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aggregation
Yevgeniy G. Burya, Igor K. Yudin, Victor A. Dechabo, Victor I. Kosov, and Mikhail A. Anisimov
Dynamic light scattering with an original optical scheme has been used for the investigation of opaque
共strongly light-absorbing兲 asphaltene colloids in crude oils and hydrocarbon mixtures. Diffusion-limited
aggregation and reaction-limited aggregation as well as a crossover between these two regimes have been
observed. A simple interpolation for the crossover kinetics is proposed. Asphaltene colloidal struc-
tures, originally persisting in crude oils, have been detected. Addition of a precipitant above a threshold
induces asphaltene aggregation. Depending on the nature of the precipitant, different crude oils re-
spond differently on its addition: 共a兲 exponential-in-time growth of aggregates to huge flocks or 共b兲 fast
formation of stable-in-size particles. © 2001 Optical Society of America
OCIS codes: 000.2190, 000.2170.
correlation between asphaltene stability and the col- where kB is Boltzmann’s constant and T is the tem-
loidal properties of crude oils. perature.
The kinetics of the aggregation of colloidal particles Equation 共2兲 is valid for noninteracting particles.
has been a subject of extensive experimental and the- If the particles are involved in an aggregation pro-
oretical study. Numerous studies of the structure cess, they certainly interact. However, Eq. 共2兲 is still
and the aggregation of gold colloids, silica, polysty- applicable to the monitoring of the change in the
rene latex, and melanin particles have been report- apparent particle size if the characteristic time of
ed.4,5 The universality of the aggregation regimes aggregation is much greater than the time of a single
for these classical colloidal systems is discussed.4,6 – 8 measurement. It is worthy to note that, because of
Nevertheless, the mechanism of aggregation, the pro- the low resolution of particle sizing in asphaltene
cess of formation of fractal aggregates, and a cross- opaque systems, one can measure a mean particle
over between different regimes of aggregation, size only. The opacity of the asphaltene solution
especially for complex colloidal systems, still requires prevents reliable measurements of the angular dis-
further investigation. In this paper, we present the tribution of the light-scattering intensity as well.
results of a study of the aggregation kinetics of as- Detailed information concerning polydispersity, rota-
phaltene colloidal particles in hydrocarbon media by tional diffusion, and particle fractality4,11–14 for these
dynamic light scattering. very complex systems still cannot be obtained.
We used an original optical scheme that enables us
2. Method and Technique to perform dynamic light-scattering measurements
A photon-correlation spectrometer with an original in disperse petroleum systems and, in particular, to
optical scheme and a multifunctional single-board study aggregation phenomena in opaque solutions of
correlator to perform dynamic light-scattering mea- petroleum asphaltenes.9 Two suitable light-
surements was used in the experiments.9 scattering geometries were used for particle sizing in
The desired information about particle motion can opaque petroleum dispersions. In the backscatter-
be obtained from the correlation function of the ing geometry 关Fig. 1共a兲兴 a rectangular sample cell is
scattered-light intensity, which has a characteristic placed at an angle of 45° with respect to the incident
decay time tc. The diffusion coefficient D of the par- laser beam that emanates from a low-intensity
ticles suspended in liquid media is related directly to He–Ne laser 共2 mW, 632.8 nm兲 with the intensity of
the decay rate of the time-dependent correlation func- the laser beam further attenuated by a neutral glass
tion. For the homodyne spectrum the relation be- filter to avoid thermal lens effects. The photon-
tween D and tc reads10 detecting system is located such that its optical axis
is normal to the surface of the sample cell. The scat-
D ⫽ 1兾2t c k 2, (1) tered light is collected from the region where the laser
beam enters the sample. To obtain optimal condi-
where k is the wavenumber of the scattered light, k ⫽ tions for collecting scattered light and for suitable
共4n兾兲sin共⌰兾2兲, n is the refractive index of the me- alignment of the incident laser beam required the
dium, is the light wavelength in vacuum, and ⌰ is design of an optical plate. The position of the scat-
the scattering angle. tering volume can be adjusted to study light scatter-
The Stokes–Einstein equation interrelates the dif- ing near the wall of the cell 共approximately 200 m
fusion coefficient D, the shear viscosity of the me- away from the wall to exclude the influence of the
dium, and the mean hydrodynamic radius of the surface兲 as well as in the bulk of the fluid. Such a
particles R by scheme allows one to measure particle size in any
opaque liquid. The corner geometry 关Fig. 1共b兲兴 is
D ⫽ k B T兾6R, (2) suitable for semitransparent dispersions. Such a
SARA Values
Crude Oil Saturates 共%兲 Aromatics 共%兲 Resins 共%兲 Asphaltenes 共%兲