ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2015, Vol. 49, No. 3, pp. 287–296. © Pleiades Publishing, Ltd.

, 2015.
Original Russian Text © M.S. Mullakaev, G.I. Volkova, O.M. Gradov, 2015, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2015, Vol. 49, No. 3, pp. 302–311.

Effect of Ultrasound on the Viscosity–Temperature Properties

of Crude Oils of Various Compositions
M. S. Mullakaeva, G. I. Volkovab, and O. M. Gradova
a
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
b Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences,
Akademicheskii pr. 3, Tomsk, 634021 Russia
email: mullakaev@mail.ru
Received December 27, 2013

Abstract—The effect of ultrasonic treatment on the viscosity–temperature properties of crude oils of various
component compositions has been studied. The efficiency of ultrasonication depends on the group compo
sition of oil and treatment time. The ultrasonic treatment of lowparaffinic oils with a high tar and asphaltene
content leads to a substantial decrease in viscosity and the pour point, and the efficiency of ultrasonication
increases with an increase in the treatment time. For crude oils with a high nalkane content, ultrasonic treat
ment is not effective, which is due to the intensification of crystallization of highmolecular nalkanes. Cal
culations that evaluate the effect of ultrasonic treatment on variations in the viscosity of oils are performed
based on the fatigue mechanism, which have shown that experimental data are in agreement with the calcu
lated values.

Keywords: ultrasound, ultrasonication, ultrasonic treatment, crude oil, petroleum disperse system, asphalt
enes, paraffins, shear stress, shear rate, dynamic viscosity, effective viscosity, pour point, associates
DOI: 10.1134/S0040579515030094

INTRODUCTION Various methods of influence are used to overcome

At present, when evaluating the prospects of crude
oil production in the world, it can be stated that the
epoch of lowcost and easily produced oil has come to
an end. At the same time, the world’s resources of
heavy and viscous oils are estimated to be 700 billion
tons, which is comparable to the world’s reserves of
ordinary oil.
When the critical concentration of tar–asphaltene
components in oil is reached, there is an abrupt
change in rheological properties and structural
mechanical properties begin to manifest to a consider
able extent, which is explained by intermolecular
interactions of tar–asphaltene components with all of
the molecules of a disperse medium.
The mechanisms of structure formation in oil sys
tems under the effect of external factors and the inter
relationship between structure formation and rheolog
ical properties are discussed in [1, 2]. The authors sub
stantiate the direct relationship between conditions for
the formation and destruction of supramolecular
structures (associates, micelles, etc.) in petroleum dis
perse systems and the behavior of tar–asphaltene
components in the processes of preparing, transport
ing, and processing highviscosity oils.
difficulties that arise during the production and trans
portation of problem oils, including thermal, mechan
ical, chemical, physical, and acoustic. An effective
method of enhancing chemical processes in liquids is
cavitational treatment [3, 4]. The pretreatment of
crude oil in ultrasonic and electric fields for the pur
pose of demineralization and dewatering is more
effective for the agglomeration of water particles com
pared with treatment only in an electric field [5]. The
possibility of decreasing the viscosity of diesel fuel due
to the use of an ultrasonic energy produced in long
channels with small diameters was experimentally
proven in [6]. The effect of ultrasonic waves at differ
ent frequencies and powers on the variations in viscos
ity for three types of petroleum products was studied in
[7], and it was found that viscosity decreased in all of
the experiments.
The variations in the rheological characteristics for
various samples of crude oil after ultrasonic irradiation
at different operating parameters for different shear
rates were investigated in [8]. It is found that, after
ultrasonic treatment, the flow of oil is of a pseudoplas
tic character and the decomposition of highmolecu
lar components takes place over a certain interval of
treatment time.

287
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Table 1. Physicochemical properties and group composition of crude oils under study

μ, mPa s Tz, °C Content, wt %

No.
(at 20°C) oils (including nalkanes) tars asphaltenes
1 227 18 98.6 (10.1) 1.4 Trace amounts
2 850 18 72.0 (20.0) 25.9 2.1
3 382 19 80.3 (18.9) 15.6 4.1
4 82 –8 77.7 (5.9) 15.5 6.8
5 363 –5 63.1 (3.0) 35.7 1.2
6 75 –18 73.5 (2.8) 21.9 4.6
7 295 –17 83.4 (0.9) 15.4 1.2
8 1014 –17 65.3 (1.4) 28.6 6.1
9 5800 –19 59.0 (1.1) 31.1 9.9
10 1046 –20 81.6 (4.5) 12.5 5.9
11 78 –28 81.3 (2.2) 15.4 3.3

It is shown [9–11] that, after ultrasonic treatment,
there is a change in the rheological properties of crude
oil due to dispersing the heavy components of a colloid
and asphaltenes contained in oil. Combined treatment
by ultrasound and chemical reagents [12–14] or ther
moacoustic treatment [15–17] is more effective.
When the process is scaled up, it is expedient to per
form cavitational treatment using hydrodynamic radi
ators [18–20].
The objective of this study is to investigate the effect
of ultrasonic treatment on the viscosity and congela
tion temperature of crude oils with different composi
tions regarding nalkanes and tar–asphaltene compo
nents, calculate the dependence of viscosity on the
sizes of associates of supramolecular asphaltene struc
tures before and after ultrasonic irradiation, and
experimentally verify the calculation results.
EQUIPMENT AND METHODS OF ANALYSIS
The experimental procedure consisted in treating a
fixed amount of oil (300 mL) in a steel batch reactor
using an MSP 1/24 transducer connected to an MUG
4/1827 generator with a power of 4 kW. Elastic vibra
tions were introduced into a load using a rod
waveguide with a working end 20 mm in diameter, the
vibration amplitude of which was 5–10 μm at a reso
nance frequency of 24.3 kHz.
The original and ultrasonically treated samples of
oil were temperature controlled for 30 min at a tem
perature of 20°C, and rheological parameters were
then determined using a Brookfield DVIII ULTRA
viscometer over a wide range of shear rates. The mea
surements results were processed using the Rheocalc
software. The error of measurements for tangential
stress was ±3 rel %.
Effective viscosity was determined using an INPN
SX measuring instrument for lowtemperature char
acteristics of petroleum products, which is a rotational
viscosimeter that measures the torsional moment at a
constant shear rate of 250 rad/s. The accuracy of mea
suring the temperature of a sample was ±0.2°С, and
the accuracy of determining the viscosity was 2%. The
procedure takes into account the requirements of the
ASTM D2602 and ASTM D4684 international stan
dards.
The pour point of the samples was determined
using an INPN KRISTALL device, the operating
principle of which is based on the exposure of a sample
to infrared radiation in the near wave band. The results
of measurements are processed using a builtin micro
processor, and the current information is displayed on
a liquidcrystal screen. A cryostat is manufactured
using Peltier elements. The accuracy of measuring the
temperature of the sample is ±0.2°C.
The average radii of associates were measured using
a laser photon correlation spectrometer that consisted
of an opticalmechanical unit, a system for thermosta
bilization and temperature measurement, an FEU
136 system for counting photons, and an LG38
helium–neon laser (λ = 0.6328 μm and Р = 50 mW)
at 20°C for an oiltohexane ratio of 1 : 100. The vol
ume of samples was 1 cm3, and the error of measure
ments was 3–5%.
RESULTS AND DISCUSSION
The physicochemical properties and group compo
sition of the oils under study are given in Table 1.
Highparaffinic oils 1, 2, and 3 were subjected to ultra
sonic treatment for 1–10 min. The temperature in the
reactor was maintained to be 25–30°C, since paraffins
crystallized on the walls of the reactor at lower temper

JOURNAL OF THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 49 No. 3 2015