chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Droplet breakage and coalescence models for the

flow of water-in-oil emulsions through a valve-like
element

João F. Mitre a,1 , Paulo L.C. Lage a,∗ , Marcos A. Souza b , Eli Silva b ,
Luiz Fernando Barca b , Antonio O.S. Moraes a , Raquel C.C. Coutinho c ,
Elizabeth F. Fonseca c
a Programa de Engenharia Química – COPPE, Universidade Federal do Rio de Janeiro, PO Box 68502, Rio de Janeiro,
RJ 21941-972, Brazil2
b Núcleo de Separadores Compactos (NUSEC), Instituto de Engenharia Mecânica, Universidade Federal de Itajubá,

Av. BPS 1303, Itajubá, MG 37500-903, Brazil

c CENPES/PETROBRAS, Rio de Janeiro, RJ 21949-900, Brazil

a b s t r a c t

An experimental and theoretical study was carried out regarding the evolution of droplet size distributions for the
flow of water in oil emulsions through a valve-like element that simulates a mixing valve. The water droplets had
diameters in the 0.1–100 ␮m range, which includes droplets that are either smaller or larger than the Kolmogorov
length scale for the experimental conditions. Droplet breakage and coalescence models that can be used for this
size range were proposed. A simplified population balance model was developed to interpret the experimental data
and solved by the method of classes. The model parameters were estimated by the orthogonal distance regression
method. The simplifying assumption of the model was verified by global optimization using a parallel implementa-
tion of the particle swarm optimization method. The agreement between simulated and experimental droplet volume
size distributions was good. The predictions of the DeBroukere mean diameter, d43 , were unbiased with mean errors
of 8%.
© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Mathematical modeling; Parameter estimation; Population balance; Emulsion; Coalescence; Breakage

1. Introduction key variables in defining the separation efficiency (Raghavan

During oil production, the mixture of water and oil is sub-
mitted to large shear rates generating water–oil emulsions
(Raghavan et al., 1971; Paiva, 2004; Eow and Ghadiri, 2002;
Cunha, 2008) which have a large salt content. Electrostatic
demulsification of water-in-oil emulsions is largely applied in
the oil industry to desalt the crude dead oil prior to its refin-
ing (Manning and Thompson, 1995; Stewart and Arnold, 2008,
2009; Noïk et al., 2006). Droplet sizes and salt concentration are
et al., 1971; Paiva, 2004; Eow and Ghadiri, 2002; Cunha, 2008).
The oil is received at the refinery with a small fraction of
water but with a large concentration of salts. Before the desalt-
ing equipment, fresh water is added to wash the oil, increasing
the concentration of water droplets. A globe valve is com-
monly used to promote adequate mixing by generating droplet
breakage and coalescence.
The emulsion flow is a polydisperse multiphase flow
that can be simulated by couplinga population balance

∗
Corresponding author. Tel.: +55 21 2562 8346; fax: +55 21 2562 8300.
E-mail address: paulo@peq.coppe.ufrj.br (P.L.C. Lage).
Available online 4 April 2014
1
Present address: Departamento de Engenharia Química e de Petróleo, Escola de Engenharia, Universidade Federal Fluminense, Campus
Praia Vermelha, Rua Passos da Pátria, 156, Bloco D, Sala 305, Niterói, RJ 24210-240, Brazil.
2
http://www.peq.coppe.ufrj.br/areas/tfd/.
http://dx.doi.org/10.1016/j.cherd.2014.03.020
0263-8762/© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
2494 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

Nomenclature
xk pivot of class k
a(v, v ) aggregation frequency of the particles with vol- y vector of continuous phase variables
ume v and v z spatial position
A Hamaker constant Ż particle velocity vector
Ac flow cross section area
b(v) breakage frequency of the particle with volume Greek symbols
v ˛ vector of model parameters
BB production of particles by breakage ˇ dimensionless constant equal to 8.2
BC production of particles by coalescence ı error in explanatory variable
c minimum clearance in the test section  variation
Cb parameter of the breakage frequency model  dissipation rate of turbulence energy
Cc parameter of the coalescence frequency model ε error in response variable
Ce parameter of the coalescence efficiency model  Kolmogorov length scale
Ca capillary number  collision frequency
d particle diameter  coalescence efficiency
dc,mb critical diameter of Martínez-Bazán et al.  dynamic viscosity
(1999a) kinematic viscosity
deq equivalent diameter in the collision of drops i
explanatory variable
and j, d−1 −1 −1
eq = 0.5(di + dj )
 density
dpq mean diameter given by  interfacial tension
 ∞ ∞ 1/(p−q) ς mean number of daughter particles
0
dp f (v)dv/ 0 dq f (v)dv
 water volume fraction
DB destruction of particles by breakage
˚ multiresponse model
DC destruction of particles by coalescence
 response variable
Dpq mean diameter given by
 ∞ ∞ 1/(p−q)
0
dp F(v)dv/ 0 dq F(v)dv Subscripts
e relative error crit critical value
e mean of the relative errors d dispersed phase
|e| mean of the magnitude of the relative errors exp experimental
emax maximum error in magnitude in at the inlet of the test section
f particle number distribution function max maximum
F particle volume distribution function n refers to normalized distribution
G objective function out at the outlet of the test section
h film thickness sim simulated
H particle net production rate v refers to volume distribution
L turbulent length scale
l depth of the test section (l = 5 mm)
M number of valid experimental runs
N zeroth-order sectional moment model (Ramkrishna, 2000) with computational fluid dynam-
NT particle number density ics (Marchisio et al., 2003; Marchisio and Fox, 2005; Silva et al.,
n number of classes 2008; Silva and Lage, 2011). The accuracy of this approach
P(v |v) daughter particle breakage conditional proba- heavily relies on the adequacy of the employed breakage and
bility coalescence models, which are not generally applicable and
p pressure have adjusted parameters that usually depend on the charac-
Q emulsion volumetric flow teristics of the multiphase system (Lasheras et al., 2002; Liao
Re Reynolds number and Lucas, 2009, 2010; Mitre et al., 2010).
ReT Reynolds number based on the Taylor length Coalescence is believed to occur in three stages (Marrucci,
scale 1969; Friedlander, 1977; Coulaloglou and Tavlarides, 1977; Ross
S collision cross-section of particles with diame- et al., 1978; Kim and Lee, 1987; Prince and Blanch, 1990;
ters d and d Chesters, 1991; Kamp et al., 2001; Liao and Lucas, 2010).
StK Stokes number based on Kolmogorov time scale First, there is a collision between two fluid particles, which
t time become separated by a thin fluid film. Then, the fluid in this
tres particle residence time film is drained until it reaches a critical thickness at which
u velocity fluctuation molecular attractive forces dominate, promoting the film rup-
ud particle characteristic velocity ture and leading to coalescence. In turbulent flows, particle
U mean velocity collisions are mainly controlled by particle–turbulence inter-
v particle volume actions, which also cause intense particle deformation that
Ve effective volume of the valve-like element leads to fluid particle breakage (Hinze, 1955; Lasheras et al.,
W mass flow rate 2002).
W matrix of weights of the errors in the objective The breakage and coalescence modeling in turbulent flows
function depends on the size ratio between the fluid particle and the
We Weber number Kolmogorov length scale, . If the particle is smaller than , it is
in the sub-Kolmogorov size range. If the particle size is smaller
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508
than the dissipation-inertial size limit (∼20), it is in the tur-
bulence dissipation range (Pope, 2000). On the other hand,
if the particle is larger than this limit and smaller than the
integral scale, it is in the inertial subrange of the turbulence
spectrum.
There are several models for breakage and coalescence of
fluid particles in the inertial subrange of the turbulence spec-
trum (Coulaloglou and Tavlarides, 1977; Hsia and Tavlarides,
1983; Tsouris and Tavlarides, 1994; Prince and Blanch, 1990;
Chen et al., 1998; Martínez-Bazán et al., 1999a,b; Hagesaether,
2002, 2002b; Andersson and Andersson, 2006) but, for the sub-
Kolmogorov size range, there is just one model for coalescence
(Chesters, 1991) but no model for breakage. Besides, there is
no model that can be continuously applied for all length scales
(Chesters, 1991; Kamp et al., 2001; Joshi, 2001; Lasheras et al.,
2002; Jakobsen and Dorao, 2005; Frank et al., 2007; Liao and
Lucas, 2009, 2010).
There are a few reviews of breakage and coalescence of
fluid particles (Chesters, 1991; Lasheras et al., 2002; Liao and
Lucas, 2009, 2010) that describe and compare most of the
existing models. The coalescence models are based on similar
hypotheses being quite similar to each other. However, there
are some inconsistencies in almost all of the breakage models
(Lasheras et al., 2002).
Coalescence in liquid–liquid and gas–liquid systems are
considered to behave differently only because of their dif-
ferent interface behaviors (Chesters, 1991). The interface can
be assumed to be rigid or deformable. Being deformable, the
interface may be immobile, partially mobile or fully mobile
(Chesters, 1991; Liao and Lucas, 2010).
Some models (Coulaloglou and Tavlarides, 1977; Hsia and
Tavlarides, 1983; Tsouris and Tavlarides, 1994; Chen et al.,
1998) were developed for liquid–liquid dispersions and others
(Prince and Blanch, 1990; Luo and Svendsen, 1996; Martínez-
Bazán et al., 1999a,b; Hagesaether, 2002b; Wang et al., 2003)
for gas–liquid systems. However, there is no feature that dis-
tinguishes the application of these models for gas–liquid or
liquid–liquid systems. Martínez-Bazán et al. (1999a,b) pointed
out that their breakage model should be applied only to
gas–liquid systems due to the assumption of negligible inter-
nal viscous deformation forces. Some works (Eastwood et al.,
2004; Andersson and Andersson, 2006; Maaß et al., 2010)
showed that the internal flow is critical to differentiate
between the breakage of drops and bubbles and that this may
explain the large number of particles formed in drop breakage.
Several works analyzed single drop breakage experiments.
Eastwood et al. (2004) analyzed the breakage of drops in a
turbulent water jet, showing that drops usually are consid-
erable deformed prior to the breakage event, specially for
highly viscous dispersed phases. This behavior was attributed
to drop interaction with large turbulent scales. Their data
showed the occurrence of multiple daughters on drop break-
age. Andersson and Andersson (2006) observed drop breakage
events in a static mixer, confirming that the binary breakage
is not a good assumption for drops.
Galinat et al. (2005, 2007) analyzed the drop breakage down-
stream of a pipe restriction. Their single drop experiments
indicated that the number of daughter droplets is an increas-
ing number of the global Weber number, which they defined
using the pressure drop through the orifice. For dispersed
phase fractions lower than 20%, Galinat et al. (2007) found
out that the breakage in the dispersions was similar to that
observed in the single droplet experiments. For larger dis-
persed phase fractions, the turbulence field was modified,
2495
leading to a different breakage dependence on the Weber
number. Recently, Maniero et al. (2012) modeled and simulated
the deformation of single droplets in the flow downstream of
a duct orifice. They simulated the continuous-phase flow by
DNS and used a Lagrangian drop tracking model that included
the dynamics of drop deformation. The Taylor Reynolds num-
ber was about 40 and the 2 mm droplets were in the inertial
subrange. The results were in agreement with the experimen-
tal data of Galinat et al. (2005, 2007). These results indicates
that for low turbulent flows and millimeter-sized droplets,
breakage is a non-local phenomena.
There are several works that analyzed the behavior of
liquid–liquid dispersions in turbulent flows, but we focused on
those works that developed breakage or coalescence models
for liquid–liquid emulsions.
Chen et al. (1998) carried out experiments in a continu-
ous flow screw-loop reactor using a water–paraffin oil system
in order to validate their breakage model. The droplet size
distributions of the emulsions were determined by a laser
diffraction method. The droplet diameter ranges from 0.4 to
200 ␮m. Chen et al. (1998) modified the model of Coulaloglou
and Tavlarides (1977) to include the internal viscous defor-
mation forces. The experimental data was used to model the
probability distribution of the daughter droplets. Chen et al.
(1998) adjusted the 6 model parameters and stated that the
model describes the process fairly well. Droplet coalescence
was neglected.
Raikar et al. (2009) experimentally analyzed the produc-
tion of soybean oil-in-water emulsions in a high pressure
homogenizer. Droplet size distributions were measured in a
light-scattering equipment. They used two models for the
droplet breakage rate. The first one assumes that breakage
originates from droplet collision with turbulent eddies, being
derived following Chen et al. (1998) but neglecting the effect
of the dispersed phase viscosity on drop deformations. The
second model assumed that breakage occurs due to turbulent
shear. They solved a pure breakage PBE model by a sec-
tional method using a 100-node uniform mesh. Their model
assumed binary breakage with a truncated normal distribu-
tion as the daughter droplet probability distribution. There
are 4 parameters in this model that were estimated from the
drop volume distributions. The model predict only qualitative
trends of the evolution of the drop size distribution but failed
to predict the effect of the pressure drop in the equipment.
Afterwards, Raikar et al. (2010) improved the model by
including a model for drop breakage due to laminar shear,
considering non-binary breakage with the Hill-Ng distribu-
tion. They showed that the formation of multiple daughter
drops could explain much better the experimental data on
the droplet size distribution, which were best represented
with a mean number of daughters equal to 20. Their results
were good for large surfactant–oil ratios, when the effect of
coalescence was small. However, the accuracy of the experi-
mental data was not enough to determine the values of the
two parameters of the model for the breakage rate due to
laminar shear.
Recently, Maindarkar et al. (2012) incorporated the coales-
cence model of Coulaloglou and Tavlarides (1977) to Raikar
et al. (2010) model. The breakage rate was assumed to be the
sum of the rates originated from the mechanisms of drop-
eddy collisions and turbulent shear (Raikar et al., 2009). The 6
model parameters were adjusted and the best fit was obtained
considering a mean value of 80 daughters in the breakage
process.
2496 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

Raikar et al. (2011) aimed to increase the model applica-

bility over a wide range of pressures. The most significant
improvements were obtained by increasing the mean num-
ber of daughter drops in a breakage event to 20–150 and by
introducing a maximum stable diameter, below which drops
could not break (Vankova et al., 2007). They concluded that
the usage of an appropriate number of daughter drops and a
critical droplet diameter were essential to model the emulsion
formation.
All the above cited works analyzed breakage and coales-
cence in emulsions that were not made with crude oil.
Recently, Keleşǒglu et al. (2013) determined droplet size dis-
tributions for water-in-crude oil emulsions with digital video
microscopy and nuclear magnetic resonance, but they did not
attempted to analyze its evolution during the emulsion flow.
Our aim was to develop breakage and coalescence models
for the turbulent flow of water-in-crude oil emulsions through
valve-like elements. Experimental data were obtained by flow-
ing the emulsion through a duct containing a variable accident
that acts like a valve. A population balance model was used
to relate the inlet and outlet droplet size distributions. A new
breakage model was proposed based on the theoretical work of
Cristini et al. (2003) and a coalescence model based on previous Fig. 1 – The test section: (a) side view of the whole section
knowledge was employed. The parameters of these models and (b) side view of the flow path restricted by the gates.
were adjusted considering the experimental uncertainty of The duct depth is 5 mm. ˝ is the central valve opening
all variables. To the authors’ knowledge, this is the first time distance. The effective volume of the valve-like element
that breakage and coalescence models have their parameters was modeled as the sum of volumes V1–V5.
estimated for an emulsion with an actual crude oil.

experimental tests. This limited the size of the cross section

area of the test section.
2. Materials and methods

2.1. Premises of the experimental setup design 2.2. The test section

As stated above, we were interested in studying the effect of
a valve-like element, similar to a mixing valve, on the size
distribution function of water droplets in a emulsion of dead
crude oil. This imposes severe restrictions on the design of the
experimental setup.
First, in order to isolate the effect of the valve-like element,
the flow in the test section must be laminar in its absence
and, when it is present, it must generate enough turbulence
to break the droplets. Therefore, a test section with mov-
able gates was designed and the operational conditions were
defined to meet these requirements.
Second, as the crude oil is completely opaque, there is no
optical access to measure the flow variables, as the turbulence
characteristics or the droplet size distributions. Therefore,
the analysis must consider only global variables, that is, the
droplet size distribution functions at the inlet and outlet of
the test section and an estimate of the turbulence induced by
the valve-like element. A procedure to sample the emulsion
to determine the droplet size distributions was developed and
validated.
Finally, the dead crude oil must not contain any additives,
demulsifiers or surfactants, in order not to affect the coales-
cence and breakage phenomena. The addition of demulsifiers
in crude oil prior to refining is common practice (Al-Sabagh
et al., 2011) but this impedes the generation of the emul-
sion and, thus, the analysis of the coalescence and breakage
phenomena. Therefore, special care was taken to get a large
sample of a crude oil without any additives. However, due
to storage limitations, the emulsion flow rate had to be kept
smaller than 6 l/min to allow the execution of all the planned
The test section consists of a duct of square cross section with
5 mm in side and 200 mm in length. The central part of the
duct has three movable gates with 5 mm width. These gates
can be precisely put at chosen positions using dial indicators
(Digimess, model 121.302) with 0.01 mm accuracy, generating a
large variety of geometric configurations for this valve model.
Fig. 1 shows the details of this test section.
2.3. Experimental setup
The flowchart of the experimental apparatus is shown in Fig. 2.
A 5000-l oil tank (T-01) has a 60 l/min double diaphragm pump
(DP-01, Versa-matic, model E1) for homogenization. From the
tank, a progressive cavity pump (P-01, Weatherford with rotor
HD 20, 6.8 l/min) makes the oil flows through a 18 kW heater
(H-01, Eltra, model ADO-180) to facilitates its emulsification in
the mixer (M-01, an inverted flow venturi). Water is fed to the
mixer from an insulated 100-l tank (T-02) with a 3 kW electrical
resistance by a second progressive cavity pump (P-02, Netzsch
with rotor NM11). Pumps P-01 and P-02 are driven using fre-
quency converters (Adleepower, model AS2-IPM) in order to
independently control their flow rates to fix the concentration
of the water in the emulsion within 1% of the desired value.
It should be pointed out that the emulsion generator always
operates in the same conditions in order to minimize vari-
ations in the produced emulsion. Two pumps (P-03, P-04,
Weatherford with rotor HD 15, up to 3 l/min) in parallel,
driven using frequency converters (Adleepower, model AS2-
IPM), feed part of the overall emulsion flow rate to the test
section. A 500 W line heater (H-02) placed just before the test
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508 2497

Drain
T-01

Crude
Oil DP-01

P-03
Drain
(emulsion)

P-01 H-02
(crude oil) TI TI

T-02
H-01
Test Section
TI Hot
Water
TI P-04
(emulsion) PI PI PI
PI

Shear
M-01
Valve Sample A Sample B
P-02
(water)
PI

T-01 Crude Oil Tank Progressive Cavity Pump "T" Mixer

T-02 Water Tank (heated)

PI Pressure Indicator
TI Temperature Indicator Diaphragm Pump
Globe Valve
Check Valve
Ball Valve
Heater

Fig. 2 – Schematics of the experimental setup.

section controls the emulsion temperature in the test section
within ±1 ◦ C for all runs.
Preliminary tests showed that the emulsion generated in
the conditions described above had droplets too small to break
further in the test section. Therefore, before the test section, a
tube with 12.7 mm in diameter and 20 meters long arranged in
a spiral with a diameter of 2 m (see Fig. 2) was included. This
long tube with large cross section area proved to be adequate
to promote droplet coalescence in order that the droplet sizes
at the inlet of the test section were large enough to break by
the turbulence generated by the valve-like element.
There are drains before and after the test section. The
emulsion flow can be completely deviated from the main line
to each drain in order to sample the emulsion flow for the
experimental determination of the drop size distribution func-
tion.
Flow rate in the test section is measured by an oval gear
flow meter (Metroval, model OI-06Ag19/F5) with a 0.3% accu-
racy. The pressure drop in the test section was determined
by pressure transmitters (Yokogama, model EJX430A-EAS4G-
912EB) with 2% accuracy. The operating temperature was
measured before and after the test section by two resistance
thermometers (PT-100 Ohm).
Oil density, viscosity and water–oil surface tension were
determined as a function of temperature in the range 55–65 ◦ C
by a glass density meter with accuracy better than 5 kg/m3 , a
Brookfield LV-DVII+viscometer with 1.0% accuracy and a Du
Noüy ring tensiometer (Kruss, K9 model) with accuracy better
the emulsion was determined from a sample by the volumetric
(Mettler Toledo, Model DL38) and coulometric (Mettler Toledo,
Model DL37) Karl Fischer titration methods (Paiva, 2004). Oil
properties at the desired operational temperature are given in
Table 1.
2.4. Experimental procedure
In order to guarantee the homogenization of the oil in the tank,
pump DP-01 was used to circulate it during 2 h at 60 l/min.
Then, oil and water were fed to the mixer at the specified flow
rates for the given experimental point. Finally, the gates of the
test section were positioned to the desired gaps.
After the stabilization of temperature, flow rate and pres-
sure drop across the test section, an additional waiting period
of 5 min was taken before the emulsion was sampled. Emul-
sion samples were first obtained for the test section outlet and
then for its inlet, in order not to disturb the flow, because the
sampling procedure diverts the overall flow rate to the corre-
sponding drain.
Table 1 – Properties at 60 ◦ C.
Property Value
 (kg/m3 ) 865
 (Pa s) 0.0115
(m2 /s) 1.33 × 10−5
 (N/m) 0.0223
than 0.1 mN/m, respectively. The water mass concentration in
2498 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

The samples were collected manually by taking emulsion
drops using a glass stick and then put in a beaker containing
a highly viscous mineral oil to prevent water droplets coales-
cence. This oil was transparent, making possible the use of the
particle analyzer by laser diffraction. The beakers with mineral
oil were put to rest for 24–48 h in order to eliminate the bubbles
that may be entrained in the sampling procedure. The sam-
ples were homogenized using a magnetic stirrer very gently in
order not to produce drop coalescence. Then, the normalized
droplet size distribution was determined for each sample.
This determination was carried out using a laser diffraction
particle sizer (Malvern® Mastersizer 2000). Such equipment
was modified to allow that all sample volume can be flowed
through the detector by gravity without any agitation or suc-
tion in order to avoid changing the droplet size distribution.
Under ordinary conditions, this analyzer provides an error of
10% in the determinations of the normalized volume distribu-
tion function of droplets and errors around 2% for the mean
diameters.
2.5. Experimental conditions
The test conditions are based on a full factorial experimental
planning with two levels of water concentration, three levels
of mass flow rate and five levels of positioning of the gates.
The temperature of all runs were nominally set at 60 ◦ C.
The two external gates of the test section were kept in
the same positions, defining openings of 2.0 mm for all runs.
The opening of the central gate, ˝, was varied among four
positions (see Fig. 1). This simulates the characteristics of a
globe valve. The chosen values of ˝ were 0.5, 1.0, 1.5 and
2.5 mm. Besides, a blank experiment, where all gates were
fully opened, was added to the experimental planning in order
to periodically check if the drop size distributions before and
after the valve-like element were approximately equal. The
blank experiments were also used to show that the procedure
of sampling and determination of the droplet size distribu-
tions gives reproducible results.
The nominal water concentrations were selected to be 8
and 15% (w/w), which reflect typical industrial operational
conditions. The selected emulsion mass flow rates were 1.7,
3.0 and 4.3 kg/min. These values were chosen in order to guar-
antee that the flow was laminar in the test section with all
gates fully opened.
4.3 kg/min, respectively. The pressure loss in the test section
varied in the ranges 0.04–0.18 bar when the gates were fully
opened and 0.5–8.40 bar for the other conditions. Therefore,
except for the blank experiments, most of the pressure drop
in the test section was caused by the valve-like element.
From the 103 runs shown in Table 2, 19 were those with
fully opened gates that were performed to guarantee that the
valve-like element was the main factor affecting the evolution
of the droplet size distribution in the test section. They cannot
be used in the estimation of the model parameters. Other six
runs were eliminated due to inconsistencies in the measured
drop size distributions. Therefore, 78 valid experimental runs
were used for parameter estimation.
3. Population balance model
The mean number of particles per unit volume of the parti-
cle state space is the particle number distribution function, f.
Considering only one internal variable, the particle volume, v,
f (t, v, z) is called the particle number size distribution func-
tion (PSDF). In order to predict the evolution of the PSDF,
it is necessary to solve the population balance equation
(PBE). Considering breakage and coalescence of particles and
neglecting nucleation and particle growth, the PBE can be writ-
ten in the following Lagrangian form (Ramkrishna, 2000):
Df ∂f  
= + Ż · ∇z f (v, z) = H( f ; v, z, y) − f (v, z)∇z · Ż (1)
Dt ∂t
where Df/Dt is the material derivative of f, Ż is the velocity
of the particle with volume v at spatial position z, y is the
vector of continuous phase properties and H is the particle
net production rate:
H = BB − DB + BC − DC (2)
where BB , DB , BC and DC represent, respectively, the parti-
cle production (birth) and destruction (death) by breakage
and the birth and death by coalescence, which are given by
(Ramkrishna, 2000):

  ∞
BB ( f ; v, z, y) = ς(v , y)P(v|v , y)b(v , y)f (v , z)dv (3)
v

For each experimental condition, up to 5 replicates were  

attempted. The experiments were grouped by mass flow rate DB ( f ; v, z, y) = b(v, y)f (v, z) (4)
and water concentration, but the position of the central gate

was randomized. In order to identify the experimental data,   1
v

a code was established to each run, given by: ptXgY, where BC ( f ; v, z, y) = f (v − v , z)f (v, z)a(v − v , v , y)dv (5)
2 0
X and Y are integer numbers varying in the 1–10 and 1–15

ranges, respectively. In this code, Y is related to the replicate at   ∞
a mass flow rate level and X is related to the gate positioning DC ( f ; v, z, y) = f (v, z)f (v , z)a(v, v , y)dv (6)
and water concentration levels. Table 2 associates each run 0

code to its conditions. The dash in this table indicates that

In the above equations, it was assumed that the breakage
the corresponding run was eliminated from the analysis due
and coalescence functions are affected by the position only
to detected experimental problems.
through y. From now on, in order to simplify the notation, y
From the 150 performed runs, 47 were discarded due to
and z are omitted.
the problems detected at the experimental level. For the
Considering volume conservation in the breakage process,
remaining 103 runs, the temperature varied within 56–62 ◦ C,
the conditional daughter particle probability density function,
whereas the measured water concentrations varied in the
P(v |v), has the property (Ramkrishna, 2000):
ranges of 8.1–8.5 and 14.5–14.6% (w/w) for the 8 and 15%
(w/w) nominal values, respectively. The measured emulsion  v
mass flow rates varied within the ranges of 1.67–1.72, 2.97–3.01 ς(v) P(v |v)dv = v (7)
and 4.25–4.37 kg/min for the nominal values of 1.7, 3.0 and 0
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508 2499

Table 2 – Code map for all experimental runs.

Nominal mass Nominal water concentration (w/w, %)
flow rate (kg/min)

15 8

˝ Open 2.5 1.5 1.0 0.5 0.5 1.0 1.5 2.5 Open
Y\X 1 2 3 4 5 6 7 8 9 10

4.3 1 – – – – – – – – – –
2 pt1g2 pt2g2 – – pt5g2 pt6g2 pt7g2 pt8g2 pt9g2 pt10g2
3 pt1g3 pt2g3 pt3g3 pt4g3 pt5g3 – pt7g3 pt8g3 pt9g3 pt10g3
4 pt1g4 pt2g4 pt3g4 pt4g4 pt5g4 pt6g4 pt7g4 pt8g4 pt9g4 –
5 – pt2g5 pt3g5 pt4g5 – pt6g5 pt7g5 – pt9g5 pt10g5

1.7 6 – – – – – – – – – –
7 pt1g7 pt2g7 pt3g7 pt4g7 pt5g7 pt6g7 pt7g7 pt8g7 pt9g7 pt10g7
8 pt1g8 pt2g8 pt3g8 pt4g8 pt5g8 – pt7g8 – – –
9 pt1g9 pt2g9 pt3g9 pt4g9 pt5g9 pt6g9 – pt8g9 pt9g9 pt10g9
10 pt1g10 pt2g10 – – – – pt7g10 pt8g10 pt9g10 pt10g10

3.0 11 pt1g11 pt2g11 pt3g11 pt4g11 pt5g11 pt6g11 pt7g11 pt8g11 pt9g11 pt10g11
12 pt1g12 pt2g12 pt3g12 – pt5g12 pt6g12 pt7g12 pt8g12 pt9g12 –
13 – pt2g13 pt3g13 pt4g13 – pt6g13 – pt8g13 pt9g13 pt10g13
14 – – pt3g14 pt4g14 pt5g14 – – pt8g14 pt9g14 pt10g14
15 pt1g15 pt2g15 pt3g15 – pt5g15 pt6g15 pt7g15 pt8g15 pt9g15 –

3.1. Simplified model for experimental analysis Therefore, Ve was firstly considered to be equal to the volume
shown in this figure. Afterwards, this assumption was verified.
As the PB-CFD simulation demands a large computational Moreover, as the experimental pressure drop in the test
effort, its usage for determining the parameters of the break- section is almost completely due to the valve-like element, the
age and coalescence models by optimization is nowadays mean dissipation rate of turbulent energy, , was estimated by
impractical. Besides, only the normalized PSDFs at the out-
let and inlet were known. Thus, we decided to use a simplified p
= (10)
Lagrangian model based on Eq. (1). tres 
Our simplified model assumes that the phases are incom-
pressible and all droplets move with the continuous phase where  is the oil density.
velocity. In this case, the mixture continuity equation is
∇z · Ż = 0 and the last term in Eq. (1) vanishes, giving for the
3.2. The coalescence model
steady-state:

Df   In an attempt to develop a model that can be applied to any

= Ż · ∇z f (v, z) = H( f ; v, z, y) (8) range of droplet sizes observed experimentally, the coales-
Dt
cence model was designed to be used for particles in the
These assumptions lead to phase fractions that are uniform dissipation and inertial size ranges.
in the test section. According to Chesters (1991) the coalescence frequency, a,
Furthermore, as the PSDF change occurs due to the pres- is given by
ence of the valve-like element, this model also assumes that
the final distribution can be obtained by integrating Eq. (8) in
a(d, d ) = (d, d )(d, d ) (11)
t up to the mean hydrodynamic residence time, tres , which is
defined by
where  is the coalescence efficiency and  is the collision
Ve frequency, which is given by
tres = (9)
Q

where Ve is the effective volume of the valve-like element (d, d ) = Cc Sur , (12)
and Q is the volumetric flow of the emulsion. Even though
droplet coalescence and breakage occur in different regions, where the sectional area, S, and the relative velocity, ur , are
this model assumes the same region for both phenomena, given by
which is equivalent of using mean coalescence and breakage
functions as usually done in well-mixed reactors (Coulaloglou 
(d + d )
2
S= (13)
and Tavlarides, 1977). 4
The effective volume of the valve-like element can be
considered another parameter of the model, whose value is and
different for each experimental run. However, previous stud-
ies (Lage et al., 2006) showed that the droplets break mainly ud + ud
ur = (14)
nearby the valve-like element, in a region whose volume is 2
somewhat constant and may be approximated by the sum
of the volumes V1–V5 which are represented in Fig. 1(b). being Cc a parameter which must be adjusted experimentally.
2500 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

The collision frequency was estimated using the character- According to Martínez-Bazán et al. (1999a,b), the breakup
istic velocity modeled as (Chesters, 1991): frequency is given by

⎧  ⎧ 
⎨ d  , for d <  ⎪
⎪ 2Wecrit 
⎪
⎨ ˇ(d)2/3 −
ud = (15) d
⎩ 1/3 b(d) = Cb , for d > dc,mb (19)
(d) , for d≥ ⎪
⎪
d
⎪
⎩
0, for d ≤ dc,mb
Four alternative models were tested for the coales-
cence efficiency (Chesters, 1991), corresponding to different
where ˇ = 8.2, Wecrit = 6 (the Weber number in this model is
hypotheses regarding the droplet interface behavior: rigid
defined as We = ˇ(d)2/3 d/2) and the critical particle diameter,
interface, deformable partially mobile interface, deformable
dc,mb is given by
immobile interface and deformable mobile interface. From
these models, only the first two gave good results and, thus,  2We  3/5
only them are described in the following. dc,mb = crit
−2/5 (20)
ˇ
The coalescence efficiency for droplets with rigid interfaces
is modeled as (Chesters, 1991): Cristini et al. (2003) theoretically developed an expression
  to the breakage frequency that can be written as
1 hi
 = exp −Ce ln (16)  √
4 hf  3  / d
b(d) = Cb,c Ca , Ca = (21)
2
where hi and hf are, respectively, the initial and final thick-
for Ca > Cacrit , being zero otherwise.
nesses of the thin film formed between the droplets under
It is essential that the breakage model is a continuous func-
collision. The value of hf can be estimated by
tion of its variables. Therefore, it was assumed that there is a
1/3 transition diameter such that the breakage frequencies given
Adeq by Eqs. (19) and (21) have the same value. This transition diam-
hf = (17)
16 eter, dl , was assumed to be given by

 3 6/5
As the value of hi is unknown, the ratio hi /hf is sometimes
dl = dc,mb ∼
= 1.627 dc,mb (22)
assumed to be an unknown constant which leads to a constant 2
coalescence efficiency which is incorporated in the adjusted
parameter Cc . This hypothesis is usually necessary when the which is the point where the breakage frequency given by Eq.
values of  are in a narrow range which makes the estima- (19) reaches its maximum value.
tion of Ce very difficult. This approach was used in the present Thus, by equating the breakage frequency given by Eqs. (19)
work. and (21) at d = dl , a relation between the empirical parameters
The coalescence efficiency for droplets with deformable Cb,c and Cb can be derived, which can be written as:
and partially mobile interfaces is modeled as (Chesters, 1991):
63.927
 d 4/5
Cb,c = Cb 11/5
Ca−4/5 (23)
Wecrit 2
 √    √
3 d 3/2 deq  / deq
 = exp −Ce Caeq , Caeq =
8  hf 2 where the value of ˇ was used.
(18) Using Eq. (23), the combined model for breakage frequency
is given by

where hf was given by Eq. (17) with A = 0.6 × 10−20 J. This value ⎧ 
⎪
⎪
Cb 2/3
ˇ(d) −
2Wecrit 
, for d > dl
was chosen because it is the center value of the experimen- ⎪
⎪ d d
⎨
tal range of the Hamaker constant for water-water interaction   4/5
b(d) = 63.927  2.2 d
through a hydrocarbon phase given by Israelachvili (2011) in ⎪
⎪ Cb Ca , for d ≤ dl and Ca > Cacrit
⎪
⎪
11/5
Wecrit 2
his Table 13.3. Any error in this A value is compensated by the ⎩
adjusted Ce value. 0, Ca < Cacrit
(24)

3.3. The breakage model

which have three empirical parameters, Cb , the critical Weber,
The breakage model was also designed to be used for any range
Wecrit , that determines dl , and the critical capillary number,
of particle sizes. It is composed by the Martínez-Bazán et al.
Cacrit , defined by
(1999a) model and one developed based on the work of Cristini
et al. (2003). √
 / dcrit
The breakage model of Martínez-Bazán et al. (1999a) was Cacrit = (25)
selected because it can be applied to non-binary particle
breakage. Moreover, the model of Martínez-Bazán et al. (1999a)
has extensive theoretical basis and experimental validation
when compared with other models that could have been
selected (Lasheras et al., 2002; Liao and Lucas, 2009), even
though it was developed for bubbles.
2
Cacrit was modeled by assuming that dcrit is the minimum
attainable droplet diameter at the outlet of the test section
as most of the data are for breakage dominant conditions.
Cristini et al. (2003) suggested that Cacrit is inversely pro-
portional to the flow Reynolds number. Therefore, we tried
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508 2501

to use Cacrit ∝ Re−C

max , where Remax was defined based on the
Re Following Kumar and Ramkrishna (1996), the method of
maximum fluid velocity in the valve-like element: classes was applied to Eq. (8) leading to the following expres-
sion:
(Q/Ac,min )c Q
Remax = = (26)
l

DNk 
i≥j
where Ac,min = lc is the smallest flow sectional area (l = 5 mm). = (1 − 0.5ıij )ijk ai,j Ni Nj
However, this formula could not represent the minimum Dt
i,j
attainable droplet diameter. xk−1 ≤ (xi + xj ) ≤ xk+1
Since the probability of breaking the smallest droplet in the
distribution depends on its interaction with a high energy tur- 
n 
n
− Nk Ni ai,k + ςi ϕk,i bi Ni − Nk bk (30)
bulent eddy, this probability increases with the period of time
i=1 i=k
in which the droplet is in the effective volume of the valve-
like element. Therefore, it is reasonable to assume that Cacrit
depends on the Stokes number defined by the ratio between where  i,j,k and ϕk,i are defined as:
the residence time and the turbulent time scale. Thus, we
⎧ x − (x + x )
assumed the following functional dependency: ⎪ k+1 j i
⎨ x − x , for xk ≤ (xj + xi ) ≤ xk+1
k+1 k
i,j,k = (31)
Cacrit = CCa StK Re−C
max ,
Re
tres
StK = √ (27) ⎪
⎩ (xj + xi ) − xk−1 , for x ≤ (x + x ) ≤ x
/ xk − xk−1 k−1 j i k

where CCa and CRe are experimental parameters. The min-

imum attainable droplet diameter at the outlet of the  xk+1  xk
test section could be correlated with CCa = 1.65 × 10−4 and xk+1 − v v − xk−1
ϕk,i = P(v | xi ) dv + P(v | xi ) dv
CRe = 3/20. xk
xk+1 − xk xk−1
xk − xk−1
Recent works showed that the breakage of drops is not (32)
binary (Eastwood et al., 2004; Galinat et al., 2005; Andersson
and Andersson, 2006; Raikar et al., 2010; Maaß et al., 2010), Further details about these equations can be found in the orig-
which must be considered in the modeling of the daughter inal reference.
particle probability distribution. In this work, several models It is also of interest the particle volume size distribution,
were attempted. The only one that gave good results is the F(v) = vf (v), as well as its zeroth-order sectional moments:
simple model that assumes that ς equal daughter droplets are
formed upon breakage:  vk+1
Nv,k = F(v)dv ∼
= xk Nk (33)
v
 vk
 
P(v |v) = ı v − (28)
ς
4.2. Determination of the inlet and outlet discrete
This introduces the mean number of daughter droplets, ς, as PSDFs
an adjusted parameter in the model.
The particle size analyzer provides only the first order sec-
4. Numerical procedure tional moments of the normalized particle size distributions
for all size classes, which can be given either for the number,
4.1. Solution of the population balance model Nn , or the volume, Nv,n , distributions. However, the inlet con-
ditions for Eq. (30) are the Nk values of the non-normalized
Among the several numerical methods that have been devel- particle number size distribution, defined by Eq. (29). How-
oped for the solution of the population balance equation, this ever, the dispersed phase volume fraction, , can be calculated
work used the method of classes of Kumar and Ramkrishna from the measured water concentration and the properties of
(1996) enforcing the conservation of number and volume of both phases, allowing the computation of the droplet number
the particle population. This method was chosen because it density by:
allows the direct usage of the particle size classes defined by
the particle size analyzer. Therefore, the experimental data is  6
NT = ∞ = (34)
used to define the discrete drop size distributions without any vf̂ (v)dv d330
0
manipulation.
The sectional moment of the k class, Nk , includes all parti-
where f̂ is the normalized drop number distribution and d30 is
cles with volume between vk and vk+1 , being defined by
the mean volume diameter, which is given by the particle size
 vk+1 analyzer. Then, the Nk values can be determined by:
Nk = f (v)dv (29)
vk
 vk+1  vk+1
Nk = f (v)dv = NT f̂ (v)dv = NT Nn,k (35)
vk vk
This class is represented by the pivot xk = 0.5(vk + vk−1 ). The
classes vk are defined by the particle size analyzer (Malvern®
Mastersizer 2000), being given by the geometric grid defined by where Nn,k is the zeroth order sectional moment of the nor-
vk+1 /vk = 1.514, k = 0, . . ., n, v0 = 5.24 × 10−7 ␮m3 (d0 = 0.01 ␮m), malized particle number distribution for class k as given by
with n = 100 classes. the particle analyzer.
2502 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508
4.3. Orthogonal distance regression
The parameter estimation problem was solved using the
routine ODRPACK95 (Zwokak et al., 2004). This routine imple-
ments the orthogonal distance regression, which consists of
minimizing the orthogonal distance between the experimen-
tal data and the prediction of a model that considers the errors
both on the response and explanatory variables.
Consider a multiresponse model ˚ : Rp+m → Rq given by
i = ˚(
i + ıi ; ˛) − εi (36)
where
i ∈ Rm , m≥1 are the multivariate explanatory variables,
i ∈ Rq , q ≤ 1 is the multiresponse dependent variables, ˛ ∈ Rp
are the model parameters, ıi and εi are the estimated errors in
i and i , respectively, and i = 1, . . ., M is the experiment index.
The orthogonal distance regression implies in the mini-
mization of the objective function:

M 
M
G= εTi Wεi εi + ıTi Wıi ıi
i=1 i=1
where Wıi and Wεi are the matrices of weights associated
with ıi and εi , respectively. They were assumed to be diagonal
whose elements were given by the inverse of the variances of
the corresponding variables.
The numerical procedure used in ODRPACK95 is described
in Boggs et al. (1987, 1989) and Zwolak et al. (2007). The solution
is found iteratively using a trust region Levenberg–Marquardt
method with bound constraints and scaling. Therefore, it is a
method of local minimization of the objective function. This
work used the default values for the scaling. Further details
can be found in the literature (Boggs et al., 1987, 1989; Zwokak
et al., 2004; Zwolak et al., 2007).
The explanatory variables were chosen to be the effective
volume of the valve-like element, Ve , the mass flow rate, the
mean temperature at the test section, the pressure loss in
the test section and the zeroth-order sectional moments of
the number particle size distribution, Nk , at the inlet of the
test section. In an alternative analysis, Nk were substituted by
Nv,k . The response variables were the zeroth-order sectional
moments of the corresponding distributions at the outlet of
the test section. The parameters are those related to the break-
age and coalescence models (Cc , Ce , Cb and ς) being just 3
parameters for the model with constant coalescence efficiency
(Cc , Cb and ς).
As explained later, the experimental runs could not be
replicated. Therefore, the variances of the explanatory vari-
ables were assumed to be the square of the experimental
errors. For the mass flow rate, the mean temperature and the
pressure drop in the test section, we used the measurement
errors. For the Nk or Nv,k , the 10% error reported by the particle
sizer manual was used. A 20% error was assumed for the Ve
value of each experimental run.
Due to the large computational cost of using the ODR-
PACK95 considering the experimental errors in all explanatory
variables, an exploratory optimization study was first carried
out without considering such errors. The minimal point of this
study was the initial condition used in the main optimization
run that includes all the errors in all explanatory variables.
The validity of this procedure in obtaining the global mini-
mum point was verified by performing a global optimization
as explained in the next section.
For the comparison between the experimental and sim-
ulated results of a variable i of experiment i, we used the
relative error defined by:
i,sim − i,exp
ei = (38)
i,exp
to calculate the following mean errors:
1 1
M M
e= ei , |e| = |ei | (39)
M M
i=1 i=1
The value of |e| is the mean of the magnitude of the rela-
tive errors and it represents how well a variable is reproduced
by the adjusted model, whereas e is the mean of the relative
errors that should be zero for an unbiased model when M is
large.
4.4. Global optimization
(37)
The global optimization algorithm called AIU-PPSO (Asyn-
chronous and Immediate Update Parallel Particle Swarm
Optimization) developed by Moraes (2011) was applied to esti-
mate the parameter values of the population balance model,
including the effective volumes of the valve-like element for
all experiments Ve,i , i = 1, . . . M, as new model parameters.
This global optimization was performed to confirm the
validity of the procedure described in the previous section
for locating the global minimum using the ODRPACK and the
assumption used to calculate the values of the effective vol-
ume of the valve-like element. For comparing the modeled Ve,i
values and their estimated values determined by the AIU-PSO
algorithm, error definitions given by Eqs. (38) and (39) were
used.
More details of the AIU-PPSO are given in the work of
Moraes (2011).
5. Results and discussion
5.1. Analysis of the experimental flow conditions
Considering the oil properties shown in Table 1, the Reynolds
number (Rel = lU/ ) for the pure oil flow in the test section with
all gates opened (blank experiments) are 493, 870 and 1246,
for the 1.7, 3.0 and 4.3 kg/s flow rates, respectively. Therefore,
the flow is laminar and very little effect on the droplet size
distributions was expected for the blank experiments.
For the flow in the test section with the gates partially
closed, the experimental conditions of three different cases
were used to estimate the Taylor scale Reynolds number, ReT .
Two cases were chosen because they have the minimum and
maximum flow rates and the same minimum clearance, c. As
a matter of fact, most experiments has c = 1 mm due to the
small horizontal aperture between the gates. The third case
was one of those with the largest pressure drop, caused by the
smallest gap in the central gate, ˝ = 0.5 mm.
Again, pure oil flow was considered with the properties
shown in Table 1. Table 3 summarizes the calculations. The
maximum velocity, Umax , is calculated using the minimum
area normal to the flow in the test section, Ac,min = cl. The
estimation of the turbulent variables follows Pope (2000),
including the usage of his spectra model to determine the ratio
between the longitudinal integral scale, L11 , and the length
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508 2503

Table 3 – Turbulence conditions for pure oil flow. (a) 12

inlet
Variable Conditions of run outlet
10
pt6g2 pt9g2 pt9g9
8 blank experiments:
Data pt1g2

Nv,n (%)
c (mm) 0.50 1.00 1.00 pt1g3
6 pt1g4
Ac,min (mm2 ) 2.50 5.00 5.00
W (kg/min) 4.3 4.3 1.7
4
Umax (m/s) 33.1 16.6 6.6
p (105 N/m2 ) 8.22 3.37 0.54
2
Estimates
u = 0.2Umax (m/s) 6.6 3.3 0.55
2
0
k = 1.5(u ) (m2 /s2 ) 66. 16. 2.6
5 2 3
 (10 m /s ) 6.7 2.5 0.16 101 102 103
 (␮m) 7.7 9.9 19.7 d (micra)
Le = k3/2 / (mm) 0.80 0.27 0.26
ReLe = k1/2 Le / 487. 82. 32.
L11 /Le a 0.65 0.80 0.90 (b) 12
inlet
L11 (mm) 0.52 0.22 0.24 outlet
Ret = u L11 / 259. 54. 23. 10
ReT = u LT / 72. 33. 22.

a
8 blank experiments:
Estimated from Fig. 6.24 of Pope (2000). pt10g2
Nv,n (%) pt10g3
6 pt10g5
scale Le = k3/2 /. The rate of dissipation of turbulent kinetic
energy was estimated from the pressure loss in the test sec- 4
tion, using Eq. (10), which is described in Section 3.
The estimates for the Taylor Reynolds number indicates 2
that most of the experiments were for low turbulence flow
0
conditions (ReT  30). In this case, the inertial subrange does
not really exist. The Kolmogorov length scale, , varied 101 102 103
between 7 and 20 ␮m and L11 was in the [220, 520] ␮m range. d (micra)
As the largest droplets were 100 ␮m in diameter, all droplets
Fig. 3 – Normalized droplet volume size distributions for
should have sizes in the turbulence dissipation range.
the blank experiments for runs (a) pt1 and (b) pt10. The
bars represent the standard deviation calculated from the
5.2. Analysis of the blank experiments
three experiments.

The blank experiments corresponding to the largest flow rate

were selected for this analysis. They correspond to the runs concentration of 15% (w/w) and mass flow rate of 3 kg/min.
pt1g2, pt1g3 and pt1g4 for the 15% (w/w) water-in-oil emulsion Ideally, all these distributions should be equal. The lack of
and the runs pt10g2, pt10g3 and pt10g5 for the emulsion with reproducibility was due to two reasons. First, at each startup
8% (w/w) water content. of the experimental apparatus, the generated emulsion was
The normalized droplet volume size distributions mea- somewhat different, even though all controlled variables (tem-
sured for these runs are given in Fig. 3. The relative frequency perature, water concentration and mass flow rates) were
of each size class was plotted against the size of the droplet basically equal. It was then verified that the physical prop-
with the mean volume in the corresponding class. From, erties of the stored oil suffered 5–10% changes due to aging.
this figure, it can be seen that the method for sampling and This was partially taken into account in the data analysis by
measurement of the droplet size distribution is reproducible
within 10–25% of the relative frequency of each size class. d (μm)
Fig. 3(b) shows that this agreement is better for the 8% (w/w) 101 102
concentration of water, being in the error range of the dis- 25.0 Experimental data
pt1g11 pt3g13
tribution determination. Therefore, the effects of coalescence pt1g12 pt3g14
20.0
and breakage were negligible for this case. On the other hand, pt1g15 pt3g15
Nout × 10-11 ( - )

pt2g11 pt4g11
Fig. 3(a) clearly shows that the inlet and outlet distributions 15.0 pt2g12 pt4g13
pt2g13 pt4g14
for the 15% (w/w) water-in-oil emulsion were somewhat differ- pt2g14 pt5g11
ent, especially for the smallest droplets. Although this could 10.0 pt2g15 pt5g12
pt3g11 pt5g14
be attributed to some degree of coalescence, the most proba- 5.0
pt3g12 pt5g15
ble cause is the inadequate sampling of the smallest droplets,
as discussed in the following. 0.0

10-16 10-15 10-14 10-13 10-12 10-11 10-10

5.3. Preliminary analysis of the experimental size 3
v (m )
distributions
Fig. 4 – Experimental droplet number size distributions at
Fig. 4 shows the droplet number size distributions at the the inlet of the test section for W = 3.0 kg/min and  = 15%
inlet of the test section for all experimental runs with water (w/w) conditions.
2504 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

d (μm) Table 4 – Model parameter estimates obtained by

100 101 102 ODRPACK95 considering (S2 and S3) or not (S1) the
6.0 6.0
pt2g4 inlet (exp) experimental errors in the explanatory variables.
5.0 outlet (exp) 5.0 Results S3 were obtained using the estimates for the
Nout × 10−14 ( − )

Nin × 10−12 ( − )
4.0 η dc,mb 4.0 effective volume of the valve-like element given by the
AIU-PPSO algorithm (Moraes, 2011).
3.0 3.0
Parameters S1 S2 S3
2.0 2.0
1.0 Model with constant coalescence efficiency
1.0
102 Cc 1.00 ± 0.05 1.05 ± 0.23 1.88 ± 0.06
0.0
0.0 102 Cb 0.98 ± 0.06 1.06 ± 0.80 1.08 ± 0.07
ς 26.0 ± 0.9 26.9 ± 9.4 32.7 ± 16.8
10−19 10−17 10−15 10−13
3
v (m ) Coalescence efficiency model given by Eq. (18)
102 Cc 0.90 ± 0.47 – –
Fig. 5 – Experimental droplet number size distributions at 102 Ce 1 (constant) – –
the inlet and outlet of the test section. 102 Cb 0.81 ± 0.31 – –
ς 31.2 ± 9.5 – –

determining the oil physical properties again after the g10
group of experimental runs.
Second, the experimental procedure used to sample and
measure the droplet size distributions may introduce some
perturbations due to micro-bubbles entrainment and insuffi-
cient sampling of the smallest droplet sizes. This is the most
probable reason why the number size distributions did not
reproduce well (see Fig. 4). On the other hand, as the vol-
ume size distributions depend only slightly on the smallest
droplets, they could be obtained with fairly good reproducibil-
ity, as shown in Fig. 3. This occurs because the number of
droplets needed for the convergence of the number size distri-
bution is much larger than what is necessary for the volume
size distribution convergence. Therefore, droplet number size
distributions should not be used for estimating the model
parameters, as they are mostly influenced by the smallest
droplet sizes. However, we decided to analyze both the num-
ber and volume size distributions. In order to do that, the runs
in the same operational conditions could not be used as actual
replicates. Therefore, each experimental run was considered
unique and the experimental accuracy of 10% was assumed
for Nk and Nv,k .
Fig. 5 shows the particle size distributions at the inlet and
outlet of the test section for run pt2g4. The calculated values
of the Kolmogorov length scale, , and the critical diameter
in the Martínez-Bazán et al. (1999a) model, dc,mb , were also
represented for the conditions of this run. dc,mb was evalu-
ated using Eq. (20) with Wecrit = 6. Fig. 5 shows the occurrence
of strong droplet breakage as the emulsion flows through the
test section. It also clearly shows that most of the particles
at the inlet of the test section are smaller than  and all of
them are smaller than dc,mb calculated using Wecrit = 6. For this
value of dc,mb , the Martínez-Bazán et al. (1999a) model predicts
a zero breakage frequency, as given by Eq. (19). Therefore, Wecrit
was included as a new parameter to be estimated in the pop-
ulation balance model using the breakage model described in
Section 3.3.
However, in any optimization run, the estimate of Wecrit
always corresponded to a dl value larger than the largest
droplet in the experimental PSDFs. From Eq. (24), it is clear
that only the part of the proposed breakage model based on
the work of Cristini et al. (2003) was active. This was expected
because the analysis of the flow turbulence indicates that
there is no distinct inertial subrange.
Therefore, we could conclude that all droplets in our
experimental conditions were in the turbulence dissipation
size range and the coalescence and breakage models were
modified to consider just this size range. The model for droplet
collisions became:
3 
(d + d ) 
(d, d ) = Cc (40)
8
where Cc is an experimentally adjusted parameter and the
coalescence efficiency was assumed constant or given by Eq.
(18), which introduces the adjusted parameter Ce . The break-
age frequency model was simplified to:
⎧   4/5
⎪
⎨ Cb 63.927  Ca2.2 d
11/5
, for Ca > Cacrit
b(d) = We 2 (41)
⎪ crit
⎩ 0, for Ca ≤ Ca
crit
11/5
where Wecrit = 6 was used leading to 63.927/Wecrit = 1.241.
Although this is a typical value for bubbles and not for droplets
(Galinat et al., 2005; Raikar et al., 2010; Maaß et al., 2010), this
has no consequence because the adjusted value of Cb corrects
for any inadequacy. The critical capillary number is still given
by Eq. (27) and the daughter droplet probability distribution is
given by Eq. (28).
5.4. Parameter estimation with ODRPACK
The parameter estimation procedure described in Section 4.3
was applied to the population balance models given by Eqs. (8),
(40), (41), (27) and (28) for the model with constant coalescence
efficiency and also using Eq. (18) for the coalescence effi-
ciency model for drops with deformable and partially mobile
interfaces. The discrete particle volume distribution functions
(Nv,k values) at the test section inlet and outlet were used
as explanatory and dependent variables, respectively. The
alternative use of the discrete particle number distribution
functions (Nk values) did not result in any set of parameter
values with statistical significance. This was expected due to
the errors associated to the measurement of the number dis-
tribution functions.
Table 4 shows the optimized parameter values and their
95% confidence intervals obtained using all the valid experi-
mental data, considering or not the errors in the explanatory
variables. For the constant coalescence efficiency model, the
values of the parameters are almost the same for both
optimizations, but the confidence intervals are much larger
when the errors in the explanatory variables were taken into
account. Considering the coalescence efficiency model for
droplets with deformable and partially mobile interfaces, it
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508 2505

was not possible to determine all the model parameters with

Table 5 – Errors in the prediction of mean diameters at
statistical significance. This is related to the global character- the outlet of the test section using the model with
istics of the employed population balance model. However, constant coalescence efficiency.
for PB-CFD simulations, it is very important to have a non-
pq Dpq dpq
constant coalescence efficiency. Therefore, the Ce parameter
was fixed at several values and an attempt was made to e (%) |e| (%) emax (%) e (%) |e| (%) emax (%)
estimate the other parameters. This procedure was success- 10 −0.01 8.1 25.6 189 189 780
ful only for Ce = 0.01 and when the errors in the explanatory 20 −1.69 9.3 29.6 142 142 546
variables were not considered. The results show in Table 4 30 −1.95 10.3 31.4 88 88 288
indicates that the values for the other parameters, Cc , Cb and 32 −2.37 12.6 35.3 21.3 21.3 50.6
ς, agree with those obtained for the constant coalescence effi- 43 −0.03 14.0 39.5 −0.01 8.1 25.6
ciency model, within their confidence intervals.
The large value of the number of daughter particles may peak, as shown in Fig. 6(b), which is not important to the vol-
be substantiated by other works (Eastwood et al., 2004; Galinat ume particle distribution but is very important to the number
et al., 2005; Andersson and Andersson, 2006; Raikar et al., 2010; particle distribution. Nonetheless, the mean diameter d43 is
Maaß et al., 2010), but it is important to note that the model the most important one for analyzing the desalting equip-
used for the daughter conditional probability distribution is ment and it was very well predicted. The mean diameter d32
the simplest possible. is important in polydisperse multiphase flow simulations. As
Due to space limitations, it is not possible to present all shown in Table 5, it could be predicted with a mean error of
results here. The comparison of simulated and experimental 21.3%, which is reasonably good.
data for all runs are available in Mitre (2010). Some results are
presented below. 5.5. Results from the global optimization
Fig. 6 shows the droplet volume size distributions at the
inlet and outlet of the test section obtained experimentally The global optimization AIU-PPSO algorithm (Moraes, 2011)
and by simulation using the population balance model with was applied to the estimation of Cc , Cb , ς and the Ve,i , i = 1, . . . M
constant coalescence efficiency. These results were calculated for the population balance model with the constant coales-
using an unique set of estimated values for the parameters of cence efficiency. Since M is large, the global optimization in a
the breakage and coalescence models using all 78 experimen- space with M + 3 dimensions has a very large computational
tal runs (set S1 of Table 4). Besides, it should be pointed out cost, whose order is about 3 months of CPU time in a 64-node
that, when errors are considered in the Nv,in variables, the inlet cluster. Therefore, the global optimization of the population
distribution obtained by the optimized model can be different balance model with the other coalescence efficiency model
from the experimentally measured one. These simulated inlet was not carried out.
distributions are also given in Fig. 6 where it can be seen that After the global minimization, the parameters obtained by
they agree to the experimental ones within the experimental the AIU-PPSO algorithm were fed to the ODRPACK optimiza-
errors. Fig. 6(a) presents the results with the best agreement, tion program, including the estimated values of Ve,i , i = 1, . . . M
where the droplet volume size distribution at the outlet is uni- and considering the errors of all explanatory variables. The
modal. Fig. 6(b) shows typical results where the outlet droplet resulting parameter values and their 95% confidence inter-
volume size distribution is bimodal. Despite the good agree- vals are also shown in Table 4. This procedure guaranteed that
ment obtained in the main peak, the secondary peak could the same objective function was used to generate these and
not be predicted by the model. This part of the curve is not the previous results (S2). Therefore, we can compare directly
relevant to the drop volume distribution, but is the most rel- the parameter values, their 95% confidence intervals and the
evant part for the corresponding drop number distribution. objective function value.
The inlet drop volume distribution for case pt7g2, shown in It is clear from Table 4 that the confidence intervals for Cc
Fig. 6(c), has an unusual secondary peak. But it had little influ- and Cb are much smaller when the optimized values for Ve,i ,
ence in the droplet volume size distribution predicted at the i = 1, . . . M were used. Besides, it can be seen that the values
outlet. Fig. 6(d) shows the worst result for which the main peak of Cb and ς agree within their confidence intervals, while the
of the outlet size distribution was not predicted well. Almost Cc values do not, even though they have the same magnitude.
identical results were obtained using the 4-parameter model, This result can be explained as follows. The model assumption
with a non-constant coalescence efficiency. These results are that breakage and coalescence occur in the same region, with
not shown here. volume Ve , about the valve-like element is good for breakage,
Mean diameters are usually needed for equipment design but not so good for coalescence. As high velocity collisions lead
and to couple the population balance solution with CFD sim- to bouncing, the coalescence should occur mostly after the
ulation. They can be calculated using the particle number size valve-like element in a larger region than what was assumed
distribution, dp,q , or by the particle volume size distribution, for breakage. Therefore, the optimization of the Ve,i values for
Dp,q . Since F(v) = vf (v), we have Dp,q = dp+3,q+3 . Table 5 shows all experiments affected more the Cc value than the Cb value.
the errors for the most common mean diameters. Regarding By comparing the values of the objective function, Eq. (37),
the mean diameters based on the particle volume distribu- it could be concluded that the use of the adjusted Ve,i val-
tion, Dpq , it can be concluded that the model is not biased ues produced simulated droplet volume size distributions that
because the values of e are almost zero. Besides, the mean were approximately 20% better than those obtained with the
relative errors are smaller than 15% for all mean diameters. empirical rule used to fix these values. Besides, the mean of
On the other hand, the mean diameters based on the droplet the magnitude of the relative errors between the modeled and
number distribution, dpq , were not well determined except for estimated values of Ve,i was approximately 23%, whereas the
d4,3 = D1,0 . As the parameters have been estimated using the mean of the relative errors was just 8%. This indicates that
values of Nv,k , the model fails to predict the small secondary the empirical rule to fix the Ve,i values has some error, but
2506 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508

d (μm) d (μm)
(a) (b)
101 102 100 101 102
15.0
8.0 inlet (exp) inlet (sim) 8.0 inlet (exp) inlet (sim)
outlet (exp) outlet (sim) outlet (exp) outlet (sim) 15.0

Nv,in × 103 ( − )
Nv,in × 10 ( − )
Nv,out × 10 ( − )

Nv,out × 10 ( − )
6.0 6.0 10.0
pt6g7 pt4g13 10.0

3
3

3
4.0 4.0
5.0
2.0 5.0
2.0

0.0 0.0
0.0 0.0

−17 −15 −13 −11 −19 −17 −15 −13 −11

10 10 10 10 10 10 10 10 10
v (m3) v (m3)

d (μm) d (μm)
(c) 100 101 102 (d) 100 101 102
15.0
8.0 inlet (exp) inlet (sim) inlet (exp) inlet (sim)
outlet (exp) outlet (sim) 8.0 outlet (exp) outlet (sim) 15.0
Nv,out × 10 ( − )

Nv,out × 10 ( − )

Nv,in × 103 ( − )
Nv,in × 10 ( − )
6.0 10.0
pt7g2 6.0 pt2g4 10.0
3

3
3

4.0
4.0
5.0
5.0
2.0
2.0

0.0 0.0 0.0

0.0
−19 −17 −15 −13 −19 −17 −15 −13 −11
10 10 10 10 10 10 10 10 10
3 3
v (m ) v (m )

Fig. 6 – Simulated and experimental droplet volume size distributions using the constant coalescence efficiency model: (a)
best, (b) typical, (c) unusual and (d) worst results.

it is almost unbiased. Besides, no trend could be perceived

between the Ve,i errors and the experimental operational con- d (μm)
ditions. For instance, the mean values of the magnitude of the (a) 101 102
30.0
relative errors between the modeled and estimated values of inlet (exp) outlet (sim) 14.0
25.0 outlet (exp)
Ve,i were 25%, 28% and 16% for the smallest, intermediate and 12.0
largest emulsion flow rates, and the corresponding values of
Nv,out × 10 ( − )

Nv,in × 10 ( − )
20.0 pt4g11 10.0
the mean relative errors were −10%, 19% and 10%, respectively.
3

8.0

3
15.0
6.0
5.6. Results for other models 10.0
4.0
5.0 2.0
Several combinations of coalescence and breakage models
0.0 0.0
were evaluated during this study. More than 40 combina-
−18 −16 −14 −12 −10
tions of models were tested using the coalescence models 10 10 10 10 10
3
of Chesters (1991), the breakage models of Martínez-Bazán v (m )
et al. (1999a) and that derived from Cristini et al. (2003)
work with and without some modifications. These models
d (μm)
were employed with parameters multiplying the breakage (b) 1 2
10 10
and coalescence frequencies, which were estimated using the
inlet (exp) inlet (sim)
same procedure described above for each one of the combi- outlet (exp) outlet (sim) 20.0
15.0
nations. All combinations of models that were tested can be
Nv,in × 103 ( − )
Nv,out × 10 ( − )

found in Mitre (2010). pt4g8 15.0

Most of the combinations of models could not represent 10.0
3

the experimental data nor gave parameters with statistical 10.0

significance. For example, when using the original equations 5.0
of Cristini et al. (2003), Eq. (21), the 95% confidence level of 5.0
Cb,c was almost twice the value of the parameter itself. Bad 0.0
results were also obtained when trying other models for the 0.0
−18 −16 −14 −12 −10
critical capillary number, even when considering the model for 10 10 10 10 10
3
breakage frequency developed in the present work, Eq. (41). v (m )
Regarding the probability distribution of daughter particles,
Fig. 7 – Simulated and experimental droplet volume size
the models of binary breakage with equal size daughters or an
distributions for binary breakage with (a) daughters of
uniform distribution of daughter sizes were also considered as
equal size and (b) uniform distribution of daughter sizes.
well as the models of Martínez-Bazán et al. (1999a), Hsia and
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 2493–2508
Tavlarides (1983) and Hesketh et al. (1991). A ternary breakage
model with uniform distribution of daughter sizes was devel-
oped and analyzed. In all cases, the model parameters were
estimated again.
The results considering the simple models for the prob-
ability distribution of daughter particles assuming binary
breakage are shown in Fig. 7. The employed breakage and
coalescence models are those described in Section 5.3 using
a constant coalescence efficiency. Fig. 7(a) shows a result for
assuming binary breakage with daughters particles of equal
size whereas Fig. 7(b) shows a result for uniform probabil-
ity distribution of daughter droplets. It can be noted that the
simulated distributions did not agree with the experimental
data.
6. Conclusions
This work presented an experimental and theoretical study
on the evolution of droplet size distribution in the flow of
water in oil emulsions through valve-like elements. A sim-
plified population balance model was developed to interpret
the experimental data.
Breakage and coalescence models that could be applied to
the entire range of droplet sizes were proposed. However, the
experimental data had the majority of their droplets in the tur-
bulence dissipation size range and, therefore, only the models
applicable for this size range were used to correlate the droplet
volume size distribution data. The models have 3 or 4 parame-
ters depending if a constant coalescence efficiency is assumed
or not. Thus, caution is recommended for the application of
these models for droplet sizes much larger than the turbulent
dissipation size range.
Statistically significant parameter values could be esti-
mated by local and global optimization methods. The
population balance model using the simplified breakage and
coalescence models generated unbiased results for the mean
droplet diameters based on the particle volume size distribu-
tion that show very good agreement with the experimental
data. The model also gave good results for the particle volume
size distributions at the outlet of the test section.
Acknowledgements
The authors would like to acknowledge the financial sup-
port from PETROBRAS, CNPq (Grants nos. 485817/2007-1,
301672/2008-3, 140883/2006-1, 100253/2011-3) and ESSS.
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