13C NMR, and gel permeation taken as the most appropriate to characterize the polynuclear
chromatography) define the chemical properties of the as- aromatic units. The mass calibration of the system was fixed
phaltene molecule by quantifying atoms and functional groups using polystyrene standards. In principle, standards of the
and molecular size. The density was determined using helium same molecular type as the substance analyzed should be
pycnometry at room temperature with primary vacuum (10-3
(19) Monin, J. C.; Pelet, R. Adv. Org. Geochem. 1983, 839-846.
(13) Reerink, H. Ind. Eng. Chem. Prod. Res. Dev. 1973, 12, 82. (20) Monin, J. C.; Vignat, A. Rev. Inst. Fr. Pet. 1984, 39(6), 821-
(14) Reerink, H. Prepr.sAm. Chem. Soc. Div. Pet. Chem. 1971, 16(1), 827.
D18. (21) Speight, J. G.; Wernick, D. L.; Gould, K. A. Overfield R. E. et
(15) Dickie, J. P.; Yen, T. F. J. Colloid Interface Sci. 1969, 29, 475. al. Rev. Inst. Fr. Pet. 1985, 40(1), 51-61.
(16) Ravey, J. C.; Espinat, D.; Ducouret, G. Fuel 1988, 67, 1560- (22) Sheu, R. Y.; Storm, D. A.; De Tar, M. M. J. Non-Cryst. Solids
1567. 1991, 131-133, 341-347.
(17) Ravey, J. C.; Espinat, D. Prog. Colloid Polym. Sci. 1990, 81, (23) Ducouret, G. Fractionnement des asphaltènes par chromatog-
127-130. raphie d’exclusion stérique- Caractérisation des fractions par diffusion
(18) Espinat, D.; Ravey, J. C. SPE-Oilfield Chem., Proc. of Int. Symp. des neutrons aux petits angles. Doctoral Thesis, University of Paris,
Soc. Pet. Eng., New Orleans 1993, 365-373. VI, December 1987.
Molecular Modeling of Asphaltenes Energy & Fuels, Vol. 10, No. 1, 1996 99

Table 2. Determination of Average Molecular Weight by Scheme 1. Molecular Analyses on Saturated C7+
GPC and Small Angle X-ray Scattering Fraction
polydispersed cylinder
model
units radius thickness
asphaltenes MMpa MMwb number (Å) σc (Å)
BOSCAN 10000 30800 3 21.3 0.725 10.8
a b
Calculated by GPC. Calculated by small angle X-ray scat-
tering. c Standard deviation of the distribution.

required to convert GPC chromatograms into molecular weight


distributions and to calculate average molecular weights. It
is obvious that polystyrenes do not represent the best stan-
dards for asphaltenes due to the large molecular polydispersity
of the latter. However, the equivalent polystyrene weight data
are given here to allow for some standardized reference and
calculate relative molecular weight distributions. The areas from 50 to 100 °C at 10 °C/min and from 100 to 300 °C at 3
of the recorded peaks were integrated using a GPC software °C/min. Saturates were then fractionated into n-alkanes and
developed at IFP. However, important tailing toward the low iso-/cycloalkanes by insertion into 5 Å molecular sieves. The
masses revealed the occurrence of significant adsorption iso-/cycloalkanes were quantified (in wt %) by mass spectrom-
phenomena with the PLgel. The average molecular weight etry on a Fisons Autospec with solid probe as introduction
MMp used in our model, reported in Table 2, was calculated mode, using the Hood and O’Neal method.29 The operating
by integrating the area corresponding to the first “peak” conditions were as follows: ion source 270 °C; electron energy
(higher molecular mass) in the chromatogram. The average 70 eV; ionization mode: EI; voltage acceleration 8 kV; resolu-
molecular masses obtained in these conditions are likely to tion 1000; acquisition time 3 s/decade. The solid probe was
represent the smallest unit of asphaltenes which is assembled heated from 40 to 500 °C at 30 °C/min.
by covalent bonds. A second technique, small angle X-ray The sulfur content of total aromatics was determined by
scattering, was used for measuring the average size distribu- elemental analysis. The aromatic fraction was separated
tion of asphaltenes. This technique is very sensitive to according to the number of condensed aromatic rings by
aromatic environments.24 Asphaltenes were diluted in toluene preparative normal phase HPLC (Varian Star 9010 pump) on
(2 wt %) and X-ray measurements were done at room tem- Petrospher B (Chrompack, 250 × 4.6 mm). The solvent used
perature. The MW obtained by this technique (Table 2) are for isocratic elution was n-hexane, and the flow rate was
much higher than with the previous technique. Therefore, maintained at 1 mL/min. The elution time of each aromatic
several of these covalent units separated by THF must be family was determined using a mixture of reference compounds
associated to account for the result obtained by small angle and the chromatographic column was back-flushed after
X-ray scattering. elution of pyrene. The detection was done using monitoring
Molecular Analyses. These analyses allow the identification absorption at 254 nm (Varian 9050 UV detector). Four
and the quantification of the molecular groups which consti- fractions were collected corresponding respectively to mono-
tute the “asphaltene molecule”. They were performed on the aromatics + thiophenes (F1), diaromatics + benzothiophenes
hydrocarbon fragments of the degradation products of the (F2), fluorenes + dibenzothiophenes (F3), and phenanthrenes
macromolecule obtained using anhydrous closed system py- + polyaromatics (F4). Each of these subfractions was then
rolysis. This technique has been described elsewhere.25,26 quantified by solid probe-MS (Ultima Fisons) using Fisher
About 50 mg of asphaltenes were pyrolyzed in a closed gold group type analysis.30,31 A 0.5-µL volume of the sample diluted
reactor without water added. A series of isothermal heating at 1/1000 with n-hexane was added to 2 µL of PFK (perfluo-
at 10 MPa under argon during different times were performed rokerosene) and injected. The operating conditions of the mass
in order to determine the appropriate experimental conditions spectrometer were as follows: mass range 20-600 amu,
to generate the maximum amount of hydrocarbons without electron energy 70 eV; ionization mode: EI; voltage accelera-
secondary cracking of heaviest fraction. The best conditions tion 8 kV; resolution 10 000; acquisition time 3 s/decade. The
were obtained for heating at 350 °C during 9 h. The molecular solid probe was heated from 40 to 650 °C at 50 °C/min. All
quantitation of the gas phase (H2, CO, CO2, C1-C5) was carried the results of molecular analysis are presented in Table 3, b
out by GC-TCD after a prior recovery and fractionation by a and c.
Toepler pump.25,27,28 The liquid pyrolysate was dissolved in
n-pentane, recovered, quantified by GC/FID, and finally Software
fractionated by minicolumn liquid chromatography into satu-
rates, aromatics, and NSO compounds. The molecular quan- After the complete analytical data base was gathered,
titation of saturates C7+ and aromatics was performed accord- two structure elucidation programs XMOL and SIGNA-
ing to the procedures developed at IFP (Schemes 1 and 2). TURE were used. XMOL software, developed at IFP,32,33
The total C7+ saturated fraction was analyzed by gas was originally written for modeling geological macro-
chromatography with helium (He) as carrier gas using a FID molecules such as kerogens and asphaltenes. XMOL
detector set at 300 °C (Varian 3500) equipped with an
allows the prediction and the construction of average
on-column injector (temperature programmed from 50 to 300
°C at 180 °C/min). The capillary column was a DB1 30m (i.d. chemical structures of geomacromolecules in a 3-D space
0.32 mm; f.t. 0.1 µm). The GC was temperature programmed according to their quantitative physicochemical analy-
ses. The software is divided into three modules. The
(24) Bardon, C.; Barré, L.; Espinat, D.; et al. Fuel Sci. Technol. Int.,
in press. (29) Hood, A.; O’Neal, M. J. Annual Book of ASTM Standards;
(25) Behar, F.; Leblond, C.; Saint-Paul, C. Rev. Inst. Fr. Pet. 1989, ASTM D2786; ASTM: Philadelphia, Part 24, pp 367-374.
44(3), 387-411. (30) Fisher, I. P.; Fisher, P. Talanta 1974, 21, 867.
(26) Behar, F.; Kressmann, S.; Rudkiewicz, J. L.; Vandenbroucke, (31) Bouquet, M.; Brument, J. Fuel Sci. Technol. 1990, 8(9), 961-
M. Org. Geochem. 1992, 19, 173-189. 986.
(27) Behar, F.; Ungerer, P.; Kressmann, S.; Rudkiewicz, J. L. Rev. (32) Faulon, J. L.; Vandenbroucke, M.; Drappier, J. M.; Behar, F.;
Inst. Fr. Pet. 1991, 46(2), 151-181. Romero, M. Org. Geochem. 1990, 16(4-6), 981-993.
(28) Prinzhofer, A.; Huc, A. Y. AAPG. Special Vol., in press. (33) Faulon, J. L. Thèse de l’Ecole des Mines de Paris, January 1991.
100 Energy & Fuels, Vol. 10, No. 1, 1996 Kowalewski et al.

Scheme 2. Molecular Analyses on Aromatic C7+ Fraction

first one, a prediction program, is based on the finger- enes modeling we need first to use XMOL designed to
print of the macromolecule, i.e. equations allowing on calculate the number of each molecular group to be
the one hand to quantitatively select, from a library, entered in the SIGNATURE file. The first task per-
molecular groups (aromatics, naphthenoaromatics, naph- formed by SIGNATURE program is to compute the
thenics, aliphatic chains, ...) according to molecular number of each fragments and interfragment bonds that
analyses (such as GC or MS of free hydrocarbons in best match with the quantitative data. Moreover, the
related oils or Py-GC analyses of asphaltenes) and on program is able to determine the number of nonidentical
the other hand to find the bonds that link the molecular models than can be constructed from a set of analytical
groups in order to verify atomic analyses (elemental data. One or more macromolecules randomly chosen
analysis, 13C NMR, IR, or UV spectroscopy, functional among the possible isomers is constructed by applying
groups, ...). When analytical data were not available, the prediction program (which links the fragments with
assumptions had to be made. The program calculates interfragment bonds). But SIGNATURE, having no
and lists in a construction file the number of each builder, must be used in conjunction with other molec-
molecular group and intergroup bonds selected accord- ular modeling programs to build the model in a 3-D
ing to the analyses. These numbers are computed for space. This was done using the INSIGHT II software
a given molecular weight of the macromolecule. provided by Biosym Technologies. The graphic molec-
The second module is an editor that enables to ular modeling program INSIGHT II is compatible with
construct and store atom configurations (mass, diam- the output file obtained from SIGNATURE and allows
eter), bonds (length, direction), cyclic molecular groups the user to build and modify molecular systems inter-
(including steric energy minimization), and the inter- actively. Because the 3-D BOSCAN structure generated
group bonds. The molecular structures built by the by the SIGNATURE program was not initially at a
editor are stored in a library. Due to the fact that the minimum state of energy, the model was submitted to
kerogen libraries were not specifically adapted to as- molecular mechanics (MM) and molecular dynamics
phaltene modelling, we had to create for this study a (MD) simulations. We performed these simulations
specific library which was as simple as possible and using in conjunction with INSIGHT II and DISCOVER
consistent with the type of molecular groups determined provided by Biosym Technologies. These simulations
by molecular analyses. The third module is a construc- are based upon the use of a general valence force field
tion program which allows to construct a 3-D isomer of which requires a set of equations and associated con-
the macromolecule calculated by the prediction pro- stants designed to reproduce molecular geometry and
gram. This construction program works by taking selected properties of test structures. For our study, we
molecular groups and intergroup bonds randomly from used the CVFF (covalent valence force field). MM was
the construction file and linking them inside a chosen used to find the energy minimum closest to the initial
construction volume based on the measured density and conformation. During the energy minimization, the
molecular weight of the macromolecule. For each spatial positions of atoms are perturbed in a stepwise
addition of a new molecular group, the nonintersection manner, until a minimum-energy conformation is iden-
with previous groups is verified (minimization of the tified. To identify this minimum, the minimization
steric energy is not included in the software). It is calculations were carried out using a conjugate gradient
possible to construct several isomers by changing the algorithm. Complex structures such as asphaltenes can
random sorting procedure in the program. be expected to display a number of low-energy confor-
Recently, Faulon developed a new computer-assisted mations separated by more or less high-energy barriers.
structure elucidation program called SIGNATURE which To study the possible stable conformations of Boscan
is based on graph theory.34 SIGNATURE, unlike XMOL, asphaltene, MD were employed by application of
is compatible with other molecular modeling software. quenched annealed dynamics (QAD) technique. In MD
This program allows large molecules to be assembled calculations, atoms are allowed to move with velocities
and has been already successfully applied to coal,35 depending on the temperature of the surrounding
lignin and lignocellulose.36 In order to perform asphalt-
(35) Faulon, J. L.; Hatcher, PG.; Carlson, G. A.; Wenzel, K. A. Fuel
Process. Technol. 1993, 34, 277-293.
(34) Faulon, J. L. J. Chem. Inf. Computer Sci. 1994, 34, 1204-1218 (36) Faulon, J. L.; Carlson, G. A.; Hatcher, PG. Org. Geochem. 1994,
. 21(12), 1169-1179.
Molecular Modeling of Asphaltenes Energy & Fuels, Vol. 10, No. 1, 1996 101

Table 3. Analytical Files Entered in XMOL for BOSCAN Molecule: (a) Atomic Analyses, (b) Molecular Analyses,
Saturated Hydrocarbons, and (c) Molecular Analyses, Aromatic Hydrocarbons
(a) Atomic Analyses
elemental analysis (wt %) functional analysis
carbon 79.66 oxygen functional analysis (mequiv/g)
hydrogen 7.76 total hydroxyl 0.20
oxygen 1.79 total carbonyl group 0.24
nitrogen 1.73 acid 0.16
sulfur 6.83 acid H 0.22
13C NMR (%) quinone 0.0
30-35 ppm 60.35 (c )a methoxyl 0.0
56-58 ppm 0 nitrogen distribution (%)
72-76 ppm 0.05 N-aromatic 100
92-96 ppm 0 sulfur distribution (%)
128-130 ppm 39.35 (cp)a S-aromatic 80
154 ppm 0.20 cyclosulfur and disulfur 20
178 ppm 0.05 thiol 0
210 ppm 0
dipolar dephasing 28.5
average no. condensed arom rings 3
% of functional group linked to 2 aro 1 aro and 1 ali 2 ali
ester 0 100 0
ketone 0 100 0
ether 0 100 0
amide 0 100 0
sulfur 50 50 0
(b) Molecular Analyses: Saturated Hydrocarbons
saturated hydrocarbons (%)
alkanes naphthenes
range of C wt % normal ramified isoprenoid 1 cycle 2 cycles 3 cycles 4 cycles 5 cycles 6 cycles
C1-C5 0.66 99 1
C6-C13 27.84 25 15 30 30
C14-C40 71.5 15 19.62 1.78 19.81 10.95 12.62 9.65 11.36 1
wt % wt % wt % wt %
C normal ramified C normal ramified C normal ramified C normal ramified
1 46.9 0 11 10.55 4.94 21 10.55 4.94 31 3.13 1.47
2 31.9 0 12 11.55 5.41 22 11.55 5.41 32 2.89 1.35
3 13.1 0 13 9.75 4.57 23 9.75 4.57 33 2.72 1.27
4 4.0 50 14 8.79 4.12 24 8.79 4.12 34 2.33 1.09
5 4.0 50 15 6.61 3.10 25 6.61 3.10 35 1.9 0.89
6 2.15 2.15 16 6.52 3.05 26 6.52 3.05 36 1.2 0.56
7 4.30 4.30 17 5.88 2.75 27 5.88 2.75 37 0.8 0.37
8 8.60 8.60 18 5.47 2.56 28 5.47 2.56 38 0.6 0.28
9 17.26 17.26 19 5.04 2.36 29 5.04 2.36 39 0.4 0.19
10 23.0 23.0 20 4.48 2.10 30 4.48 2.10 40 0.2 0.09
wt % wt %
pristane 74.5 phytane 25.5
(c) Molecular Analysis: Aromatic Hydrocarbons
fraction wt % fraction wt %
C6-C13 2.92 C14+ 97.08
wt % wt %
benzene 3.72 trimethylbenzene 25.11
methylbenzene 16.28 naphthalene 6.97
ethylbenzene 4.18 methylnaphthalene 16.30
xylene 27.44
aromatic structures CnH2n-pb aromatic structures CnH2n-pb
wt % wt %
p p
6 3.3 20 7.9
8 3.4 22 11.7
10 22.3 24 7.2
12 3.1 26 6.4
14 5.1 28 6.9
16 10.8 30 3.6
18 7.4
a INSIGHT II/DISCOVER nomenclature (see Glossary). b CnH2n-p: CnH2n-6 to CnH2n-10: monoaro; CnH2n-12 to CnH2n-16: diaro; CnH2n-18
to CnH2n-30: tri- and polyaro.
102 Energy & Fuels, Vol. 10, No. 1, 1996 Kowalewski et al.

system. The motions of atoms can lead the structure Table 4. Specifications for Construction
to overcome potential energy barriers and not to remain construction parameters
trapped in a local energy minimum. QAD allows the
system to overcome small energy barriers during the density 1.24
no. of groups 50
temperature relaxation and thus to settle the molecule
ratio of height in volume of construction 2
into a lower energy minimum. The interactions be- random basis 1
tween atoms are described by CVFF force field and the
motions of atoms are determined stepwise by integrat- in agreement with the literature42 and were used for
ing Newton’s equation of motion.37 All the MD calcula- BOSCAN asphaltenes.
tions were performed with an initial temperature set 4. Concerning the linkage of functional groups to
to 1100 K and for a period of time ranging from 0 to aliphatic and/or aromatic carbons, for disulfur bridge
150 ps. The temperature was then lowered from 1100 distribution, we have equally assigned the bridges: 50%
to 1 K in steps of 100 K (with 1 ps between drops). A between two aromatic structures and 50% between one
structure was saved at each change of temperature aromatic and one aliphatic structures.
(total of 10 structures). Furthermore, during each QAD 5. For oxygen distribution, we have a priori assumed
simulation, the energy of the studied structure was that carboxylic acids are 100% involved in aromatic
minimized using the MM technique as described above. structures.
To summarize, we have first examined some possible 6. Moreover, the molecular groups contained in the
structures of the BOSCAN asphaltene using computer- library have been adapted to account for the chemical
aided structure elucidation and then studied the spatial composition of hydrocarbons released by pyrolysis of
conformations of the structures with a force field (CVFF) BOSCAN asphaltenes. We have based the library on
suitable for all atom types present in this asphaltene naphthenoaromatic groups and, therefore, the average
molecule. All the computations for this study have been carbon number of molecular groups is C16 (naphtheno-
performed on an Apollo workstation (XMOL) and on a aromatic with four rings). Using the average molecular
Silicon Graphics Indigo-XZ4000 workstation (SIGNA- weight (MW) determined by gel permeation chromatog-
TURE version 1.3, INSIGHT II/DISCOVER version raphy, this results in choosing approximately 50 mo-
2.3.0). The abbreviations used are described in the lecular groups in the library for the construction file
Glossary. (Table 4).
Once the assumptions were defined, a parallelepipedic
Results and Discussion box was selected for the total volume of construction
with a height over square side in a ratio of 1/2 according
The XMOL software has been applied to BOSCAN to the dimensions obtained by small angle X-ray scat-
asphaltenes as follows. All the analytical data obtained tering. After running XMOL, the best construction file
have been entered in analytical files (Table 3) and the was selected (Table 5) and the asphaltene 3-D repre-
consistency of the data verified. The following assump- sentation achieved (Figure 1). The bulk chemical
tions have been introduced to supplement missing formula and the molecular weight given by XMOL for
analyses: BOSCAN asphaltene are summarized in Table 6. We
1. In the case of asphaltenes, the quantitative de- can notice that the constraint of 50 molecular groups
termination of functional groups is very difficult because using the molecular groups as defined in the library was
they are present in very low concentration. Thus, the pertinent: the calculated molecular weight is similar
functional groups have been estimated by relying on the to the experimental molecular weight obtained by GPC
functional group distribution of type II kerogen stan- and obviously, the same is true for the elemental atomic
dardized to the oxygen content of BOSCAN asphaltenes, ratios. The consistency of aromaticity (Csp2/Csp3 +
with the assumption that quinone and methoxy groups Csp2) is excellent. The graphic display shows a major
are absent in these asphaltenes. The chemical degrada- contribution of cycloalkanes and alkyl chains compared
tion techniques used for functional group quantitative to aromatic rings as observed with analytical results.
determination in coals and kerogens are described However, this model describes only an individual co-
elsewhere.38 valently bonded “unit” of the asphaltene molecule at an
2. According to the literature on oil heavy ends,39-41 isolated state, and not a macrostructure made of an
we have admitted that nitrogen was only in aromatic aggregation of asphaltene units linked by Π or H bonds.
structures for the studied asphaltene. As can be observed on the 3-D representation, the
asphaltene molecule constructed with XMOL is char-
3. For the sulfur compounds, according to the X-ray acterized by a globular shape. This globular shape of
adsorption near edge structure spectroscopy (XANES) asphaltenes should not be considered as the stable form
analyses performed at IFP, the distribution seems to in oil. It is directly related to the construction procedure
be divided between thiophenic moieties and sulfide involved in the program to generate the 3-D graphic
moieties such as disulfur bridges in a proportion of display. By selecting another volume of construction
roughly 80% and 20% respectively. These figures are (flatter parallelepipedic for instance), the resulting
shape would have changed. As a matter of fact, the 3-D
(37) Verlet, L. Phys. Rev. 1967, 159, 98-103. molecular model represented here does not take into
(38) Blom, L.; Edelhausen, L.; Van Krevelen, D. W. Fuel 1957, 36,
135-153. account the electronic constraints imposed by the en-
(39) Wilhelms, A.; Patience, R. L.; Larter, S. R.; Jorgensen, S. vironment (solvent, resins, aromatics, saturated hydro-
Geochim. Cosmochim. Acta 1992, 56, 3745-3750.
(40) Schmitter, J. M.; Ignatiadis, I.; Dorbon M.; Arpino, P., et al.
carbons) which is a determinant factor. The XMOL
Fuel 1993, 63, 557.
(41) Dorbon, M.; Ignatiadis, I.; Schmitter, J. M.; Arpino, P., et al. (42) Kasrai, M.; Michael Bancroft, G.; Brunner, R. W., et al.
Fuel 1993, 63, 565. Geochim. Cosmochim. Acta 1994, 58(13), 2865-2872.
Molecular Modeling of Asphaltenes Energy & Fuels, Vol. 10, No. 1, 1996 103

Table 5. Detailed Structure for the Best Solution of an average error less than 3.7% for 100 C) which are
XMOL for BOSCAN Asphaltenea listed in Table 7. These solutions have been obtained
parameter model for structures containing between 100 and 1000 carbon
molecular fragment atoms. The biggest error is due to the dipolar dephasing
sn1 12 (average error per 100 C around 20%). This error has
sn2 6 to be considered as acceptable (within the range of
sn3 4
sn4 2
experimental error). Indeed, the dipolar dephasing
sn5 1 value was determined using liquid 13C NMR (Table 1)
a1n0 2 which is less sensitive than the measurements per-
a1n1 1 formed using solid 13C NMR for asphaltenes. Figure 2
a1n2 2
a2n0 2
shows the relative error % on atomic ratios obtained for
a2n1 1 these 10 solutions; the minimum error % is obtained
a2n2 1 for the solution number 2. Therefore, the structure
a3n1 1 matching at best the analytical data is structure number
a3n2 2
a4n0 3
2 (molecular formula C647H756O11N12S20) and comprises
sl2 3 83 molecular fragments and 118 intergroup bonds. Its
sl9 2 chemical structure is detailed in Table 8. Globally, the
sl10 1 SIGNATURE solution is very close to the one obtained
sl15 1
using XMOL software (Table 9) but the random selec-
si9 1
si21 1 tion of molecular groups is different. This difference can
si22 1 be explained as follows. First, the two libraries are not
phenol 2 exactly similar, on the one hand regarding the molecular
interfragment bond groups content, and on the other hand regarding the
L0 22
L4 4 possible linkage between these fragments. With XMOL
L7 6 software, only two bonds are allowed per molecular
aroN 12 group. In the case of SIGNATURE software, up to eight
aroS 15 bonds are allowed for several fragments (i.e., a4n0 has
PDS 2
S 1 seven bonding sites). Second, heteroatoms-containing
a
molecular groups selected using the prediction program
For abbreviations, please refer to the Glossary.
of XMOL (i.e., nitrogen-containing aromatics, sulfur-
containing aromatics) have to be manually introduced
software does not calculate any energy minimization
after obtaining the 3-D representation of the molecule.
and thus the stability of the macromolecule which has
Each aromatic carbon replaced by an heteroatom must
been constructed is not checked. In order to obtain
then be reincluded into a new aromatic group. There-
minimum energy conformations (most stable conforma-
fore, the molecular groups defined in the construction
tion), application of molecular mechanics and dynamics
file (Table 5) have to be modified, specifically in the
simulations has to be performed but XMOL is not
compatible with other molecular modeling software. aromatic range. In our case, 12 nitrogen- and 15 sulfur-
Therefore, we used SIGNATURE which is compatible containing aromatics (12 aroN and 15 aroS, respectively)
with other molecular modeling software, XMOL having were redistributed in a total of 27 aromatic carbons.
been used first in order to quantify the molecular groups Then the prediction program was applied to deter-
which constitute the asphaltene unit. The input file of mine the nature and place of bonds between the frag-
SIGNATURE was similar to the construction file given ments for this solution number 2. The result is the 3-D
by XMOL and only some features were improved. On representation drawn in Figure 3. One can notice in
the one hand, the sulfur-containing aromatic molecular this figure that some bonds have unrealistic lengths
groups (15 aro-S) have been exactly defined as ben- because the program SIGNATURE does not check the
zothiophenes (bt), dibenzothiophenes (dbt), dithiophenes length of the cross-link bonds. With high cross-linked
(s2a), and naphthenothiophenes (Sa3n2) according to structures, such as our model, direct minimization leads
the quantitative data obtained by Fisher group type to a conformation that is highly distorted. Therefore,
analysis. On the other hand, we introduced as molec- we used SIGNATURE in conjunction with INSIGHT II/
ular groups for nitrogen- and oxygen-containing aro- DISCOVER. Starting from the Boscan molecule rep-
matics respectively pyridine (na1), benzopyridines (na2) resented in Figure 3, we rebuilt a new molecule using
and oxygen-containing diaromatics (oa2). After running the 3-D fragment library module of INSIGHT II. We
the elucidation program of SIGNATURE, we found 10 divided the initial macromolecule into the largest pos-
solutions in agreement with the analytical data (with sible fragments. This ensured the compatibility with

Table 6. Comparison between Experimental and Theoretical Data


formula (XMOL) MMw (XMOL) MMp (GPC)
C618H722O10N12S20 9106 10000

atomic ratios
H/C O/Ca N/Ca S/Ca aromaticity %
expt XMOL expt XMOL expt XMOL expt XMOL expt XMOL
1.17 1.17 1.69 1.62 1.86 1.94 3.21 3.23 39.6 39.6
a Multiplied by 100.
104 Energy & Fuels, Vol. 10, No. 1, 1996 Kowalewski et al.

Figure 1. 3D representation of BOSCAN asphaltene obtained using XMOL software.

Table 7. Solutions Obtained by Signature Equation for BOSCAN Asphaltene Containing between 100 and 1000 Carbon
Atoms (the Best Solution is Solution No. 2)
error per 100 C atoms dipolar dephasing
solution no. molecular formula (atoms)a error per 100 C calcd Mw
1 C637H745O10N12S20 3.04(0.19)b 20.0 9357
2 C647H756O11N12S20 3.07(0.18) 20.5 9504
3 C659H770O11N12S22 2.85(0.18) 19.0 9726
4 C661H773O11N12S22 3.03(0.21) 20.0 9753
5 C663H775O11N13S22 3.60(1.37) 17.0 9793
6 C671H784O11N12S22 3.20(0.51) 19.0 9884
7 C674H788O12N13S23 2.90(0.22) 19.0 9986
8 C692H809O12N12S22 3.00(0.65) 17.0 10177
9 C723H845O12N12S24 3.19(0.74) 18.0 10649
10 C753H880O12N13S24 3.07(0.35) 19.0 11058
a The error is the average error between the solution and the experimental data entered in the Signature input file. The solution no.

2 is the lowest-error solution. b The value of the error is underestimated not taking into account the dipolar dephasing.

the CVFF force field used in INSIGHT II/DISCOVER. process. Once the structure completed, it was relaxed,
The fragments were then connected using distance the bond constraints (bond lengths constrained to 5 Å)
constraints. The charges were fixed to 0 and the were converted to bonds, and the structure was remi-
potential types defined (potential type “op” was defined nimized. In order to improve the model (by decreasing
manually). Each fragment was defined as a subset and the total energy), the structure was modified manually
identified by different colors as represented in Figure by moving atoms in 3-D space, constraining or fixing
4. Periodically throughout the construction, due to some
them, and allowing the rest of the molecule to move
very high bond lengths, the various subsets were
subjected to rapid minimization using conjugate gradi- during energy minimization. In this manner, bonds
ents . In fact, some bond lengths were adjusted using through rings were avoided and the chain positions
mild distance constraints to avoid the distortion of the optimized. This complete procedure is summarized in
fragments during minimizations; then the minimized Figure 4. Last, the model was subjected to a final
fragments were reconnected step by step. The geometry energy minimization using conjugate gradients to locate
of the structure was gradually optimized according this the minima of this conformation. The final structure
Molecular Modeling of Asphaltenes Energy & Fuels, Vol. 10, No. 1, 1996 105

Figure 2. Relative error % on atomic ratios obtained for the


SIGNATURE solutions ((Xtheoretical - Xexptl/Xexptl) × 100).
Figure 3. 3D representation of BOSCAN asphaltene obtained
Table 8. Detailed Structure for the Best Solution using SIGNATURE software.
Obtained Using SIGNATURE for BOSCAN Molecule
(Solution No. 2 of Table 7) Table 9. Comparison between the Best Solutions
Obtained from XMOL and SIGNATURE Software
error per 100 C atoms
parameter model (analytical data - model data) software formula calcd Mw

Signature for 100 C XMOL C618H722O10N12S20 9106


h 116.9 0.05 SIGNATURE C647H756O11N12S20 9504
o 1.68 0.44
np 1.86 0.00 After this construction step, MD using QAD technique
s 3.21 0.12 was employed to study the closest energy minimum,
cp 38.55 -0.02
c 60.40 0.43 starting from the final conformation obtained previously
cp(cpcph . ) 28.5 20.5 (Figure 5). The curve represented in Figure 6 displays
molecular fragment the QAD simulation. At the beginning of the simula-
a1n2 1 3.07a
a1n3 2 tion, the total energy at an initial temperature of 1100
a2n1 3 K was increased to about 16 000 kcal/mol. Then by
sn1 7 freezing the molecule to 1 K, the total energy for the
sn2 3 most stable conformation was decreased to about 7000
sn3 3
sn4 1 kcal/mol or 4.8 kcal/(atom mol). It means that the
bt 3 energy remained relatively constant as the structure
dbt 1 moved between more or less equivalent conformations.
s2 2
s2a 5
Superimposing the different structures saved during the
Sa3n2 2 decrease of temperature, we can study the motions of
na1 8 the molecular fragments during the dynamic simulation.
na2 4 As we could expect, the core of the molecule is relatively
oa2 2
ester 3 rigid compared to the surrounding free aliphatic chains
aro-o 2 due probably to the high reticulation of the system
aro-oh 1 obtained (high cross-link density). The fact that there
sl1 3
sl2 4
was little improvement in the final energy when using
sl3 3 MD at 1100 K and then decreasing to 1 K tells us that
sl5 4 we were already near the bottom of the current energy
sl9 1 well when we started the run. Because only few
sl11 2
sl12 1 changes were found in the conformation during this MD
sl15 1 experiment, we assume that we probably did not provide
sl16 1 enough energy to the molecule; the starting temperature
sl23 1
si5 5
being too low, the molecule could not escape from the
si10 1 current energy well, possibly due to energy barriers
sp19 1 resulting from the structure of the molecule. Another
H 2 explanation is that we did not allow the simulation to
interfragment bond
ali-s 4 run for times long enough to have the opportunity to
ali-o 5 escape the current energy well. More tests of MD
ali-h 0 simulations with higher starting temperature and longer
aro-csp2 3
aro-ali 105
time would be necessary to check these assumptions.
aro-aro 1 But this may be due to an unrealistic model with too
a high cross-linking and in this case MD simulations
Total average error for 100 C.
using higher temperature and longer time should yield
is shown in Figure 5. We found a conformation with a same results. To decrease this cross-linking, work is
total energy of about 7100 kcal/mol or 4.9 kcal/(atom in progress to create a new library allowing only two or
mol). three bonds per molecular group.
106 Energy & Fuels, Vol. 10, No. 1, 1996 Kowalewski et al.

Figure 4. Rebuilding and minimization of BOSCAN using in conjunction INSIGHT II/DISCOVER. (Each number corresponds
to a fragment of the total molecule which is separately minimized. For the total molecule, each fragment is identified by different
colors.)

Figure 6. QAD simulation.


files compatible with INSIGHT II/DISCOVER, which
allow to find a stable conformation with relatively low
energy and to study the most stable(s) conformation(s).
Due certainly to the reticulation of the model found for
this asphaltene, there are probably very few possible
Figure 5. Minimized BOSCAN asphaltene “unit”. conformations and MD simulations do not improve the
structure substantially. Therefore, an attempt to de-
Conclusion
crease this high reticulation (by decreasing the number
To the best of our knowledge, this paper is the first of bonds allowed per molecular group) is in progress.
to use molecular modeling techniques to study asphal- However, to improve the realism and the rigor of our
tene structures. This effort for setting up a protocol of model, the perspective is to take into account a solvent
asphaltene molecular modeling has been reasonably environment. This should help for the understanding
successful on the BOSCAN sample. The procedure of the physicochemical behavior of asphaltenes in oil
involves several steps including complementary soft- production conditions. Work is in progress to examine
ware. The first step is the gathering of an analytical the structural fluctuations of a solvated asphaltene
data set on asphaltenes. The second step is the use of using periodic boundary conditions (PBC) which refers
the XMOL software to verify the consistency of the data to the simulation of the interactions of a molecular
set and to have a first 3-D asphaltene representation. system in a periodic lattice of identical subunits. Benzo-
Then, the SIGNATURE software generates construction furan has been chosen as the model for simulating resin
Molecular Modeling of Asphaltenes Energy & Fuels, Vol. 10, No. 1, 1996 107

interactions. By application of such conditions, the sl11 n-C11


influence of the environment can be investigated. sl12 n-C12
sl15 n-C15
sl16 n-C16
Acknowledgment. We wish to express our grati- sl23 n-C23
tude to Biosym Technologies for its assistance and the si5 isopentane (i-C5)
free use of INSIGHT II/DISCOVER software. More si9 isononane (i-C9)
specifically, we thank M. K. Seiti from Biosym. The si10 i-C10
contributions of IFP Geochemistry colleagues are grate- si21 i-C21
fully acknowledged for the gathering of the analytical si22 i-C22
data set. We thank D. Espinat and J. C. Roussel for sp19 pristane
H hydrogen
the results of SAXS-SANS measurements and 13C
phenol or phenol
NMR, respectively. aro-oh
aro-o ether-benzene
Glossary L0 molecular groups linked by 0C
L4 molecular groups linked by 4C
sn1 naphthalene with 1 cycle L7 molecular groups linked by 7C
sn2 naphthalene with 2 cycles aroN nitrogen-containing aromatic
sn3 naphthalene with 3 cycles na1 pyridine
sn4 naphthalene with 4 cycles na2 carbazole
sn5 naphthalene with 5 cycles aroS sulfur-containing aromatic
a1n0 benzene bt benzothiophene
a1n1 naphtheno (1)-aromatic (1) dbt dibenzothiophene
a1n2 naphtheno (2)-aromatic (1) s2a disulfur-containing aromatic
a2n0 naphthene Sa3n2 naphtheno (2)-sulfur-containing triaromatic
a2n1 naphtheno (1)-aromatic (2) PDS or s2 disulfur bridge
a2n2 naphtheno (2)-aromatic (2) S sulfur
a3n1 naphtheno (1)-aromatic (3) h hydrogen bonded to C
a3n2 naphtheno (2)-aromatic (3) o sp3 oxygen
a4n0 pyrene np sp2 aromatic nitrogen
sl1 methane s sulfur
sl2 ethane cp sp2 aromatic carbon
sl3 n-propane (n-C3) c sp3 aliphatic carbon
sl5 n-pentane (n-C5) cp(cpcph . ) dipolar dephasing
sl9 n-nonane (n-C9)
sl10 n-decane (n-C10) EF950106T