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Phase composition of asphaltenes

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DOI: 10.1007/s10973-013-3442-3

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Phase composition of asphaltenes

Yulia Muratova Ganeeva, Tatiana

Nicolaevna Yusupova, Gennady
Vasil’evich Romanov & Natalia Yurievna
Bashkirtseva
Journal of Thermal Analysis and
Calorimetry
An International Forum for Thermal
Studies

ISSN 1388-6150
Volume 115
Number 2

J Therm Anal Calorim (2014)

115:1593-1600
DOI 10.1007/s10973-013-3442-3

1 23
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1 23
 Author's personal copy
J Therm Anal Calorim (2014) 115:1593–1600
DOI 10.1007/s10973-013-3442-3
Phase composition of asphaltenes
Yulia Muratova Ganeeva • Tatiana Nicolaevna Yusupova
Gennady Vasil’evich Romanov •
Natalia Yurievna Bashkirtseva
Received: 11 February 2013 / Accepted: 25 September 2013 / Published online: 23 October 2013
Ó Akadémiai Kiadó, Budapest, Hungary 2013
Abstract The phase composition of asphaltenes taken
from oils of Romashskino field (Russia) was studied with
calorimetry. It was found that in asphaltenes there are
ordered amorphous phases which break in the temperature
ranges 70–130 and 130–170 °C. Polarization microscopy
data show that the liquid crystal phase appears at temper-
atures from 180 to 190 °C. Moreover, it is shown that in
asphaltenes the crystal phases of co-precipitated paraffinic
hydrocarbons and salts can be present.
Keywords Asphaltenes
Asphaltene fractions

Phase composition
Paraffin–asphaltenes interaction
Introduction
Asphaltenes are the oil components containing the heaviest
polycondensed naphtheno-aromatic compounds with het-
eroatoms (O, S, and N) in the cycles or peripheral sub-
stituents and bridges, which do not dissolve in low
molecular mass n-alkanes and do dissolve in benzene or
toluene. The great interest to asphaltenes investigation was
caused by their significant influence on the physical–
chemical properties of the oil system in whole. In oils, the
asphaltenes are in the form of stable nanoaggregates [1, 2].
With the change of external conditions (oil composition,
Y. M. Ganeeva (&)
T. N. Yusupova
G. V. Romanov
Institute of Organic and Physical Chemistry, 8 Arbuzov St.,
Kazan 420088, Russian Federation
e-mail: yuyand@yandex.ru
Y. M. Ganeeva
T. N. Yusupova
G. V. Romanov

N. Y. Bashkirtseva
Kazan National Research Technological University, 68 Karl
Marx St, Kazan 420015, Russian Federation
•
pressure, and temperature) the asphaltenes begin to join in
clusters, then—in floccules, finally form the visco-elastic
network, which sharply increases in oil viscosity, or come
out of the oil system, clogging the pores of the reservoir,
deposited on the underground and surface equipment [3, 4].
In recent times great achievements were reached in the
study of asphaltenes. The size, structure, and mass of as-
phaltene molecules was defined, the concentration bound-
aries of phase transitions of asphaltenes in benzene
solutions and oils were identified [3, 5]. The correlation
between the phase state of asphaltenes and physico-
chemical properties of the oil systems was found [6]. At the
same time, much attention is given to study the phase
composition of asphaltenes and to determine the tempera-
tures of structural transitions in them. One of the funda-
mental methods of investigation of the phase composition
of the matter is the method of differential scanning calo-
rimetry (DSC); however, the interpretation of the DSC
curves of asphaltenes is still very difficult and ambiguous.
For example, different authors have reported the glass
transition temperatures of asphaltenes: 120–130 °C [7],
186–307 °C [8], 0 and 70 °C [9], 35–40 °C [10]. Masson
et al. [9] on the non-reversing heat flow curves of bitumen
asphaltenes observed the endothermic effect in the tem-
perature range from 0 to 70 °C. The value of this endo-
thermic effect depended on the time interval between the
first heating and reheating. This effect have been attributed
to the isotropization of ordered amorphous phase (meso-
phase) in asphaltenes when heated.
Zhang et al. [7] investigated the asphaltenes of vacuum
residues of crude oils by DSC. On the DSC curves they
observed several endothermic effects, the appearance of
which was explained by evaporation of volatile compo-
nents, removal of adsorbed gases, and softening of some
components in the asphaltenes.
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1594 Y. M. Ganeeva et al.

Table 1 Physico-chemical properties and SARA analysis (mass/ %) of crude oils

No. well Density/g cm-3 Viscosity/sSn Saturated Aromatics Resins Asphaltenes

***19 0.8708 20.8 64.2 11.9 19.1 4.8

***35 0.8945 43.6 62.6 13.6 17.6 6.2
**21 0.8788 23.9 64.0 11.5 16.0 8.5
***72 0.8813 23.9 60.9 13.5 18.2 7.4
***48 0.9180 55.7 58.6 16.4 20.3 4.7

On the DSC heat flow curves of the asphaltenes of heavy
oil residues Canadian researchers observed one broad
endothermic effect in the temperature range 50–250 °C, on
which the exothermic effect in the temperature range
100–130 °C is superimposed [11, 12]. According to them,
the asphaltenes consist at least of two solid phases at room
temperature. One of the solids undergoes an endothermic
transition to liquid when heated in the temperature range
50–250 °C while another solid undergoes an endothermic
transition to the liquid crystal state followed by exothermic
dissolution as the temperature is raised.
Nalwaya et al. [13] and Unger et al. [14] reported that
asphaltenes exhibit the crystal-like phase.
The objective of this work was to investigate phase
composition of the asphaltenes of crude oils taken from
Romashkino field (Russia) and to identify the heat effects on
the heat flow curves from the comparative analysis of calo-
rimetric curves of asphaltenes and model mixtures.Table 1.
Experimental
The asphaltenes investigated in this study were precipitated
from crude oils taken from Devonian deposits of Romashkino
field (Russia) (wells ***19, ***35, **21, ***72, and *** 48)
by the addition of 40 mL of petroleum ether (40–70 °C) g-1
of crude oil. The precipitated asphaltenes were washed in a
Soxhlet apparatus with petroleum ether until the filtrate was
colorless. Then the asphaltenes with filter were washed out
with benzene, which was then evaporated.
The heat flow curves of asphaltenes were obtained with
calorimeter C80 (Setaram, France). The measurements
were performed in the temperature range from 30 to
200 °C with a heating rate of 1 °C min-1 with isothermal
periods of 3,600 °C at the beginning and the end of each
experiment. Repeated (second or third) scans were
obtained by heating under the same conditions once the
sample had been cooled at a rate of 1 °C min-1 to room
temperature. All experiments were carried out on 10 mg of
material. Temperature calibration was performed using
indium. Energy calibration was performed using the Joule
effect method in the factory and checked by measuring the
heat of fusion of naphthalene.
The fractionation of asphaltenes was carried out by the
scheme shown in Fig. 1. 1 g asphaltenes was first com-
pletely dissolved with 28 mL toluene. Petroleum ether (b.p.
40–70 °C) was then added in an amount of 52 mL. The
resulting solution put in a dark place on the 24 h and then
was filtered. Precipitated material was washed in a Soxhlet
apparatus with toluene until the solvent was colorless, dried
and weighed until there was no change in mass. Received
asphaltenes were called ‘‘1 fraction.’’ The petroleum ether
in the amount of 228 mL was added in supernatant to ratio
of 90:10 and put precipitated for 24 h. Using the above
operations, fresh precipitated material is separated which
after washing in Soxhlet apparatus with toluene and drying
was named the ‘‘2 fraction’’ of asphaltenes. ‘‘3 fraction’’ of
asphaltenes was recovered by evaporating the remaining
solvent.
Thermogravimetric analysis (TG) was carried out using
Q-1500D Derivatograph system (MOM, Hungary). Open
platinum crucibles were used in the experiments. The mass
of asphaltenes was 30 mg. The heating rate was constant
and equal to 10 °C min-1. The atmosphere in furnace was
stationary. Alumina was used as an inert substance.
For the preparation of model paraffin–asphaltenes mix-
tures the individual n-alkane C24 and oil paraffin with a
molecular mass distribution from C16 to C58 (Fig. 2a) were
used. Figure 1b shows the heat flow curves of these par-
affin under heating. The paraffin–asphaltenes mixtures
were prepared by mixing of benzene solutions of solid
paraffin with the benzene solution of asphaltenes, so that
after evaporating of benzene and bringing residue to a
Asphaltenes Toluene
"3 fraction"
Mixture
Petroleum ether
Petroleum ether
Filtration Filtration
"1 fraction" "2 fraction"
Fig. 1 The scheme of fractionation of asphaltenes

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Phase composition of asphaltenes 1595

Fig. 2 Molecular mass a b

distribution of oil paraffin 12

Exo
(a) and the heat flow curves of
n-alkane C24 (1) and oil paraffin 10 4 1
(2) (b) 2
2
8

Heat flow/mW Endo

Percentage
0
–2
6
–4
4 –6
–8
2
–10
0 –12
16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 40 60 80 100 120
Carbon number in n–alkane Temperature/°C

Fig. 3 The heat flow curves of a

asphaltenes from crude oils of
b
Exo

Exo
Romashkino field: a heating for 1 4
asphaltenes ***19 (1), ***35 3.5
2 cooling
(2), **21 (3), and ***72 (4); 3
Heat flow/mW Endo

b heating and cooling for 0 3 2.5

Heat flow/mW Endo

asphaltenes ***72 4 2
1.5
1
–1
0.5
0
–0.5
heating
–2 –1
40 90 140 190 20 70 120 170
Temperature/°C Temperature/°C
Exo

Exo

1 1
1
1

2
0.5
Heat flow/mW Endo

0.5
Heat flow/mW Endo

2 3

0 0

–0.5 –0.5
40 90 140 190 40 90 140 190
Temperature/°C Temperature/°C

Fig. 4 The heat flow curves of asphaltenes No. **62: original (1) and Fig. 5 The heat flow curves of asphaltenes No. ***19: original (1),
re-heated in 24 h after (2) re-heated in 24 h after (2), and re-heated in 96 h after (3)

constant mass in a vacuum, the paraffin:asphaltenes ratio in Results and discussion

the mixtures was 3:97, 5:95, 7:93, 10:90, or 15:85.
The X-ray phase studies were performed on an auto-
mated D8 Advance X-ray diffractometer (Bruker) equipped
with a Vario setup and a Vantec linear coordinate detector.
The CuKa1 radiation monochromated by the curved Jo-
hansson monochromator (k = 1.5406 Å) was used, and the
performance mode of the X-ray tube was 40 kV, 40 mA.
Experiments were carried out at room temperature in the
Bragg–Brentano geometry on a plane sample. Patterns
were recorded in the 2h range between 1 and 70°, in 0.008°
steps, with a step time of 0.3 s. One powder pattern was
collected and analyzed.
Asphaltenes were investigated in temperature range
30–200 °C by calorimetry (Fig. 3). On the heat flow curves
of asphaltenes one or two endothermic effects in the tem-
perature ranges of 70–130 and 130–170 °C were detected.
During the first heating, the total mass loss was about 5–10 %
what may be due to the evaporation of low molecular mass
components. While re-heating of the same asphaltenes, the
heat flow curves coincide with original curve or recover to
original curve over time. For example, the values of the first
endothermic effect of asphaltenes No. **62 on the first and
second scans are practically equal and are 34.2 and

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1596 Y. M. Ganeeva et al.

Fig. 6 The structures of the S

main types of asphaltene N

molecules and possible N

structures of nanoaggregates of S
O
them [18, 19] N

«island» (A1) «archipelago» (A2)

N
N
O O

S
S

Exo
Table 2 The threshold concentration of heptane (onset point) to 0.4
precipitate Asphaltenes from benzene solution according to DLS
1
Onset point/mL Onset point/mL 0.2
(concentration of (concentration of
Heat flow/mW Endo
2
Asphaltenes in toluene is Asphaltenes in toluene is
0
0,1 g L-1) 1 g L-1)
3
Asphaltene 68.0 64.9 –0.2
Fractions:
1 74.7 55.9
–0.4
3 [94 [94 40 90 140 190
Temperature/°C

Fig. 8 The heat flow curves of Asphaltenes (1), 3 fraction (2), and 1
35
fraction (3)
30

25
phase. The recovery of the high-temperature phase, appar-
ently, requires more time.
Mass/mg

20 Taking into account the hierarchical structure of as-

1
15
phaltenes [4, 15], it can be assumed that reversibility of
calorimetric curves of asphaltenes after heating them to
10 200 °C shows that in this temperature range the destruction
2 of the basic structural units—nanoaggregates does not
5
happen. In this temperature range the weak intermolecular
0 interactions (IMI) between nanoaggregates in clusters and
40 240 440 640 840 flocks break. While cooling these IMI are restored resulting
T/°C in reconstruction of original structure of asphaltenes [4].
Fig. 7 The TG curves of Asphaltene fractions: 1 (1) and 3 (2)
The identification (determination of qualitative compo-
sition) of the structures responsible for endothermic signals
on the heat flow curves of asphaltenes is of great interest. It
33.7 J g-1, respectively (Fig. 4). For asphaltenes No. ***19, is known that in spite of the great variety of asphaltene
the value of the first endothermic effect of original asphalt- molecules there are two basic structural types—
enes is 52.5 J g-1 and a value of endothermic effect on the the « island » and « archipelago » [17] (Fig. 6) or A1 and
second and third scans increases from 39 to 48 J g-1 for A2, which are more and less prone to aggregate, respec-
4 days (Fig. 5). On the example of asphaltenes ***72 it was tively. Figure 5 shows the possible structure of nanoag-
shown that in cooling on the heat flow curve the exothermic gregates: by stacking molecules of type A1 [18] and by
effect in the temperature range of 30–70 °C is observed conformational changes of the molecules of type A2 [19].
(Fig. 3b), indicating the regeneration of the low-temperature To examine the influence of molecules of different

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Phase composition of asphaltenes 1597

Fig. 10 Liquid crystal phases

with Maltese crosses in
asphaltenes No. ***19 (1) and
No. ***35 under cross-
polarized light at 190 °C

Fig. 11 X-ray diffraction of

1900
asphaltenes No. ***19: original 1800
(1) and heated to 190 °C (2) 1700
1600
1500
1400
1300
Lin/counts

1200
1100
1000
900
800
700 1
600
500
400
300 2
200
100
0
5 10 20 30 40 50 60 70
2θ scale

structural types on the shape of heat flow curves the frac-
tionation of asphaltenes was carried out. The fractions 1
and 3, enriched with molecules of type A1 and A2,
respectively, were obtained. To obtain the high yields of
these fractions sufficient to conduct further research, the
mixture of asphaltenes ***35, **21 and ***72 (further
denoted as Asphaltenes) was fractioned. The enrichment of
factions obtained with the molecules of type A1 or A2 has
been proved by EPR spectroscopy, dynamic light scattering
(DLS), as well as the TG.
Indeed, EPR spectroscopy revealed that the fraction 1 is
characterized by a higher content of free carbon radical
(18 9 1019 g-1 compared with 8 9 1019 g-1 for a fraction 3).
This fact testifies that polycondensed naphtheno-aromatic
core of the molecules of 1 fraction is more extended.
From the DLS data, the 1 fraction is characterized by a
lower value of onset point (Table 2). The onset point is the
amounts of precipitant (e.g., n-heptane) which must be
added to benzene solution of asphaltenes for asphaltenes to
begin to precipitate out of solution. The lower onset point
of 1 fraction testifies the greater propensity of this fraction
to aggregate and to form larger aggregates that is peculiar
to molecules of type A1.
The results of TG indicate that 1 fraction is more ther-
mally stable in the temperature range 20–510 °C. Less
mass loss in the temperature range 400–530 °C and large
mass loss in the temperature range 530–800 °C compared
to 3 fractions indicate lower proportion of peripheral alkyl
substituents and greater aromaticity asphaltene molecules
of this fraction, respectively (Fig. 7) which is also char-
acteristic of more molecules of type A1.
A comparative analysis of the heat flow curves of 3 and
1 fractions, enriched with molecules of type A2 and A1,
respectively, showed that in the first the endothermic effect
in the temperature range of 100–130 °C dominates, and in
the second there are two pronounced endothermic effects at
low (100–130 °C) and high (130–170 °C) temperatures
(Fig. 8). Thus, it can be assumed that the high-temperature
endotherm on the heat flow curves is caused by the mol-
ecules of A1 type, as well as that the molecules of A1 type
tend to form the phases with different thermal stabilities.
The possibility of formation of supramolecular struc-
tures (clusters and floccules) in asphaltenes by interaction
of their side alkyl substituents was proved by us in the
study of model paraffin–Asphaltenes mixtures.
Data on the involvement of side chain aliphatic groups
in the formation of asphaltenes aggregates are quite con-
tradictory and are mainly discussed in the aspect of the
possible interaction of asphaltenes and saturated hydro-
carbons. Despite the fact that the authors [20] had not
revealed any interaction between the paraffin hydrocarbons
and asphaltenes in the process of formation of paraffin
deposits, in [21–26] the influence of asphaltenes on the
temperature of crystallization of paraffin hydrocarbons and
gelation has been detected. It was shown that the influence
depends on chemical structure of asphaltenes, degree of

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1598 Y. M. Ganeeva et al.

Fig. 9 The heat flow curves of a b

Asphaltenes (1) and paraffin–

Exo

Exo
Asphaltenes mixtures with 3 % 0.2 1
0.5
(2), 5 % (3), and 15 % (4) of 1
0 2
n-alkane C24 (a) and oil paraffin 0.3

Heat flow/mW Endo

Heat flow/mW Endo

(b) –0.2 3
0.1 2

–0.4 4
–0.1
3
–0.6 –0.3
4
–0.8 –0.5
40 90 140 190 40 90 140 190

Temperature/°C Temperature/°C

Table 3 Calorimetric data of original paraffin and in paraffin–
Asphaltenes mixtures
System Enthalpy of
melting/J g-1
n-C24 212.9
15 % of full enthalpy of melting 31.9
n-C24 in paraffin–Asphaltenes 10.5
mixture at 15 %
Oil paraffin 160.6
15 % of full enthalpy of melting 24.1
Oil paraffin in paraffin– 20.3
Asphaltenes mixture at 15 %
* Degree of crystallinity = Enthalpy of melting/212.9 9 100 %
** Relative n-C24
their aggregation, as well paraffin/asphaltenes ratio. Stud-
ies [27–29] have shown that the interaction of asphaltene
side alkyl chains with high molecular saturated hydrocar-
bons results in the formation of paraffin—asphaltene
aggregates which tend to precipitate out of the petroleum
system. It was found [30, 31] that the properties of the
composites formed upon the interaction of asphaltenes with
paraffin differ from the properties of their components and
are rather determined by the nature of the asphaltenes and
not by the composition of the paraffin or the way of for-
mation of the composite.
Comparative analysis of the heat flow curves of Asphalt-
enes and mixtures showed (Fig. 9) that the higher the solid
paraffin concentration in mixture, the higher the magnitude of
high-temperature endotherm. The amount of crystal phase of
solid paraffin in mixtures is calculated and is compared with
crystallinity of the original solid paraffin (Table 3). It was
found that only part of them takes part in crystallization. The
other part is involved in the asphaltene structurization with
formation of high-temperature ordered phase (Fig. 9, heat
flow curves 4).
Thus, the model experiments show that the molecules of
A1 type are responsible for structuring of asphaltenes to
form the low- and high-temperature phases. Nanoaggre-
gates of molecules of this type are able to form supramo-
lecular structures of different hierarchical levels (clusters
and floccules) through the interactions of the side alkyl
substituents.
Degree of The fine powder of asphaltenes was investigated by
crystallinity/%* polarization microscopy. The appearance of Maltese crosses
100 was recorded at the temperatures of 180–190 °C (Fig. 10),
15.0 that, according to the authors of [11], indicates the appear-
4.9 ance of a liquid crystal phase. ‘‘Crosses’’ remained until the
temperature of 250 °C and did not disappear while cooling
75.2** the samples to room temperature.
11.3 The Maltese crosses disappeared when asphaltenes were
9.5 heated above 250 °C and did not reappear when sample of
asphaltenes was re-heated. Previously, the formation of a
liquid crystal phase in oil systems has been reported. The
formation of liquid crystal phases in carbonaceous material
was found in a study of macroscopic carbonization of
resinous components of some coals and crude oils [32], as
well as at the water–oil interface in oil–water emulsions
with a high pH [33]. It was also reported that the appear-
ance of a liquid crystal phase significantly effect on the
type of diffraction patterns. The position of the diffraction
lines is changed and is closed to the values typical for
infinite graphite network [32].
However, the appearance of Maltese crosses in the as-
phaltenes heated to 190 °C is not impacted on their XRD
patterns. Diffraction patterns of the original asphaltenes
and asphaltenes heated to 190 °C are practically identical
(Fig. 11) and are typical for petroleum asphaltenes [15].
The profiles contain two main peaks: a c band at 20° and
graphene band at 25°, which are produced by aliphatic and
aromatic portions, respectively. In addition, the bands at
32° and 46° are also recorded which are produced by
sodium chloride crystals.
On the heat flow curve of asphaltenes ***48 the narrow
endotherm in the temperature range of 80–100 °C was
found (Fig. 12). Gas–liquid chromatography has shown
that this sample of asphaltenes contains n-alkanes with
carbon numbers from 13 to 60 with a maximum at 54–56
(Fig. 13). It is known that in oils produced by long-term
water flooding the asphaltenes and high molecular mass
paraffin are accumulated. High molecular mass paraffin
is co-precipitated with asphaltenes during a standard

123

Phase composition of asphaltenes
–1
Exo
Heat flow/mW Endo
–1.5
–2
40 90
Temperature/°C
Fig. 12 The heat flow curve of asphaltenes No. ***48
12
10
8 tion temperatures of Turkish asphaltenes. Fuel. 2007;86:1737–48.
Percentage
6 structure of bitumen and its fractions by modulated differential
4 10. Evdokimov IN, Losev AP. Electrical conductivity and dielectrical
2 11. Fulem M, Becerra M, Hasan MDA, Zhao B, Shaw JM. Phase
0 Fluid Phase Equilib. 2008;272:32–41.
10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58
Carbon number in n–alkane
Fig. 13 Molecular mass distribution of n-alkanes in asphaltenes No.
***48
procedure of asphaltenes precipitation [16]. Thus, it is
obvious that endotherm at 80–100 °C is caused by the
melting of crystalline phase of the paraffin co-precipitated
with asphaltenes.
Thus, the complex phase composition of asphaltenes
from Devonian oils of Tatarstan fields was revealed. In
asphaltenes there are low-ordered phases, breaking in the
temperature ranges 70–130 and 130–170 °C and recover-
ing under cooling. It is shown that the asphaltenes mole-
cules with extended polycondensed aromatic structures and
side alkyl substituents are responsible for structuring as-
phaltenes in whole. It is established that the liquid crystal
phase is formed at 180–200 °C in asphaltenes. In addition,
it is shown that in asphaltenes there may be the crystal
phases of co-precipitated high molecular mass paraffin and
metal salts.
Acknowledgements The authors thank S. Reza Bagheri from the
Department of Chemical and Materials Engineering, University
Alberta, Edmonton, Canada for taking photo of liquid crystal phase in
asphaltenes and Vladimir N. Kouryakov from Oil and Gas Research
Institute of Russian Academy of Science, Moscow, Russia for the
experiment by DLS.
Author's personal copy
1599
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