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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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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 %.

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

1999). This method has also been used in the distribution of mass statistics in polymers (Chen. chemical structure and state of the flocculation process. Based on the Carr-Purcell Gill Meiboom sequence concept (CPMG) (Car.2011). for example.and it will be in coherence phase (Fig. its physical principles is based in the application of magnetic field gradient (Johnson. 2008). 1995). in diffusion process. With the respective spectra results.2 (Hurd. This change allows to determine the coefficients of diffusion or rate of movement of each molecule through an exponential function described in Eq. the DOSY technique was used to determine asphaltene size and onset of asphaltene flocculation varying the concentration of solvent n-heptane. 2005). if the spins move between the offset and focusing gradients.).). then if the magnetic field is homogeneous the spins will rotate at the same frequency according to Eq.1954). the Larmor frequency will depend on the position and the gradient magnetic field applied. The introduction of new techniques such as diffusion- ordered 2D NMR spectroscopy (DOSY). (Nielsen. (1) (2) (3) . 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. In this stage is impossible to obtain a signal.1996). 1980). 1 (Khatchikian. some properties are still under discussion such as: weight of the asphaltenes. 1b. characterization of polymer additives (Jayawicrama.2 SPE-185558-MS of its molecules. 1a. Nuclear Magnetic Resonance (NMR) has been used to determine asphaltenes structure in oil hydrocarbons (Dickinson. and analysis of complex hydrocarbon mixtures (Kamur. 2009).3 (Gantes. 2009). 1995). 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. however in the case of applying a magnetic field intensity (G) for a certain time (∂) in the z-axis. the signal strength will change. a second gradient of magnetic field with the same duration (∂) and intensity (G) is applied after a certain time (Δ) (Fig. To determine the self-diffusion coefficient from the magnetic field gradient. To refocus the magnetization vectors. 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. because it is necessary that the spins be in the same phase. obtaining different phases at each slice as analyzed in Fig. 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. as shown in Eq. nevertheless. size of the molecule. 1998). (Emanuelle. 1c. In this paper.

when only an external fixed gradient is applied. Eq. A the amplitude of the signal resulting from the application of the magnetic field gradient. which consists of applying a positive offset gradient for a time equal to ∂/2. (4) . Finally. after that it is applied a 180 ° pulse of rediofrecuency. It depends directly on self-diffusion coefficient. however in this paper the sequence of bipolar pulse to diffusion experiments (BPPESTE) was employed. B0 the intensity of the magnetic field. a negative gradient during the same time (∂/2) was generated to refocus as shown in Fig. This coefficient depends on three factors: size and shape of solute. Before applying the refocusing gradient. After applying a homogeneous magnetic field. which represents the rate of movement of a solute molecule in a solvent.SPE-185558-MS 3 Figure 1—Behavior of the magnetization vectors. (a). in other words. To determine the diffusion coefficient there are several sequences with DOSY NMR. system temperature and solvent viscosity as shown on the Stokes-Einstein equation. these motion cause collisions between molecules and generate changes in its directions. (c). 2. Where w and wz are the Larmor frequency for a fixed external magnetic field and magnetic field gradient in the z direction respectively.e. 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. The main advantage of this secuence is to reduce the problem caused by the Eddy current and finally avoid distortions in the resulting spectrum.4. Before applying the offset gradient. and A0 the amplitude of signal when gradient is equal to zero i. (b). the distance that a molecule can travel in a solvent during a time interval. γ is the gyromagnetic constant .

it is possible to calculate the asphaltene hydrodynamic radius. i. 2008). because the asphaltenes do not have these characteristics.e. which takes into account the shape and size of the solute (Macchioni.15°K). which was used in their respective extraction. the diffusion coefficient of the asphaltenes will decrease and the size of the aggregates can be determined.2007).e. a plot between the diffusion coefficients and the chemical shift. the sample was divided into 50 liner steps (slices). Whose concept is based on the fact that the diffusion coefficient is altered after the addition of another molecule. it will be used to determine the moment when the asphaltenes start to cluster. however for the present work is assumed equal to 1 (Durand. ŋ solvent viscosity and Rh the hydrodynamic radius of the solute particle. by preparing a homogenous mixture with 18 % asphaltenes from which the next 1H DOSY NMR spectrum . the asphaltenes were extracted from heavy oil and these were subjected to rotoevaporation to remove n-heptane traces.7) (7) The diffusion velocity can be used to study the interations between molecules (Ackerman. it is necessary to use a new equation (Eq. these mixtures were prepared with different n-heptane concentrations and placed into 5- mm NMR tubes at 25 °C (298.6): (6) fs is the shape factor. is considered as a spherical particle. the equation to determine the hydrodynamic radius from the diffusion coefficient obtained from the DOSY NMR spectra can be seen below. point known as onset of asphaltene flocculation (Samir. T temperature. (Eq. 2002). The dry asphaltenes were mixed and homogenized with toluene in a sealed container during several hours at 40°C. defined in the following equation (Eq. at the moment when the system is unstable by the presence of precipitating solvent. KB is the Boltzman constant. in this case. (5) Where c is a factor that depends on the ratio of the radius of the solute and the solvent molecule (Chen. SAMPLE PREPARATION FOR DOSY NMR To achieve the aim of the present work. For each sample tube an H-DOSY spectrum were obtained.4 SPE-185558-MS Where. RESULTS AND DISCUSSION Asphaltene hydrodynamic radius through1H DOSY NMR spectrum The first analysis reach was the determination of the asphaltenes hydrodynamic radius in solution. after that. Therefore. Finally. The equation number 4 describes the diffusion process to spherical particles when the solute is five times larger than the radius of the solvent. i. Each of these tubes was taken into a Bruker Avance III equipment whose frequency is 400 MHz. 2009). 1984). nevertheless in this work cannot be used. For this reason. With the obtained diffusion coefficients from the spectra and the Newton-Stokes equation.5).

asphaltenes and toluene). 4 through Fig 6. 7.95 and 2. these spectrums have n-heptane. corresponds to the signal of toluene.). .01. 1 Figure 3—18 wt % asphaltenes H DOSY NMR spectrum in toluene The shape of signals and chemical shift values 7.655 and for toluene is . 20% and 30% respectively.e.SPE-185558-MS 5 was gotten (Fig. equation 5 and numerical methods it was possible to estimated the hydrodynamic radius. are shown the spectrums of differtent solvent n-heptane concentrations 10%. where was possible to identify. 6. by the associated chemical shift values on the x-axis. With the asphaltene diffusion coefficient on spectrum. In Fig.13 ppm in Fig. which was equal to about 16. 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.8 Å.3).3. The asphaltene signal is shown on aliphatic zone 1. the main components of the mixture (i. different amounts of solvent n-heptane was added in each of the tubes to obtain a wide range of concentrations. even though there are some aromatic protons of asphaltenes. Onset of asphaltenes flocculation To determine the onset of asphaltene flocculation to the prepared mixture of toluene and asphaltenes. toluene and asphaltenes signals.313 ppm.3. 3. for this reason is easy to separate their signals (Fig. the asphaltenes diffusion coefficient is equal to −9.

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 .

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 . 6 the mixture with 30% n-heptane have two asphaltenes species with hydrodynamic radius equal to 16. 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.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. 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. 6. according to the Fig.8 Å and 62. however in Fig. Finally. we can observe two diffusion coefficient values of asphaltenes at the same chemical shift value. then.405 Å. due to the destabilization caused by the solvent precipitant. 5 are similar. Therefore the size of the asphaltenes increases. 4 and Fig. in this figure (Fig. this indicates that the asphaltenes hydrodynamic radius do not changed with the n-heptane concentration. This means that the asphaltenes have begun the floculation processes. in this figures were observed that asphaltenes signals have the same diffusion coefficient. since the increasing in the size of asphaltenes is directly linked with the precipitant solvent amount in solution.

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