SPE-185558-MS

Onset of the Asphaltene Flocculation and Asphaltene Hydrodynamic Radius

Determination Using H-Diffusion- Ordered Spectroscopy DOSY NMR

M. I. Sandoval and S. F. Muñoz Navaro, Universidad de Santander, Grupo de Investigación Recobro Mejorado; D.
Molina Velasco, Universidad Industrial de Santander

Copyright 2017, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Latin America and Caribbean Petroleum Engineering Conference held in Buenos Aires, Argentina, 18-19 May 2017.

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Abstract
During EOR recovery processes, asphaltenes macromolecules can flocculate and cause drastic changes in
the petrophysical properties of the reservoir, therefore it is very important to determine the time at the
flocculation begins and further the size of the aggregates, since ultimately this depends on whether these
can be trapped in the porous media. This work aims to evaluate the change in the asphaltene hydrodynamic
radius of at different concentrations of n-heptane and to detect the onset asphaltene floculation using a new
technique known as 1H Diffusion ordered spectroscopy-NMR (DOSY-NMR). H-DOSY NMR is a method
based on the pulsed field gradient spin-echo from nuclear magnetic resonance (PFGSE NMR) and it allows
the identification of the molecular components of a mixture sample and at the same time obtain information
of their size through the diffusion coefficient. For our specific case, the asphaltene hydrodynamic radius
was 16.8 Å and the onset of asphaltene floculation can be observed when the concentration of solvent n-
heptane was 30 wt %.

INTRODUCTION
Asphaltenes contained into oil are a constant concern at petroleum engineering (alexander, 2004), (Rogel,
2004). During several recovery processes, these macromolecules can flocculate and deposit causing drastic
changes in the petrophysical properties of the reservoir and economic losses (Mousavi, 2004). Asphaltenes
are defined as the heaviest and most polar part of the hydrocarbon oil, because they are composed by
large systems of polynuclear aromatic rings (4 to 20 rings) attached to the aliphatic side chains and with
heteroatoms distributed in both components of the molecule (Gwrys, 2006), asphaltenes are insoluble in
alkanes (n-heptane and pentane) and soluble in toluene (Nassim, 2014). These can be dissolved or suspended
in the oil according to the size of the molecules (Kawanka, 1988). The stability of these particles can be
disrupted by addition of solvents which cause desorption of the resin molecules from the asphaltene-particle
surface (e.g. n-heptane). When two asphaltene particles collide on their resin- uncovered spaces, aggregation
occurs, therefore, we may expect that at a particular solvent concentration the aggregation process will be
initiated rather vigorously. This point is defined as the onset of asphaltene flocculation (Escobedo, 1996).
These can be dissolved or suspended in the oil according to the size of the molecule. Because the complexity
2 SPE-185558-MS

of its molecules, some properties are still under discussion such as: weight of the asphaltenes, size of the
molecule, chemical structure and state of the flocculation process. (Emanuelle, 2009).
Nuclear Magnetic Resonance (NMR) has been used to determine asphaltenes structure in oil
hydrocarbons (Dickinson, 1980), (Nielsen, 2008). The introduction of new techniques such as diffusion-
ordered 2D NMR spectroscopy (DOSY), that represents results of diffusion in two-dimensional spectrum
in which the first dimension is a conventional NMR spectrum with the species chemical shift and the second
one represents their diffusion coefficient (Morris, 1995). This method has also been used in the distribution
of mass statistics in polymers (Chen, 1995), characterization of polymer additives (Jayawicrama, 1998),
and analysis of complex hydrocarbon mixtures (Kamur, 2005).
In this paper, the DOSY technique was used to determine asphaltene size and onset of asphaltene
flocculation varying the concentration of solvent n-heptane. With the respective spectra results, the diffusion
coefficients and the Stokes Einstein equation it was possible to determine the hydrodynamic radius of the
asphaltenes and the onset of asphaltene flocculation due to iteractions between asphaltenes molecules, this
last one can be determined with the change of this radius as the solvent concentration was increasing over
time

THEORETICAL BASIS
DOSY NMR theory
Diffusion ordered spectroscopy (DOSY) is a method devised by Morris and Johnson, its physical principles
is based in the application of magnetic field gradient (Johnson, 1999), Based on the Carr-Purcell Gill
Meiboom sequence concept (CPMG) (Car,1954). To determine the self-diffusion coefficient from the
magnetic field gradient, it is necessary to assume that the sample of nuclear magnetic resonance is divided
into slices through z-axis and the magnetization vectors of different spins located in each of these areas
precess depending on the magnetic field that is applied, then if the magnetic field is homogeneous the spins
will rotate at the same frequency according to Eq. 1 (Khatchikian,2011),and it will be in coherence phase
(Fig. 1a.), however in the case of applying a magnetic field intensity (G) for a certain time (∂) in the z-axis,
the Larmor frequency will depend on the position and the gradient magnetic field applied, as shown in Eq.2
(Hurd,1996), obtaining different phases at each slice as analyzed in Fig. 1b. In this stage is impossible to
obtain a signal, because it is necessary that the spins be in the same phase. To refocus the magnetization
vectors, a second gradient of magnetic field with the same duration (∂) and intensity (G) is applied after
a certain time (Δ) (Fig. 1c.), nevertheless, if the spins move between the offset and focusing gradients,
for example, in diffusion process, the signal strength will change. This change allows to determine the
coefficients of diffusion or rate of movement of each molecule through an exponential function described
in Eq.3 (Gantes, 2009).
(1)
(2)

(3)
SPE-185558-MS 3

Figure 1—Behavior of the magnetization vectors. (a). After applying a homogeneous magnetic
field. (b). Before applying the offset gradient. (c). Before applying the refocusing gradient.

Where w and wz are the Larmor frequency for a fixed external magnetic field and magnetic field gradient
in the z direction respectively, γ is the gyromagnetic constant , B0 the intensity of the
magnetic field, A the amplitude of the signal resulting from the application of the magnetic field gradient,
and A0 the amplitude of signal when gradient is equal to zero i.e. when only an external fixed gradient is
applied.
To determine the diffusion coefficient there are several sequences with DOSY NMR, however in this
paper the sequence of bipolar pulse to diffusion experiments (BPPESTE) was employed, which consists
of applying a positive offset gradient for a time equal to ∂/2, after that it is applied a 180 ° pulse of
rediofrecuency. Finally, a negative gradient during the same time (∂/2) was generated to refocus as shown
in Fig. 2. The main advantage of this secuence is to reduce the problem caused by the Eddy current and
finally avoid distortions in the resulting spectrum.

Figure 2—Basic scheme of bipolar gradients of duration ∂/2

Molecular self-diffusion and Self-diffusion coefficient

Molecular self-diffusion is a random and incoherent motion due to kinetic energy of molecular systems,
these motion cause collisions between molecules and generate changes in its directions. It depends directly
on self-diffusion coefficient, which represents the rate of movement of a solute molecule in a solvent, in
other words, the distance that a molecule can travel in a solvent during a time interval. This coefficient
depends on three factors: size and shape of solute, system temperature and solvent viscosity as shown on
the Stokes-Einstein equation. Eq.4.

(4)
4 SPE-185558-MS

Where, KB is the Boltzman constant, T temperature, ŋ solvent viscosity and Rh the hydrodynamic radius
of the solute particle. The equation number 4 describes the diffusion process to spherical particles when the
solute is five times larger than the radius of the solvent, nevertheless in this work cannot be used, because the
asphaltenes do not have these characteristics. For this reason, it is necessary to use a new equation (Eq.5),
which takes into account the shape and size of the solute (Macchioni, 2008).

(5)

Where c is a factor that depends on the ratio of the radius of the solute and the solvent molecule (Chen,
1984), defined in the following equation (Eq.6):

(6)

fs is the shape factor, however for the present work is assumed equal to 1 (Durand, 2009), i.e. is considered
as a spherical particle.
Finally, the equation to determine the hydrodynamic radius from the diffusion coefficient obtained from
the DOSY NMR spectra can be seen below. (Eq.7)

(7)

The diffusion velocity can be used to study the interations between molecules (Ackerman, 2002), in this
case, it will be used to determine the moment when the asphaltenes start to cluster, point known as onset
of asphaltene flocculation (Samir,2007), Whose concept is based on the fact that the diffusion coefficient
is altered after the addition of another molecule. Therefore, at the moment when the system is unstable by
the presence of precipitating solvent, the diffusion coefficient of the asphaltenes will decrease and the size
of the aggregates can be determined.

SAMPLE PREPARATION FOR DOSY NMR

To achieve the aim of the present work, the asphaltenes were extracted from heavy oil and these were
subjected to rotoevaporation to remove n-heptane traces, which was used in their respective extraction. The
dry asphaltenes were mixed and homogenized with toluene in a sealed container during several hours at
40°C, after that, these mixtures were prepared with different n-heptane concentrations and placed into 5-
mm NMR tubes at 25 °C (298.15°K). Each of these tubes was taken into a Bruker Avance III equipment
whose frequency is 400 MHz, the sample was divided into 50 liner steps (slices). For each sample tube
an H-DOSY spectrum were obtained, i.e. a plot between the diffusion coefficients and the chemical shift.
With the obtained diffusion coefficients from the spectra and the Newton-Stokes equation, it is possible to
calculate the asphaltene hydrodynamic radius.

RESULTS AND DISCUSSION

Asphaltene hydrodynamic radius through1H DOSY NMR spectrum

The first analysis reach was the determination of the asphaltenes hydrodynamic radius in solution, by
preparing a homogenous mixture with 18 % asphaltenes from which the next 1H DOSY NMR spectrum
SPE-185558-MS 5

was gotten (Fig.3), where was possible to identify, the main components of the mixture (i.e. asphaltenes
and toluene), by the associated chemical shift values on the x-axis.

1
Figure 3—18 wt % asphaltenes H DOSY NMR spectrum in toluene

The shape of signals and chemical shift values 7.3, 7.01, 6.95 and 2.13 ppm in Fig.3. corresponds to
the signal of toluene. The asphaltene signal is shown on aliphatic zone 1.313 ppm, even though there
are some aromatic protons of asphaltenes, but they are no detected because the signal-to-noise ratio is
too low compared to the toluene signal. The diffusion coefficient of solute and solvent are very different,
for this reason is easy to separate their signals (Fig. 3.), the asphaltenes diffusion coefficient is equal to
−9.655 and for toluene is . With
the asphaltene diffusion coefficient on spectrum, equation 5 and numerical methods it was possible to
estimated the hydrodynamic radius, which was equal to about 16.8 Å.

Onset of asphaltenes flocculation

To determine the onset of asphaltene flocculation to the prepared mixture of toluene and asphaltenes,
different amounts of solvent n-heptane was added in each of the tubes to obtain a wide range of
concentrations.
In Fig. 4 through Fig 6. are shown the spectrums of differtent solvent n-heptane concentrations 10%,
20% and 30% respectively, these spectrums have n-heptane, toluene and asphaltenes signals.
6 SPE-185558-MS

1
Figure 4—Mixture of toluene and asphaltenes H DOSY NMR spectrum analyzed at 10 wt% n-heptane.

1
Figure 5—Mixture of toluene and asphaltenes H DOSY NMR spectrum analyzed at 20 wt% n-heptane
SPE-185558-MS 7

1
Figure 6—Mixture of toluene and asphaltenes H DOSY NMR spectrum analyzed at 30 wt% n-heptane

The spectrums shown in Fig. 4 and Fig. 5 are similar, in this figures were observed that asphaltenes signals
have the same diffusion coefficient, this indicates that the asphaltenes hydrodynamic radius do not changed
with the n-heptane concentration, however in Fig. 6, we can observe two diffusion coefficient values of
asphaltenes at the same chemical shift value. This means that the asphaltenes have begun the floculation
processes, due to the destabilization caused by the solvent precipitant, Therefore the size of the asphaltenes
increases, then, according to the Fig. 6 the mixture with 30% n-heptane have two asphaltenes species with
hydrodynamic radius equal to 16.8 Å and 62.405 Å.
As the n-heptane concentration continue increasing we can observe notorious changes in mixtures of
toluene and asphaltenes spectrum at 40 wt% and 50 wt% n-heptane, since the increasing in the size of
asphaltenes is directly linked with the precipitant solvent amount in solution.
Finally, on the Fig 7 and Table 1 are shown the results of the weighted average hydrodynamic radius of
the asphaltenes at different concentrations of solvents, in this figure (Fig. 7) the beginning of the flocculation
30% n-heptane can be identified.

Figure 7—The weighted average hydrodynamic radius of the asphaltenes

at different concentrations of solvents and onset of flocculation
8 SPE-185558-MS

Table 1—The weighted average hydrodynamic radius of the asphaltenes at different concentrations of solvents

Diffusion weighted average

Solvent Asphaltene
Cohefficient. hydrodynamic
Concentration Radius Å
m2/s radius Å

0 3.19E-10 16.8 16.80

10 3.19E-10 16.8 16.80

20 3.19E-10 16.8 16.80

3.19E-10 16.8
30 23.92
5.90E-11 62.405

3.19E-10 16.8

5.9E-11 62.405
40 35.00
4.93E-11 75.45

4.35E-11 85.45

3.19E-10 16.8

4.35E-11 85.45
50 38.08
3.89E-11 95.45

3.22E-11 115.40

CONCLUSION
The aim of this research was to study the asphaltenes size and the onset of flocculation by NMR techniques
with the concept of diffusivity. We measured and analysed the diffusion coefficient of asphaltenes-toluene
solution and asphaltenes-toluene-n-heptane. The asphaltene concentration was 18 wt % and the n-heptane
fraction varied from 0 up to about 50 wt %, covering the onset of flocculation. The solute size determined
from 1H DOSY NMR spectrum, when n-heptane was equal to zero, was 16.80 Å. To the n-heptane
concentrations 10 wt% and 20 wt% the asphaltenes diffusion coefficients remained constant. Nevertheless,
a clear separation in the diffusivity dimension between two different kinds of asphaltenes was observed
from concentration of 30 wt %, reflecting the beginning of the flocculation.

ACKNOWLEGDEMENT
The authors wish to thank Dr. Daniel Molina and Dr. Maria Helena Torres in the NMR Laboratory at
Guatiguara Technological Park. As well as Professor Luis Felipe Carrillo for providing the asphaltenes
samples and the GRM reaserch group staff for the helpful discussions.

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