Ultrasonics - Sonochemistry 48 (2018) 383–395

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Ultrasonics - Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Experimental and theoretical study of crude oil pretreatment using T

low-frequency ultrasonic waves
⁎
Ali Khajehesamedinia, Ali Sadatshojaieb, Payam Parvasic,d, Mohammad Reza Rahimpourd, ,
Mohammad Mehdi Naserimojarade
a
Programa de Engenharia Química/COPP, Universidade Federal do Rio de Janeiro, Rio de Janeiro 21941-972, Brazil
b
Chemical and Petroleum Engineering Department, Sharif University of Technology, Tehran, Iran
c
Department of Chemical, Petroleum and Gas Engineering, Shiraz University of Technology, Shiraz, Iran
d
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
e
School of Mechatronic Systems Engineering, Simon Fraser University, Vancouver, Canada

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, an ultrasound experimental setup was designed to investigate the feasibility of using low-frequency
W/O Emulsion ultrasonic waves as a substitute to reduce the consumption of chemical demulsifiers in the pretreatment of crude
Low-frequency ultrasonic waves oil. The experiments were planned to study the effects of irradiation time, ultrasonic field intensity and initial
Population balance model water content on the efficiency of separation. The results of experiments showed that by selecting a proper
Coalescence model
irradiation time and field intensity, it is possible to decrease the usage of demulsifiers by 50%. Moreover, a
Crude oil
population balance model was proposed to explicate the experimental data. A hybrid coalescence model was
developed to determine the frequency of aggregation. The parameters of the model were estimated by linear
regression. The parameter estimation was performed using a parallel execution of the particle swarm optimi-
zation algorithm. The results of the model showed a decent agreement with the experimental data.

1. Introduction
The complex nature of water-in-oil (W/O) emulsions is a principal
obstacle to develop a satisfactory separation technique in the petroleum
industry [1]. In spite of the recent attempts to develop a reliable de-
mulsification technique, most of the water-in-crude oil emulsions
cannot be broken in small timespans [1]. The stability of W/O emul-
sions originates from the creation of a rigid film at the water-oil in-
terface [2]. The indigenous materials of crude oil such as asphaltenes
and resins tend to accumulate at the interface, resulting in a film that
performs as a structural barrier to the aggregation of the droplets [2].
The solidity of the film increases by time, as the accretion of the in-
digenous materials at the interface rises [3].
Electrocoalescence is known as the common industrial process to
break the w/o emulsions and separate the disperse water droplets from
crude oil [4]. The application of high potential electrical fields to the
w/o emulsions polarizes water droplets and accelerates their coales-
cence [4]. Although the electrocoalescence has proved to be sufficient
for breaking the w/o emulsions, a pretreatment process might be ne-
cessary for desalination of some crude oils. The high stability of the
interfacial film, especially in high viscosity crude oils, demands a pre-
treatment/destabilization to facilitate the desalination process [5].
Chemical demulsification is known to be the most common method
for the pretreatment of crude oil [1]. Due to the high interfacial activity
of chemical demulsifiers, they tend to adsorb/displace the indigenous
species present in crude oil, which results in weakening of the inter-
facial film [6]. However, Chemical demulsifiers have shown to have
practical problems. The substance is costly and not recyclable after
injection. Moreover, a part of the material is added to the wastewater,
along with the water separated from the crude oil. Most of the de-
mulsifiers contain synthesized chemical compounds, which enter to
effluents and cause environmental problems [7]. Therefore, due to the
limitations of thermal and chemical demulsification, new technologies
are desired for the pretreatment of crude oil.
Over the past few decades, the competency of radiation technolo-
gies to manipulate small particles in liquid suspensions has been used as
a basis for various filtration and recovery processes [8,9]. Several se-
paration phenomena are observed in the demulsification of emulsions
under the influence of ultrasonic field [10]. The molecular transfer of
pressure pulses to the material creates a vibrating motion along the

Abbreviations: AC, alternative current; API, American Petroleum Institute degree; SARA, Saturate, Aromatic, Resin and Asphaltene
⁎
Corresponding author.
E-mail address: rahimpor@shirazu.ac.ir (M. Reza Rahimpour).

https://doi.org/10.1016/j.ultsonch.2018.05.032
Received 17 April 2018; Received in revised form 23 May 2018; Accepted 26 May 2018
Available online 29 May 2018
1350-4177/ © 2018 Elsevier B.V. All rights reserved.
A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

Nomenclature t time (s)

tr irradiation time (s)
a diameter of droplet (m) T temperature (K)
a1 diameter of the smaller droplet (m) ud droplet velocity (m/s)
â ratio of the smaller droplet diameter to the larger droplet u12 relative velocity of two droplets (m/s)
diameter u∘ velocity of a droplet due to the body forces (m/s)
B (v, t ) birth aggregation (mol.m−3.s−1) v particle volume (m3)
C (ai , aj ) coalescence frequency of the particles with diameter ai and Vol volume (m3)
aj V voltage (kg·m2·s−3·A−1)
delectrodes distance between the electrodes (m) W ratio of the drag force to the buoyancy force
∘
D12 relative diffusivity due to Brownian motion x position of the droplet relative to the pressure antinode
D (v, t ) death aggregation (mol.m−3.s−1) (m)
Dd diffusion coefficient of dispersed phase (m2.s−1) xi pivot of class “i” (m)
E electrical field (N/C) Y ratio of the first ultrasonic force to the buoyancy force
Eac average energy density of the acoustic field (j.m−3) z special position (m)
F acoustic contrast factor
FF objective function of optimization (minimization) for Greek symbols
parameter estimation
g gravity acceleration (m.s−2) μ viscosity (kg·m−1·s−1)
G particle growth μ̂ ratio of the water viscosity to the oil viscosity
G (s ) near-field relative mobility function ρ density (kg.m−3)
H (s ) near-field relative mobility function ρ̂ ratio of the water density to the oil density
I unit tensor σ̂ ratio of the water compressibility to the oil compressibility
Ir ultrasonic intensity (W.cm−3) φ12 total interparticle force potential
k wave number of the acoustic field (1/m) ηd dehydration rate
K Boltzmann constant (kg.m2.s−2.k−1)
L (s ) far-field relative mobility function Subscripts
M mass of separated water in bottle test
M (s ) far-field relative mobility function cal calculated by model
N number of drops exp experimental value
Nexp number of experimental points init initial (t = 0)
Ni number of drops with size of class “i” o oil phase
n number density of particles (1.m−3) sep separated water
r droplets’ center-to-center distance (m) tot total water
s dimensionless droplet separation w water phase

direction of wave propagation [11]. The resulting compressions and
rarefactions of ultrasonic waves increase the temperature and decrease
the viscosity of the fluid which facilitates the separation [12]. Due to
the compressibility and density differences between the continuous and
disperse phases, a net force is applied to the droplets. When the distance
between a pair of droplets is less than the wavelength of the ultrasonic
field, the droplets migrate to the node or antinode of the standing waves
(droplets approach). Further coalescence of droplets is due to the inter-
droplet forces [13]. This is normally the case of low frequency
(20–100 kHz) ultrasonic waves, where the droplets coagulation is ex-
pected to be the main factor in the separation of phases [14]. In this
range of frequency, commonly known as “power ultrasonic”, the waves
are able to deliver a high specific energy density (10–1000 W/cm2) to
the medium by the phenomena known as acoustic cavitation [15]. The
application of intense pressure ultrasonic waves causes the formation of
bubbles in the solution that might expand and collapse. Consequently,
for the aim of demulsification, the intensity of ultrasonic waves should
not exceed the cavitation’s level (threshold) of the emulsion [16].
Further explanations about the demulsification ultrasonic setups and
the coalescence of droplets are presented in Sections 2.1 and 3.2, re-
spectively.
Ultrasonic waves have specifically been used in the demulsification
of W/O emulsions. Different kinds of transducers with frequencies be-
tween 10 kHz up to 2 MHz and electrical power from 50 w to 1000 w
have been used to facilitate the separation of water from crude oil. Xie
[17] studied the utilization of ultrasonic standing waves in a resonant
cavity to capture water droplets and improve oil separation. The em-
phasis of their work was to analyze the influence of ultrasonic
irradiation on the properties of w/o emulsion, such as water droplet
size, flocculation size of asphaltene, and the shear strength of the oil-
water interfacial film. Mohsin [18] designed an experimental setup to
investigate the feasibility of using a 20 kHz ultrasonic wave in de-
mulsification of W/O emulsions with different water contents. Their
experiments had a proper repeatability and indicated that the emulsion
layer with a lower amount of water content (i.e. 10–40%) broke sig-
nificantly faster. Moreover, they performed a finite-element-based si-
mulation using COMSOL Multiphysics software to study the distribution
of ultrasonic waves inside the treater and determine the rate of floc-
culation. Atehortúa [19] designed a chamber of ultrasonic demulsifier
system operating in the 1 MHz range. The chamber had a control system
which could track the operating frequency and compensate the changes
due to temperature variation. They analyzed the effect of ultrasonic
waves on the emulsions with different amounts of initial water content
and demulsifier. Antes [20] investigated the effect of ultrasound waves
on the demulsification of different average droplet size distribution
(DSD) w/o emulsions in an ultrasonic bath. They analyzed the influence
of different ultrasonic frequencies on the efficiency of separation. In
their experiments, when the applied frequency was higher than 45 kHz,
no changes could be observed in the characteristics of the crude oil
emulsions. Luo [21] studied the effects of irradiation time, acoustic
intensity, frequency, oil viscosity, and oil-water interfacial tension on
the separation characteristics of the emulsion. They showed that there
exists an optimum acoustic intensity, optimal irradiation time and oil-
water interfacial tension to achieve the maximum separation efficiency.
To improve the understanding about the coalescence of disperse
particles under the effect of ultrasonic waves, attempts have been made

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to model the phenomena. Pangu [22] introduced the microscopic dro-
plet pair model to predict the relative trajectory of binary droplets
approaching together in w/o emulsion. They explored the effect of body
and interdroplet forces in the droplets approach under the effect of the
ultrasonic field. Parvasi [23] extended the droplet pair model for o/w
emulsion and added the effect of surfactant agent to the system of
equations. Mathew [24] developed a two-dimensional dynamic model
to trace the path of microparticles subjected to the ultrasonic field. He
found that the trajectory of microparticles which approach together
consists of transient and steady phases.
Population balance model (PBM) is an appropriate way to model the
particulate systems. PBM has been used to simulate a diverse kind of
dispersed phase systems, including liquid-liquid extraction, dispersed
phase reactors, electrocoalescence and many more [25-27]. The preci-
sion of the PBM approach relies on the adequacy of the particle-particle
interaction models, which are not commonly compatible and depend on
adjustable parameters that are determined using experimental data
[28].
There exist very few works in the literature which address the ap-
plication of population balance equation (PBE) to model the demulsi-
fication under the effect of ultrasonic waves. Pangu [29] developed a
simplified PBM to study the coalescence of oil droplets in o/w emulsion.
They used the binary model developed by Pangu [22] to predict the
relative motion of two droplets approach together. They implemented
the relative velocity of two droplets as a representation of the coales-
cence model in the PBE. The results of their model to predict the evo-
lution of the droplet size distribution had a good qualitative agreement
with the experiments. They attributed the inconsistencies between the
modeling and experimental results to the spatial non-uniformities of the
acoustic field used in the experiments and the related lateral radiation
forces.
Most of the above-cited works who used the ultrasonic waves to
demulsify the w/o emulsion tried to introduce the ultrasound tech-
nology as an alternative to the industrial electrocoalescence process
which objectively in practice seems difficult. They didn’t attempt to
examine the application of ultrasonic waves as a possible substitute to
reduce the consumption of chemical demulsifiers in the pretreatment of
crude oil. Additionally, the few population balance based works such as
Pangu [29], who tried to model the separation under the effect of ul-
trasonic waves, were not meant to study the coalescence of water
droplets in w/o emulsion.
The aim of this paper was to study the utilization of low-frequency
ultrasonic waves in enhancing the breakup of water-in-oil emulsions.
Due to the limitations that our research group in the Shiraz University
(Shiraz/Iran) faced to buy laboratory equipment, it was decided to
design an experimental setup to perform the ultrasonic tests. The ex-
periments were planned to investigate the effects of irradiation time,
ultrasonic field intensity and initial water content on the efficiency of
separation. A PBM was used to explore the evolution of droplets size. A
new coalescence model based on the theoretical works of Zhang [30],
Pangue [13] and Parvasi [23] was proposed. The work is concluded by
making some remarks on the possibility of partially substituting ultra-
sonic waves with chemical demulsifiers in the pretreatment of crude oil.
To the authors’ knowledge, this is the first time where the population
balance equation has been used to model the coalescence of water
droplets in W/O emulsion under the effect of ultrasonic waves.
distribution of ultrasonic filed. The ultrasonic setups that have been
proposed for the desalination of crude oil are generally based on ul-
trasonic bath [20] and ultrasonic horn system [19]. An ultrasonic bath
has large transducer areas that produce a high-powered ultrasonic in-
tensity throughout the entire vessel. An ultrasonic horn is a dwindling
bar of metal which is usually used to enlarge the amplitude of oscilla-
tion displacement. Although both techniques apply ultrasound to the
samples, there are significant differences in their effectiveness, effi-
ciency and process capabilities [31]. The experimental analysis per-
formed by Dhanalakshmi [32] showed that the sonication produced by
the ultrasonic probe-type device is stronger and more uniform than the
one produced by the ultrasonic bath. While there is still no ultimate
verification to the preference of probe-type sonication over bath soni-
cation, the horn type seems to be preferred in most of the demulsifi-
cation works [16].
Second, the acoustic intensity should be less than the maximum
threshold of the desired crude oil. The application of high intensities of
ultrasonic waves can decompose the structure of crude oil and form
bubbles that expand and collapse.
Finally, the frequency of ultrasonic waves should be appropriate for
the aim of demulsification. Although the frequency of the ultrasonic
field is still being debated in the literature, most of the works have
shown that low-frequency waves are more competent in the demulsi-
fication of crude oil and high-frequency waves are more suitable for
emulsification purposes.
2.2. Experimental setup
In this work, we intended to design an ultrasonic batch setup which
is also capable of being employed in the continuous process of crude oil
desalination. Therefore, it was resolved that a cylindrical container si-
milar to the crude oil pipeline can be appropriate for the geometry of
ultrasonic setup. Fig. 1 shows the ultrasonic systems that were designed
to perform the experiments. The setups were made of stainless steel and
glass containers. Due to the better reflection of ultrasonic waves inside
the metal vessel, the metal container has a better efficiency in com-
parison to the glass one. Whereas, the glass container can be utilized to
observe and shot the separation process. The length and diameter of the
vessels are 25 cm and 4.8 cm, respectively.
As shown in Fig. 1, the transducers were aligned/coordinated at the
two ends of vessels to create ultrasonic standing waves inside the
container. The application of an ultrasonic field to the w/o emulsion
makes the water droplets to accumulate at the node or antinode of
standing waves which accelerates the separation and precipitation of
disperse phase. To prevent any leakage from the two ends of containers,
two especial Teflon gaskets were employed to cover the space between
the transducers and the container. Therefore, the transducers could
easily be clamped or removed from the container without any further
welding or screwing. The inlet and outlet gates on the upper and lower

2. Materials and methods

2.1. Basis of the experimental setup design

As expressed in the introduction, the idea of this work is to study the

influence of the ultrasonic field on the separation of disperse water from
oil phase in w/o emulsions. This imposes several constraints on the
design of the experimental setup.
First, the ultrasonic setup should be able to produce a proper Fig. 1. Ultrasonic system for the crude oil pretreatment.

385
A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

added to the dead (dehydrated) crude oils to prepare 100 cc sam-

ples;
2. The mixture was homogenized with the help of a pendulum agitator
(Ika, RW 20 digital);
3. The emulsions were then prepared under vigorous stirring of an
Ultra-Turrax dispersing system (Polytron PT3100, Biovera);
4. The initial droplet size distribution (DSD) of the emulsion was
measured by light scattering with the Mastersizer 2000 equipment,
equipped with the Hydro S dispersion unit (Malvern);
5. The RP-6348 demulsifier (Parslian/Tehran/Iran) for Cheshmeh
Khosh oil and V-4654 demulsifier (Pars HalalShimi/Tehran/Iran)
for Gachsaran1 oils were added to the mixtures at the concentration
Fig. 2. The main components of the ultrasonic transducer.
of 50 ppm, followed by further homogenization;
6. The 100 cc samples of emulsions were poured into the ultrasonic
sides of the vessel were considered to allow the employment of ultra- container, allowing the ultrasonic treatment to begin;
sonic setup in the continuous desalination process. The vessels were 7. The treated samples were analyzed to study the effect of ultrasonic
fastened by two polyethylene holders to a wooden plate to neutralize field on the emulsions.
the possible vibration of containers during the transmission of ultra-
sonic waves. These steps were carried out for all experimental points. The sam-
The HNT-8AE-2520(5X4) model transducers (Hainertec) which are ples were prepared and put under the effect of different ultrasonic in-
able to produce 20 KHz and 100 w ultrasonic waves were utilized in the tensities in the container. The objective of the experiments was to
experimental setup. The main component of the HNT-8AE-2520(5X4) evaluate the influence of the following variables on the demulsification
transducer is shown in Fig. 2. of emulsion:
Since there were no pre-constructed electrical circuits to provide the
necessary electrical potential for the transducers, two electrical circuits a) Ultrasonic intensity
were designed for each transducer. A computer application using b) Initial water content
LabVIEW software (National Instruments) was programmed and in- c) Irradiation time
stalled on the ICs to control the function of transducers. Therefore, it
was possible to alter the power of transducer to 25 w, 50 w and 75 w in In this study, as a result of the low concentration and unclarity of
addition to 100 w and observe the effect of ultrasonic intensity on the dispersed phase in the treated emulsion, it was not possible to measure
emulsification of crude oil. the DSD and observe the coalescence of droplets. Therefore, another
method should have been used to investigate the influence of ultrasonic
2.3. Experimental procedure waves on the demulsification of W/O emulsion.Bottle test [33] is a
renowned technique in the chemical industry to evaluate the capability
The crude oil that was used in the experiments was supplied from of demulsifiers in the separation of water from crude oil. The procedure
Gachsaran (Ilam /Iran) and Cheshmeh Khosh (Kohgiluyeh and Boyer- of bottle test is to place the treated samples in an oven at 60 °C for 12 h
Ahmad/Iran) oilfields. The characteristics of the three oils used in this and measure the separation/segregation of aqueous and oil phases [6].
work, here named as Cheshmeh Khosh, Gachsaran1 and Gachsaran2 are The difference between the amount of separation/segregation in the
shown in Table 1. cases when the agent is added and not added shows the performance/
Table 1 shows that the crude oils of the Gachsaran reservoirs are influence of demulsifier. The amount of separation in bottle test, which
lighter than the one from Cheshmeh Khosh field. Moreover, the Gach- is desired in the Cheshmeh Khosh and Gachsaran desalinization units is
saran crude oils have a lower concentration of Asphaltenes and Resins. in the range of 75%–85% volume [6]. Since in this work, the ultrasonic
Therefore, it was expected that the demulsification of Cheshmeh Khosh waves were introduced as an alternative to the demulsifiers in the
crude oil to be more difficult in comparison to the samples from pretreatment of crude oil, the bottle test was employed to examine the
Gachsaran oilfield. influence of ultrasonic field on the demulsification of W/O emulsion.
Throughout the experiments, the W/O emulsions were artificially The treated samples of ultrasonic experiments were poured into grad-
generated. The procedure to prepare the samples and run the experi- uated cylinders for conducting the bottle test. Similarly, the difference
ments was as follows: between the amount of separation in the cases when the ultrasonic
waves are applied and not applied to the emulsion shows the perfor-
1. Different volume percent of distilled water with pH = 6.5 was mance/influence of ultrasound field. This technique was utilized to
study the effects of ultrasonic intensity, initial water content and irra-
Table 1
diation time on the efficiency of separation by ultrasonication. The
Characteristics of the crude oils. efficiency of separation was evaluated by dehydration rate ηd, which is
the ratio of the removed water volume in bottle test Volsep to the initial
Crude Oil Cheshmeh Gachsaran1 Gachsaran2 volume of the distilled water Voltot added to the crude oil:
Khosh
Volsep
Density API (ASTM D4052) 21 28 31.5 ηd = × 100%
Kinematic viscosity mm2/s 25 °C 19.1 20.3 21.4
Voltot (1)
(ASTM D445)
Resins %w/w (Sara Analysis) 22.6 20.7 18.1
Asphaltenes %w/w (Sara Analysis) 2.4 1.1 0.5 2.3.1. Electrocoalescence in series with ultrasonication
Interfacial tension mN/m 19.3 15.9 14.1 In this section, a set of experiments were performed to compare the
(Tensiometer DSA100, Kruss) performance of demulsifiers and ultrasonic waves in the pretreatment
Conductivity nS/m (ASTM D2624) 21 18 23 of crude oil prior to the electrocoalescence. For this purpose, the control
Salinity concentration ppm (IP 77-72) 28 21 19
sample was prepared by adding 100 ppm of V-4654 demulsifier (Pars
Water content % (ASTM D4007-02) – – –
HalalShimi/Tehran/Iran) to a 100 cc emulsion of Gachsaran1 crude oil
with 15% initial water content. The reason for choosing the Volw,init

386
A. Khajehesamedini et al.
Fig. 3. The batch electrostatic cell and its power source.
% = 15 is that it is the most probable composition in the oilfields of
Gachsaran (Ilam/Iran). Moreover, the demulsifier and its concentration
are the ones employed in the Gachsaran desalinization unit for the
pretreatment of the crude oil. In a separate experiment, the 100 cc
emulsion was prepared by injecting 50 ppm of V-4654 demulsifier and
then poured into the ultrasound container for a 5 min 1.0 kw.cm−3
ultrasonication. In both cases, a 3000 ppm of salt (NaCl) was added in
the preparation of the two emulsions to examine the ability of the
treatments to desalt the samples. Next, the two pretreated samples were
poured into a batch electrostatic vessel and put under the effect of a
4 kV electrical field and 60 °C for 20 min. The electrostatic cell and its
electrical source are shown in Fig. 3.The electrostatic vessel consists of
two grid electrodes. The upper electrode is the ground and the lower
one is connected to a high voltage electrical source. During the ex-
periments, the distance between the electrodes was set to 4 cm and the
voltage of the lower electrode was provided by a sinusoidal 4 kV AC
current. Therefore, the average electrical field between the electrodes
(E = ΔV / delectrodes ) was equal to 10 e5V/m which is in the range of in-
dustrial value. The height of the electrostatic vessel is 11.2 cm and its
inside diameter is 4.5 cm. The elevations of the lower and upper elec-
trodes from the bottom of the vessel were maintained 4.7 cm and 8.7 cm
during the experiments, respectively.
To compare the effects of demulsifier and ultrasonic waves, the
water and salt content of the initial emulsion and the desalted samples
were measured. In this work, the ASTM D4007-02 and IP 77-72 stan-
dards were used to determine the water and salts content, respectively.
3. Population balance modeling
The average number of droplets per unit volume of droplet state
space is the droplet number density function, n . To predict the evolu-
tion of the number density function, the population balance equation
(PBE) should be solved. The general differential form of the one-di-
mensional PBE is presented in Eq. (2) [34]. In this representation, the
number density: n , is a function of v which characterizes the size of
droplets and the spatial position of droplets: z.
∂ ∂n (v, z , t )
−∇ [ud n] + ∇ [Dd ∇n]− [Gn] + S =
∂V ∂t (2)
The first and second terms on the left-hand side of the equation
represent the convection and diffusion of droplets, respectively. The
third term on the left-hand side of the equation is related to the growth
of the droplets. The term S denotes the nucleation, breakage, and ag-
gregation of the droplets. The right-hand side of Eq. (2) indicates the
accumulation of droplets in the system. Based on the characteristics of
the phenomena happening in a specific particulate system, the appro-
priate terms of population balance equation are considered in the for-
mulation of a PBM.
387
Ultrasonics - Sonochemistry 48 (2018) 383–395
3.1. Simplified model for experimental analysis
A PBM was proposed for the ultrasonic setup explained in Section
2.2, to predict the coalescence of water droplets in w/o emulsions under
the effect of ultrasonic field. Based on the characteristics of the parti-
culate system of the ultrasonic setup, the following assumptions were
made to derive the PBM:
– The diffusion and convection of droplets are insignificant in com-
parison to their coalescence.
– The ultrasonic treater is homogeneous; thus, the axial and radial
gradients inside the vessel were not considered.
– Due to the low frequency (20 KHz) and intensity (100 w) of the
applied ultrasonic fields in the experiments, the droplet breakage is
negligible [14].
Therefore, the general PBE (Eq. (2)) will be reduced to Eq. (3) for
the ultrasonic setup.
dn (v, t )
= B (v, t )−D (v, t )
dt (3)
In this equation, the B (v, t ) and D (v, t ) terms are the birth and death
aggregation of the droplets, respectively. When two droplets coalesce
together, they form a bigger droplet. The birth aggregation term ad-
dresses the creation of the big droplet; while, the death aggregation
denotes the loss of the two initial droplets. The mathematical re-
presentations of birth aggregation and death aggregation are given by
Ramkrishna [34]:
1 v
B (t , v ) =
2
∫0 C (u, v−u) n v (v−u, t ) n v (u, t ) du
(4)
∞
D (t , v ) = n v (v, t ) ∫0 C (v, u) n v (u, t ) du (5)
where B (v, t ) represents the birth of a droplet with the size of ‘v ’
through the coalescence of droplets with the size of ‘u ’ and ‘v−u ’. Also,
D (t , v ) signify the death of a droplet with the size of ‘v ’ to another
droplet with the size of ‘u ’ while the coalescence of droplet ‘v ’ to other
droplets. C (t , u, v−u) is the coalescence frequency which indicates the
number of collisions that result in the coalescence of the droplets ‘u’ and
‘v − u’. The functionality of this coefficient is dependent on the char-
acteristics of the particulate system. In the following section, an effort
has been made to develop a coalescence frequency for the ultrasonic
system.
3.2. The coalescence model
An attempt was made to develop a coalescence frequency that can
be applied to the range of droplet sizes witnessed in the ultrasonic
experiments. In this work, the method suggested by Zhang [30] was
used for the determination of coalescence frequency. Thus, the term
C (t , v, u) in Eqs. (4) and (5) can be calculated by
C (ai , aj ) = βπ (ai + aj )2|uij | (6)
where ai and aj are the diameters of two droplets coalescing together. In
this equation, uij is the relative velocity of two droplets coalescing to-
gether and β is an adjustable parameter which is dependent on the
characteristics of the crude oil. Here, the data extracted from the ul-
trasonic experiments were used to estimate the β parameter. The pro-
cedure of parameter estimation is explained in Section 4.3.
In this work, the droplet pair model developed by Pangu [35] and
Parvasi [23] was used to calculate the relative velocity of two droplets.
The model considers the application of a one-dimensional standing
ultrasonic waves to a low concentration emulsion. Due to the small size
of droplets, the inertial forces can be neglected. Therefore, every col-
lision which is a result of a binary droplet interaction leads to an irre-
versible coalescence of the droplets. The model is limited to large Peclet
A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

numbers, where the Brownian diffusion can be disregarded compared
to other effective forces of the system [35].
The formulation of the droplet pair model is based on the balance of
forces that apply to the droplets while coalescing together [36]. The
forces are subcategorized to body forces and interdroplet forces. The
body forces are the ones that act on droplets as individuals; while, in-
terdroplet forces are the ones that act on a droplet because of its close
vicinity to another. In the particulate system of ultrasonic setup, the
body forces are the gravity, buoyancy, drag and primary acoustic force.
The velocity of an individual droplet can be calculated by solving the
balance equation of the body forces. The Eq. (7) is proposed by Pangu
[22] for the calculation of this velocity:
4. Numerical procedure
4.1. Solution of the population balance model
To estimate the parameters of Eq. (6), first, the population balance
equation should be solved. Among the several numerical procedures
that have been suggested to solve the PBE, this work used the method of
classes developed by Kumar [41]. The method enforces the conserva-
tion of volume and number of the droplet population and permits the
direct use of initial droplet size classes defined by the particle size
analyzer. The sectional moment of the ith class, Ni, including all parti-
cles with a volume between vi and vi + 1, is defined as:
vi + 1

u∘ =
1 ⎛
1−Y 2 ⎜sec2 ⎜⎛δ +
k 1−Y 2 ⎞ ⎞ ⎛ 1−Y 2 ⎞
t⎟⎟⎜
Ni = ∫v i
n (v ) dv
(15)
2 ⎟
(1 + P ) ⎝ W ⎠⎠⎝ W ⎠ (7)
⎝ This class is represented by the pivot x i = 0.5(vi + vi + 1) . Based on the
where: experimental data reported by the particle size analyzer (Malvern®
Mastersizer 2000), the diameter of water droplets in the initial emul-
1 + 3μ ̂ / 2

W=
3 ( 1+μ̂ )μ
o
sion was in the range of 0.1−100 μm . Therefore, the classes vi were de-
termined by a geometric grid defined by vi + 1/ vi = 1.514 , k = 0, …, n ,
a 2̂ (ρw −ρo ) g (8) v0 = 5.24 × 10−7 μm3 (d 0 = 0.01 μm) with n = 100.
Applying the procedure proposed by Kumar [41] to Eq. (3) leads to
3kEac F the subsequent set of ordinary differential equation (ODE):
Y=
(ρw −ρo ) g (9) j⩾k M
dNi (t ) 1
dt
= ∑ (1− δj, k ) ηj, k, i Cj, k Nj (t ) Nk (t )−Ni (t )
2
∑ Ci, k Nk (t )
ρ ̂ + (2/3)(ρ − ̂ 1) 1 j, k k=1
F= − 2 xi − 1⩽ (xj + xk ) ⩽ xi + 1
(1 + 2ρ )̂ 3σ ρ ̂ (10)
(16)

k 1−Y 2 ⎞ where ηj, k, i is defined as:

P= 1−Y 2 tan ⎛⎜δ +
⎝ W
tan(kx 0) + Y ⎞
δ = tan−1 ⎛⎜
⎝ 1−Y 2
t ⎟−Y
⎠ (11) x − (x + x )
⎧ i+1 j k x j ⩽ (x j + xk ) ⩽ x i + 1
⎪ xi + 1 − xi
ηj, k, i = (xj + xk ) xi − 1
⎨ x i − 1 ⩽ (x j + xk ) ⩽ x i
⎟
⎪ xi − xi − 1
⎩ (17)
⎠ (12)

and x 0 is the initial distance of the droplet from the pressure antinode
[22].The relative velocity of two individual droplets (uij∘ = ui∘−uj∘ ) 4.2. Determination of the final amount of separated water using the
should be corrected by adding the influence of interdroplet forces. The population balance model
interdroplet forces are conceptually different from the body forces as
their strength increases when the droplets approach together. The pri- In this work, as a result of the low concentration and unclarity of
mary acoustic force makes the droplets move to the closest pressure disperse phase in the treated emulsion, it was not possible to measure
antinode. Throughout this motion, the droplets approach each other the distribution of water droplets. Therefore, the volume of separated
and the interdroplet forces become important. The interdroplets forces water in the bottle test could be the only experimental data to evaluate
acting on droplets are the Van der Waals [12,37] and the attractive the PBM. Here, a criterion in the PBM should have been considered to
secondary acoustic [22,38,39] forces. The corrected relative velocity of denote the volume of separated water. According to the study of
the droplets uij is presented as [40]: Meidanshahi [42], it was assumed that the population of water droplets
which are larger than 20 μm represents the volume of separated water
rr rr Dij∘ rr from oil phase in the bottle test. The first moment of the number
uij = uij∘·⎡ 2 L (s ) + ⎛I − 2 ⎞ M (s )⎤− ⎡ G (s ) + ⎛I − rr ⎞ H (s )⎤·∇ (φij )
⎣r ⎝ r ⎠ ⎦ kT ⎣ r
2
⎝ r2 ⎠ ⎦ function (N) in the PBE (Eq. (16)) represents the total volume of the
(13) droplets (Kumar, 1996):
∞
In this equation s = 2r /(a1 + a2) is the dimensionless droplet se- Voltotal = ∫0 N (v ) dv (18)
paration, r is the droplets’ center-to-center distance and I is the second-
order unit tensor. The first two terms on the right side of Eq. (13) de- Therefore, the volume of the separated water phase can be calcu-
scribe the contributions of body forces to the relative velocity, while the lated by
last two terms indicate the interdroplet effects. Also, Dij∘ is the relative ∞
diffusivity of two widely separated droplets due to the Brownian mo- VolSep = ∫20μ N (v ) dv
(19)
tion:
and similar to Eq. (1), the dehydration rate can be calculated as the
KT (μ ̂ + 1)(1 + a −̂ 1) ratio of separated water volume to the total water volume:
Dij∘ =
2πμo (3μ ̂ + 2) ai (14) ∞
∫20μ N (v ) dv
ηd = ∞
The relative mobility functions for the motion along the center of two ∫0 N (v ) dv (20)
droplets center: L (s ) , G (s ) , and normal to the droplets centerline: M (s ) ,
H (s ) denote the influences of hydrodynamic interactions between the The following section explains the estimation of the β parameter by
two droplets [40]. A detailed explanation of the droplet pair model can comparing the value calculated by Eq. (20) and the experimental
be found in the original references [23,35]. amount.

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A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

4.3. Estimation of model parameter

The aim of this section is to use the experimental data to estimate

the parameter of PBM (β). The objective function used for parameter
estimation was the minimization of the quadratic mean of the differ-
ences between the experimental and calculated values of the dehydra-
tion rate, according to Eq. (21):
NE
1
FF = ∑ (η −η
Nexp d,exp, p d, cal, p
)2
p=1 (21)
where NE is the number of experimental points and the subscript p in-
dicates the points of the experimental matrix.
In this work, the Asynchronous and Immediate Update Parallel
Particle Swarm Optimization (AIU-PPSO) algorithm developed by
Moraes [43] was employed to determine the parameter of the PBM (β).
In this work, the computer programs were written using Matlab 2017a
(Mathworks) software.

5. Results and discussion

5.1. Analysis of the ultrasonic experiments

In this section, the results of the ultrasonic experiments performed

for the samples of the three crude oils described in Table 1 are pre-
sented. Primarily test showed that it is not possible to have any de-
mulsification/separation without the injection of demulsifiers. That is
the reason, it was necessary to add some demulsifier in the preparation
of emulsions to create an initial driving force to start the demulsifica-
tion. The RP-6348 and V-4654 demulsifiers are the ones used in the
desalination units of Cheshmeh Khosh (Kohgiluyeh and Boyer-Ahmad
/Iran) and Gachsaran (Ilam/Iran), respectively. The amount of de-
mulsifier which is added to the crude oils in the desalination units of
Gachsaran and Cheshmeh Khosh is 100 ppm. However, in this work, to
investigate whether the demulsifiers can partially be substituted with
ultrasonication, the amount of injected demulsifier was 50 ppm.
The experiments analyzed the effects of ultrasonic intensity, initial
water content and irradiation time on the amount of separation in the
bottle test. The samples were prepared in 10%, 15%, 20% and 25% of
water content at 60 °C. The emulsions were put under the effect of 0.25,
0.5, 0.75 and 1 w.cm−3 ultrasonication for 1, 2 and 5 min. The ex-
periments were conducted in triplicates and the reported values of the
results showed that the experimental errors were less than 5%. The
effects of variables are discussed in the following sections. The com-
plete data of ultrasonic experiments are provided in Appendix A.
5.1.1. The effect of irradiation time
The effect of irradiation time on dehydration rate of the emulsion is
shown in Fig. 4. The dehydration rate of the emulsion without ultra-
sonic irradiation at tr = 0 is due to the effect of chemical demulsifier.
Based on the findings of Razi [6], the relation between the dehydration
rate and the amount of injected demulsifier is normally not linear.
Therefore, it can be expected that for example, to increase the efficiency
of separation from 70 to 80%, the amount of demulsifier needs to be
doubled [6].
As shown in Fig. 4, the dehydration rate increased with the increase
of irradiation time. However, the dehydration rate decreased slightly
(e.x. Fig. 4(b)) and was basically unchanged (e.x. Fig. 4(a)) with the
further increase of irradiation time. It took a long time for the droplets
that are far from the pressure node to migrate to the banding zone due
to the primary acoustic force [22]. Therefore, the extended irradiation
time is advantageous to the aggregation of the droplets. Moreover, the
secondary acoustic force increases as the droplets get closer together
and aggregate [22], which enhances the dehydration efficiency.
Nevertheless, the dehydration rate of emulsion decreased slightly for a
long irradiation time. Excessive long irradiation time would raise the
Fig. 4. The effect of irradiation time on dehydration rate of the emulsion: (a)
Ir = 0.5 W.cm−3 & Volw,init % = 20, (b) Ir = 1.0 W.cm−3 & Volw,imit % = 25.
temperature of the emulsion, which reduces the acoustic cavitation
threshold [16]. Acoustic cavitation would disperse the aggregating
droplets and reduce the separation efficiency. Therefore, an optimal
irradiation time can be reached, when the separation efficiency has its
highest value and further irradiation would have little effect on im-
proving the dehydration. This is more apparent in higher acoustic in-
tensities as the temperature can rise in a smaller period of time (e.x.
Fig. 4(b)). Furthermore, our tests showed that the emulsion might
evaporate in a longer period of irradiation. That is the reason, we were
not able to perform the experiments for longer than 5 min.
The difference between the dehydration rates of the three samples
can be mainly attributed to the difference of viscosity and interfacial
tension of the crude oils. The higher viscosity of Cheshmeh Khosh crude
oil applies a higher drag force on the droplets in comparison to the
samples of Gachsaran crude oils. Consequently, it is expected that the
droplet migration velocity is smaller for the Cheshmeh Khosh emul-
sions. The other reason is the higher interfacial tension of Cheshmeh
Khosh crude oil in comparison to the samples of Gachsaran. The high
amount of interfacial tension hinders the segregation of water droplets
from the oil phase and their migration to the banding zone.
Fig. 4 portrays the dehydration rate of emulsions at Ir = 0.5 w.cm−3
& Volw,init % = 20 and Ir = 1.0 w.cm−3 & Volw,init % = 25. However,
the profile of separation efficiency versus irradiation time had similar
trends in other ultrasonic intensities and initial water contents
(Appendix A).
5.1.2. The effect of acoustic intensity
Acoustic intensity is an important factor in ultrasonic demulsifica-
tion. The effect of acoustic intensity on dehydration rate of the emul-
sions is the portrayed in Fig. 5. Similarly, the dehydration rate of the
emulsion without no ultrasonication (Ir = 0 W.cm−3), which represents
the initial segregation of phases is due to the effect of chemical de-
mulsifier.
As shown in Fig. 5, the increase of acoustic intensity (i.e. increase of
primary and secondary acoustic forces), decreases the time required for
the droplets to migrate to the banding zone. Therefore, the dehydration

389
A. Khajehesamedini et al.
Fig. 5. The effect of acoustic intensity on dehydration rate of the emulsion: (a)
tr = 5 min & Volw,init % = 15, (b) tr = 2 min & Volw,init % = 25.
rate increases with an increase of acoustic intensity. However, there
exists an optimal acoustic intensity where the separation efficiency
achieves its maximum value [17,44]. If acoustic intensity exceeds the
cavitation threshold, local turbulence and shear forces would be created
which implode and break the dispersed droplets [16]. The acoustic
cavitation threshold is influenced by factors such as viscosity, inter-
facial tension and saturated vapor pressure [16]. As Fig. 5 expresses, an
optimal acoustic intensity was obtained for Gachsaran crude oil sam-
ples. While, the Cheshmeh Khosh samples had more monotonic change
with the increase of ultrasonication as the acoustic cavitation threshold
increases with the increase of liquid viscosity in the same condition.
The point which can be inferred by comparing Figs. 4 and 5 is that the
acoustic cavitation threshold is more sensitive to the increase of irra-
diation time which is consistent with the previous findings [21].
Fig. 5 depicts the dehydration rate of emulsions at tr = 5 min &
Volw,init % = 15 and tr = 2 min & Volw,init % = 25. Nevertheless, the
profile of separation efficiency versus ultrasonic intensity had similar
trends in other irradiation times and initial water contents (Appendix
A).
5.1.3. The effect of initial water content
The effect of initial water content on dehydration rate of the
emulsion is the depicted in Fig. 6. The increase of initial water content
increases the load on the ultrasonic waves to make a higher number of
droplets to migrate to the bonding zone. On the other hand, the increase
of initial water content, increase the number/size of the droplets which
boost their collision and coalescence. Therefore, it is expected that the
amount of separated water increases with the increase of initial water
content while the dehydration rate decreases.
The point that should be mentioned in Fig. 6(b) is the sharp
390
Ultrasonics - Sonochemistry 48 (2018) 383–395
Fig. 6. The effect of initial water content on dehydration rate of the emulsion:
(a) Ir = 0.25 W.cm−3 & tr = 2 min, (b) Ir = 0.75 W.cm−3 & tr = 5min.
decrease of dehydration rate between the initial water contents of 20
and 25%. As the water content of the emulsions increases, the satura-
tion vapor pressure increases [16]. This case is particularly evident at
high irradiation time and/or ultrasonic intensity (Fig. 6(b)) as the
temperature of the emulsion increases quickly. Therefore, the acoustic
cavitation threshold decreases which disperse the aggregated droplets
and reduce the separation efficiency.
Fig. 6 represents the dehydration rate of emulsions at
Ir = 0.25 W.cm−3 & tr = 2mins and Ir = 0.75 W.cm−3 & tr = 5mins.
Nonetheless, the profile of separation efficiency versus initial water
content had similar trends in other irradiation times and ultrasonic
intensities (Appendix A).
To summarize the results of Section 5.1, for a constant initial water
content, the dehydration rate is more responsive to the irradiation time
in comparison to acoustic intensity. This can be justified as the increase
of acoustic intensity is dominant over the increase of irradiation time to
make the W/O emulsion reach the threshold temperature and acoustic
cavitation. By increasing the initial water content, the responsiveness of
dehydration rate to both irradiation time and ultrasonic intensity in-
creases as the saturation vapor pressure increases. Therefore, con-
sidering the energy consumption, the optimum dehydration rate was
seen at Ir = 0.25–0.5 W.cm−3 & tr = 2 min for the three crude oil
samples at a constant initial water content.
5.2. Analysis of the ultrasonic experiments in series with electrostatic tests
In this section, the results of the electrostatic tests after chemical
and ultrasonic pretreatments are presented. As stated in Section 2.3.1,
the objective of this section was to compare the performance of ultra-
sonic wave and in the pretreatment of the Gachsaran1 crude oil.
However, since it was not possible to have any demulsification with
pure ultrasonication, it was necessary to add some demulsifier in the
preparation of samples. The preparation and experimental conditions of
A. Khajehesamedini et al.
Table 2
Preparation and experimental conditions of the two samples.
Parameter Control Sample Ultrasonic Sample
Initial Water Content (%) 15 15
Initial Salt Content (g/m3) 3000 3000
Demulsifier Injection (ppm) 100 50
Ultrasonic field intensity of (W/cm3) – 1
Irradiation time (min) – 5
Electrostatic field Intensity (kV/cm) 1 1
Electrostatic time (min) 20 20
the control and ultrasonic samples are presented in Table 2. Specifi-
cally, the experiments examined whether the ultrasonication can
compensate the 50% reduction in demulsifier injection.
It should be mentioned that the procedures that have been used to
measure the water/salt content after the ultrasonic/chemical pretreat-
ments and electrostatic separation were different. The reason is that
there was no clear separation between the phases immediately after the
ultrasonic/chemical pretreatments. Therefore, in order to evaluate the
efficiency of pretreatment, the bottle test procedure was used which
lasts 12 h. As presented in Appendix A, the dehydration rate of Volw,init
% = 15 Gachsaran1 crude oil after 5 min, 1 W/cm3 ultrasonic is
92.27%; and based on the work of Razi [6], the amount of dehydration
rate after the pure chemical is in the range of 87–90%. Besides, it is
expected that the salt shouldn’t have any significant change after the
pretreatment as a distinct phase separation is not observed after the
pretreatments. However, the electrostatic tests were performed im-
mediately after the pretreatment and there is a segregation between the
aqueous and oil phases after the electrostatic treatment. Therefore, it
would be possible to immediately measure the water/salt contents
using the ASTM D 4007-02 and IP 77-72 standards. The results of the
analysis are shown in Fig. 7.
As shown in Fig. 7, the water and salt contents of the two desalted
samples had comparable values. Moreover, the results were in the range
of desired values of in the industry. Therefore, it can be deduced that
the ultrasonic waves have the potential to partly substitute with
Fig. 7. Analysis of the desalted samples: (a) water content, (b) Salt content.
391
Ultrasonics - Sonochemistry 48 (2018) 383–395
chemical demulsifiers pretreatment of crude oil prior to electrostatic
desalinization.
5.3. Parameter estimation
The parameter estimation procedure described in Section 4.3 was
applied to determine the parameter β of the coalescence frequency Eq.
(6). The initial discrete droplet volume distribution (Nv,k) and the de-
hydration rate were utilized as the independent and dependent vari-
ables, respectively. Since in this the work, demulsifier was added in the
preparation of emulsions, the separation of phases after ultrasonication
cannot be only ascribed to the effect of ultrasonic waves. Therefore, it
was assumed that effect of the 50 ppm demulsifier which can be asso-
ciated with the characteristics of the emulsions is encompassed in the β
parameter.The coalescence frequency parameter of the PBE is an em-
pirical/semi-empirical term to address the effect of variables that have
not been implicitly or explicitly considered in the modeling [34]. In the
PBE of Eq. (3), the initial water content is seen through the distribution
of droplets. However, the effect of initial water content on the flow
pattern is not reflected in the PBM. Different initial water contents
create dissimilar flow regimes which influence the rate of aggregation
[1]. Besides, the ultrasonic intensity is considered through the primary
and secondary forces in the relative velocity of two droplets (Eq. (13))
in the PBE. The relative velocity of two droplets is a function of dis-
parity of droplets which is absolutely stochastic. Therefore, in this
work, we assumed that the β parameter is a function of initial water
content (Volw,init) and ultrasonic intensity (Ir). for this reason, an em-
pirical equation was considered for the parameter of aggregation fre-
quency as:
β = A × (Vol w, init %) B (22)
where
A = A1 × Ir + A2 (23)
B = B1 × Ir + B2 (24)
The idea of choosing this form of equation was to investigate the sen-
sitivity/functionality of the β parameter to the initial water content
(Volw,init) and ultrasonic intensity (Ir). To perform the parameter esti-
mation, 75% of the experimental data for each crude oil sample (i.e.
0.75 * 4 * 3 * 4 = 36 points) were randomly selected and the other 25%
(i.e. 0.25 * 4 * 3 * 4 = 12 points) were used to validate the model.
Moreover, the average value of the triplicates in experimental results
was used for the calculations. The A1, A2 , B1 and B2 coefficients were
estimated by minimizing the distance between the experimental and
simulated data (Eq. (21)) using the AIU-PPSO optimization algorithm
[43]. The estimated/optimized values of the coefficients for the three
crude oil samples are presented in Table 3.The sensitivity of β para-
meter to Volw,init and Ir can be analyzed by studying the A and B variable
in Eq. (22). Based on the results of parameter estimation (Table 3) and
Eqs. (23), (24), the range of variation of the B variable is much larger
than the A . This issue denotes that the variation of the β is more sen-
sitive to the initial water content (Volw,init). The effect of ultrasonic
intensity appears to be sufficiently expressed through the u12 in Eq. (6).
However, the assumption made in droplet pair model to incorporate the
Table 3
The coefficients of the aggregation frequency parameter (β ) .
Crude Oil A1 A2 B1 B2
Cheshme Khosh 1.009 × 10−9 −2.845 × 10−10 0.6674 −0.7979
Gachsaran1 1.796 × 10−9 −6.791 × 10−10 −0.232 −0.04143
Gachsaran2 2.331 × 10−9 −8.516 × 10−10 −0.429 −0.02919
A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

Table 4 presented in Table 4. The error shown in Table 4 is calculated by Eq.

Simulated and experimental dehydration rate of the validation points: (a) (21).
Gachsaran1, (b) Gachsaran2, (c) Cheshmeh Khosh crude oil samples. As can be seen in Table 4, the error of the model to predict the
Irradiation Ultrasonic Initial water ηd,exp (%) ηd, cal (%) dehydration rate at the validation points was acceptable. Although, the
time (min) intensity (W/cm3) content (%) biggest error was seen for the Cheshmeh Khosh crude oil samples. This
can be associated with the high concentrations of asphaltene and resin
(a)
in the crude oil which was not well addressed in the model. Further-
2 1.0 10 86.3 90.57
5 0.25 10 92.6 84.42 more, the highest local deviation from the PBE model was specifically
5 0.75 10 93.3 85.51 realized at the points with a high value of irradiation time/ultrasonic
5 1.0 10 92.7 85.20 intensity. This could be due to the insufficient proficiency of the model
1 0.25 15 80.2 85.63
to predict the ultrasonic cavitation threshold to avoid the over-
1 1.0 15 79.8 87.87
5 0.5 15 92.0 95.34
estimation of the model.
2 0.75 20 83.9 77.19
5 0.75 20 88.7 92.75
5 1.0 20 91.3 84.19 6. Conclusion
1 1.0 25 80.2 73.23
5 1.0 25 80.3 82.86
Error (%) 6.29
This work presented an experimental and theoretical study on the
pretreatment of crude oil using low-frequency ultrasonic field coupled
(b)
with chemical demulsifiers. A simplified PBM was proposed to explicate
1 1.0 10 80.9 86.27
5 0.5 10 94.3 98.17 the experimental data.
5 0.75 10 95.7 88.31 The results of the experiments showed that it is not possible to
2 0.75 15 86.3 79.09 completely omit the consumption of chemical demulsifier. However, for
5 0.5 15 93.3 85.26
a W/O emulsion, it would be possible to decrease the injection of de-
2 1.0 20 83.9 74.19
5 0.5 20 90.1 88.58
mulsifier by 50% using an appropriate irradiation time and intensity of
5 0.75 20 88.3 91.36 ultrasonic waves. Based on the experiments, for a W/O emulsion with a
5 1.0 20 90.7 95.04 definite initial water content, the increase of irradiation time is more
1 0.75 25 79.9 80.51 effective than the increase of acoustic intensity in boosting the dehy-
2 1.0 25 86.3 78.58
dration rate as the acoustic cavitation is delayed. The results of elec-
5 0.75 25 80.5 83.17
Error (%) 5.83 trostatic experiments verified the potential of the ultrasonic waves in
pretreatment of W/O emulsion. The salt/water contents that is reached
(c)
1 1.0 10 75.5 65.31 in the electrocoalescence process after the ultrasonic and chemical
1 0.75 15 75.0 75.67 treatment could be comparable.
2 1.0 15 80.0 75.32 The PBM using the derived coalescence model, generated unbiased
5 0.5 15 82.5 83.74 results for the amount of separated water in bottle test that presented a
5 0.75 15 84.3 81.58
5 1.0 15 85.2 82.92
decent agreement with experimental data. The droplet-pair model
2 0.5 20 79.9 71.33 showed to be a proper approach in predicting the coalescence fre-
2 0.75 20 77.8 71.24 quency. Based on the parameters estimated for the aggregation fre-
5 0.5 20 77.7 64.84 quency coefficient, the frequency of aggregation has a significant
1 0.5 25 70.4 81.76
functionality on the initial water content. The ideas that are suggested
1 1.0 25 71.3 75.42
2 0.25 25 74.8 86.41 to improve the model is to (a) consider a multidimensional distribution
Error (%) 7.65 of the ultrasonic waves, (b) add the surface tension force to the balance
equation of body forces, and (c) obtain a functionality for the con-
centration of demulsifier in the equation of coefficient of aggregation.
effect of ultrasonic intensity can be compensated through the β para-
meter. Here, it should be noted that the β parameter would have a
sensible functionality to the concentration of injected demulsifier in the Acknowledgments
preparation of samples. However, since in this work a constant amount
of demulsifier (50 ppm) was used during the experiments, it was not The authors would like to thank the Iranian Central Oil Fields
meaningful to propose any functionality for that. Company (ICOFC) for providing informational and financial supports.
The comparison between the simulated and experimental dehy- Also, the authors are grateful to the Radman Sanaat Nasr Company for
dration rate of the validation points for the three crude oil samples are its technical consultation in constructing the ultrasonic setup.

Appendix A

In this section, the detailed experimental data of the ultrasonic tests is provided. The results of the experiments for Gachsaran1, Gachsaran2, and
Cheshmeh Khosh crude oil samples are presented in Tables 5–7, respectively.

392
A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

Table 5
Dehydration rate (%) of the ultrasonic tests for the Gachsaran1 crude oil samples.
Volw,init(%)

tr(s) 10 15 20 25

3
Ir = 0.25 (W/cm )
0 74.40 72.88 71.24 69.27
1 82.18 80.24 78.39 79.94
2 87.84 86.51 83.92 85.93
5 92.59 90.63 89.10 80.27

Ir = 0.5 (W/cm3)
0 74.40 72.88 71.24 69.27
1 82.29 80.01 77.67 80.26
2 87.55 86.14 83.02 85.56
5 92.93 92.02 88.39 79.37

Ir = 0.75 (W/cm3)
0 74.40 72.88 71.24 69.27
1 81.92 79.93 78.49 79.60
2 87.63 85.01 83.90 85.91
5 93.27 90.20 88.69 79.91

Ir = 1 (W/cm3)
0 74.40 72.88 71.24 69.27
1 80.92 79.79 78.31 80.24
2 86.30 86.63 85.02 86.81
5 92.66 92.27 91.32 80.28

Table 6
Dehydration rate (%) of the ultrasonic tests for the Gachsaran2 crude oil samples.
Volw,init(%)

tr(s) 10 15 20 25

3
Ir = 0.25 (W/cm )
0 75.54 74.05 72.20 69.45
1 85.47 82.35 81.40 81.59
2 90.12 87.99 87.48 86.49
5 97.06 93.08 92.70 81.26

Ir = 0.5 (W/cm3)
0 75.54 74.05 72.20 69.45
1 82.86 80.08 79.50 80.26
2 88.14 85.66 84.34 85.58
5 94.29 93.34 90.09 79.61

Ir = 0.75 (W/cm3)
0 75.54 74.05 72.20 69.45
1 83.72 81.54 78.12 79.88
2 89.51 86.26 83.59 85.79
5 95.66 92.50 88.32 80.54

Ir = 1 (W/cm3)
0 75.54 74.05 72.20 69.45
1 80.92 79.70 78.19 80.55
2 85.99 85.78 83.95 86.32
5 91.94 92.04 90.73 80.51

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A. Khajehesamedini et al. Ultrasonics - Sonochemistry 48 (2018) 383–395

Table 7
Dehydration rate (%) of the ultrasonic tests for the Cheshmeh Khosh crude oil Samples.
Volw,init(%)

tr(s) 10 15 20 25

3
Ir = 0.25 (W/cm )
0 68.56 67.01 64.26 63.81
1 76.37 71.95 73.34 69.19
2 81.69 79.24 77.59 74.80
5 86.79 81.40 77.67 71.63

Ir = 0.5 (W/cm3)
0 68.56 67.01 64.26 63.81
1 75.36 70.94 73.64 70.38
2 79.33 77.23 79.87 76.71
5 86.07 82.53 77.74 72.69

Ir = 0.75 (W/cm3)
0 68.56 67.01 64.26 63.81
1 74.99 74.97 73.78 69.63
2 79.64 81.12 77.81 76.93
5 86.39 84.32 77.08 73.15

Ir = 1 (W/cm3)
0 68.56 67.01 64.26 63.81
1 75.51 72.65 74.21 71.33
2 81.85 80.04 80.51 78.99
5 87.29 85.21 78.62 74.84

Appendix B. Supplementary data

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.ultsonch.2018.05.032.

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