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Dilution of heavy crude oils for pipeline transportation purposes: The

asphaltene instability issue

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 HOLA - 119

Dilution of heavy crude oils for pipeline transportation

purposes: The asphaltene instability issue

Miguel Orea, ChemiConsult, C.A.; Yasmina Mujica, ChemiConsult, C.A.; Anix Diaz, ChemiConsult,
C.A.; Gustavo Lizardo, ChemiConsult, C.A.; Jenny Bruzual, ChemiConsult, C.A.; Gregory
Bazdikian, ChemiConsult, C.A.; Tito Árraga, Pacific E&P.

This paper has been selected for presentation and/or publication in the proceedings for the 2015 Heavy Oil Latin America
Conference & Exhibition. The authors of this material have been cleared by all interested companies/employers/clients to
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HOLA2015 and other relevant industry personnel.

ABSTRACT approach can be used as a tool to ensure fluid quality and

During the last decades the decline of conventional middle
and light crude oil reserves has shifted the petroleum business
to the exploitation of heavy crude oils. However, the high
viscosity, lack of mobility, and poor transportability properties
shown by these fluids make the transport stage a real
challenge for any producer. Dilution of heavy oils with a light
solvent (natural gas condensates, naphtha, kerosene fraction or
a light crude oil) is usually the most common practice for
transporting heavy oils through pipeline systems.
Nevertheless, this procedure perturbs the delicate balance of
asphaltenes, so that segregation and solid phase separation can
take place inside transmission pipelines, storage tanks and
equipment, causing flow obstructions and pressure buildups.
In this research, we present a systematic approach −based on
the well-known Heithaus titration method− to assess the
peptization state of asphaltenes in heavy oil dilutions intended
for pipeline transportation. Changes in asphaltene stability of
the mixtures caused by the storage time were also evaluated.
We show that, in stable heavy oil dilutions, the peptization
state of asphaltenes fluctuates during a period of time before
reaching a plateau. The fluctuation period has been called the
“destabilization window” and it is characterized by the
appearance of a point of minimal stability. The width of the
destabilization window depends on the composition of the oil,
its initial stability, and on the added amount of diluent. This
phenomenon can be of great interest for the oil industry since
it represents a potential fouling risk for pipeline transportation
operations, especially if the mixture has to travel long
distances through pipeline systems of varying elevations. This
pipeline integrity during the delivery and storage of diluted
heavy oils.
KEY WORDS
Heavy oil, dilution, asphaltene stability, Heithaus titration,
peptization, pipeline, transport.
INTRODUCTION
The decline of conventional middle and light crude oil
reserves has shifted the petroleum business to the exploitation
of heavy crude oils (Gordon, 2012). However, the high
viscosity, lack of mobility, and poor transportability properties
of these fluids impose real challenges to any producer,
especially during the transport stages (Saniere et al., 2004,
Gateau et al., 2004).
It is well known that transport through pipelines is the most
economical and safest option for delivering large volumes of
crude oils and petroleum products (Hart, 2014; Gray, 2015).
The fluid to be transported must fulfill several key
specifications to ensure adequate flow rates, maintain product
quality, minimize corrosion and allow safe pipeline operation
(Gray, 2015). Most pipeline systems require kinematic
viscosity values lower than 350 mm2/s at pipeline temperature,
API gravities higher than 18 °API, BS&W lower than 0.5
mass%, and a maximum Reid vapor pressure of 14.5 psi
(99.97 kPa) (Banerjee, D. K., 2012; Gray, 2015). The problem

Heavy Oil Latin America 2015 Full Paper Template Page | 1

for transporting heavy oils through pipelines is that these
fluids display kinematic viscosities ranging from few
thousands to 10000 mm2/s and API gravities lower than 19
°API (Huc, 2011). To meet specifications, producers have to
improve the transportability properties of the heavy oil either
by reducing its viscosity or by reducing the friction between
the fluid and the internal wall of the pipe (Saniere et al., 2004;
Hart, 2014). Of these two alternatives, the first one is the most
common in the heavy oil production industry.
Heavy oil viscosity can be reduced by increasing the fluid’s
temperature, by forming oil-in-water emulsions, or by diluting
the heavy oil with a light solvent (Yaghi & Al-Bemani, 2002;
Hasan et al., 2010). Although these procedures have their own
advantages and disadvantages, most of the time dilution is the
preferred option (Yaghi & Al-Bemani, 2002, Saniere et al.,
2004, Gateau et al., 2004). In this case, a volume fraction of a
light solvent (natural gas condensate, naphtha, kerosene
fraction or a light crude oil) is added to a volume fraction of
the heavy oil up to attain acceptable transportability limits
(Gateau et al., 2004). As there is an exponential relationship
between the viscosity of the resulting mixture and the volume
fraction of diluent, small amounts of the diluent can cause a
marked reduction in the oil’s viscosity (Guevara et al., 1998).
The problem with this procedure is that the delicate
equilibrium of asphaltenes can be substantially affected as to
produce segregation and solid phase separation inside
transmission pipelines, storage tanks and equipment. Thus,
causing obstructions that reduce fluid flow and pressure
buildups that put at risk the integrity of the pipeline
(Shigemoto et al. 2006, Hart, 2014; Speight, 2015).
Despite its relevance, the issue of asphaltene stability in
diluted heavy oils has not received the proper attention. Most
reports are concern with studying changes in viscosity and in
other transportability properties, rather than evaluating the
peptization state of asphaltenes in the resulting mixtures. To
the best of our knowledge, the works of Shigemoto et al.
(2006) and Rahimi et al. (2009) constitute the few reported
attempts to assess the stability of asphaltene in diluted heavy
oils for transportation purposes. Even though, these works do
not address the asphaltene stability issue with the rigorousness
it deserves, they opened a new window for future
investigations.
In this research, we present a systematic approach −based on
the well-known Heithaus titration method− to assess the
peptization state of asphaltenes in heavy oil dilutions intended
for pipeline transportation that were prepared by mixing
natural gas condensates with heavy oils. Changes in
asphaltene stability of the mixtures caused by the storage time
were also evaluated. We show that after solvent addition, the
initial stability of diluted heavy oils fluctuates during a period
of time at which it passes through a point of minimal stability
Heavy Oil Latin America 2015 Full Paper Template
before reaching a plateau. This phenomenon can be of great
interest for the oil industry because it represents a potential
fouling risk for pipeline transportation operations, especially if
the mixture has to travel long distances through the pipeline
systems. This approach can be used as a tool to ensure fluid
quality and pipeline integrity during the delivery and storage
of diluted heavy oils.
THEORY AND DEFINITIONS
In colloidal chemistry, peptization is defined as the
disintegration of aggregated particles in order to form a stable
colloidal suspension in the presence of a stabilizing agent −the
peptizing agent, so that the dispersed particles are prevented
from flocculation (Schramm, 2000). The term “peptization
state of asphaltenes” refers to how well asphaltenes are
dispersed in the maltenes forming a stable colloidal
suspension with a minimal risk of solid phase separation
(Heithaus, 1962). As this particular state depends on both the
chemical nature and the relative distribution of crude oil’s
pseudo-components (i.e. saturate and aromatic hydrocarbons,
resins and asphaltenes (Gaestel et. al., 1971)), it can be altered
by changing oil composition or by varying thermodynamic
conditions such as pressure and temperature (Hirschberg et.
al., 1984; Rivas, 1995).
Changes in crude oil stability are commonly described as
variations in the peptization state of asphaltenes (Hirschberg
et. al., 1984, Pauli, 1996; Pauli & Branthaver, 1998; Wiehe,
2008). Methods intended for evaluating such variations
consist in altering the composition of the crude oil by adding a
solvent (commonly an aromatic solvent) together with the
progressive addition of an asphaltene-precipitant agent (an
alkane hydrocarbon) up to produce the precipitation of solid
asphaltenes.
Heithaus’ titration method is based on these principles
(Heithaus, 1962). The procedure consists in weighing portions
of 1.0, 2.0, and 3.0 grams (with approximation of 0.1 mg) of
the sample to be tested and mixing them with 2.0 mL of an
aromatic solvent (usually toluene or o-xylene) to total
dissolution. Keeping the mixture at constant temperature
(usually 25.0 ± 0.1 °C) and at constant stirring, the precipitant
agent (n-heptane or iso-octane) is added dropwise at a
controlled addition speed while the mixture is constantly
stirred. Flocculation onset is detected by inspecting the
mixture automatically or manually. Automatic detection is
performed by using light-scattering detectors (Pauli, 1996;
Pauli & Branthaver, 1998), while manual detection is carried
out by observing a drop of the solution through an optical
microscope (Buckley et al., 2007) or by transferring the drop
to a filter paper to observe the formation of a characteristic
double-ring spot (Heithaus, 1962; Pauli, 1996; Pauli &
Branthaver, 1998).
Page | 2
The mass (W) of the crude oil sample, the volume of solvent
added (Vs) and the volume of titrant spent to reach the
flocculation onset (VT) are used to calculate the flocculation
ratio FR and the concentration C, according to the following
equations (Heithaus, 1962; Pauli, 1996):
[1]
[2]
The graphical representation of FR as a function of C yields a
straight line that intersects the ordinate axis at the point FRmax,
and the abscissa axis at the point Cmin (Figure 1). FRmax
represents the solvent and titrant ratio at which the oil is
soluble in all the concentrations, while the Cmin corresponds to
the minimum amount of oil that must be present in a specific
titrant concentration to keep its complete solubility (Heithaus,
1962).
Figure 1 Graphical representation of FR and C obtained after
the Heithaus titration of a hypothetical crude oil.
Heithaus parameters Pa, Po, and P can be calculated from FR
and Cmin as follow:
[3]
[4]
[5]
The parameter Pa measures the tendency of asphaltenes to
remain as a stable dispersion in the maltene fraction. This
parameter is directly related to the chemical nature of
asphaltenes, their structures and their tendency to form
aggregates (Heithaus, 1962). Values of Pa range between 0
and 1. Values close to 1 mean that asphaltenes are easily
dispersed in the maltenic media, with few possibilities to
flocculate (Heithaus, 1962; Pauli & Branthaver, 1998).
Heavy Oil Latin America 2015 Full Paper Template
Likewise, the parameter Po measures the ability of the maltene
fraction to disperse asphaltenes. It is referred to as the
“peptizing power” of the maltenes (Heithaus, 1962; Pauli &
Branthaver, 1998) and is intimately related to the distribution
of maltenic pseudo-components, i.e., saturates, aromatics, and
resins. As chemical features of these family compounds
govern the modes of interaction with asphaltenes (Stapf et al.,
2014), they affect Po values. High values of Po indicate that
maltenes are good at keeping asphaltenes properly dispersed
in the oily medium whereas low values mean a poor peptizing
power (Pauli & Branthaver, 1998).
The term P refers to the overall peptizability of the system
(Heithaus, 1962; Pauli & Branthaver, 1998). It measures the
combined effect of the peptizing power of maltenes and the
peptizability of asphaltenes to form a stable dispersed system.
P can range from values very close to cero up to 10; however,
the most accepted criteria is that samples with P values lower
than 1 are defined as unstable, whereas those with values
higher than 2 are considered highly stable. Samples with P
values between these limits are considered of moderate
stability (Heithaus, 1962, Tojima et al., 1998; Pauli &
Branthaver, 1999; Schabron & Pauli, 1999).
The Heithaus titration method was initially develop to
evaluate the peptization state of asphaltenes in asphalt
samples. Then it was extended for testing materials such as
fuel oils and oil residua. The method is not intended for
assessing asphaltene stability in heavy oils diluted with natural
gas condensates, naphtha or with a kerosene fraction.
However, this constraint has not been a limitation, since
recently Rahimi et al. (2009) successfully adapted the method
for testing mixtures obtained after diluting heavy oils and
bitumen with natural gas condensates (NGC) and synthetic
solvents. Due to its simplicity and the success claimed by
Rahimi et al. (2009), we have also adopted the Heithaus
titration method to assess the peptization state of asphaltenes
in dilutions of heavy oils intended for pipeline transportation.
DATA AND OBSERVATIONS
The Heithaus titration procedure was performed by using o-
xylene and iso-octane (J. T. Baker, HPLC grade) as the
solvent-titrant pair. 2.000 ± 0.002 mL of o-xylene were added
to 1.0; 2.0 and 3.0 g (approx. of 0.1 mg) of the sample. The
mixture was equilibrated at 25.0 ± 0.1 °C for 10 minutes under
constant stirring (20 rpm), and then, the titrant was added at
0.100 mL/min. The flocculation onset point was detected
manually after observing a drop of the mixture through an
optical microscope (Carl Zeiss, model Axio Lab A1) at a
magnification of 100× (Figure 2).
Page | 3
 same way, but at concentrations of 14.0, 18.0, 22.0, 28.0, and
35.0 vol% NGC. COL1 dilutions were storage in 30 mL vials
hermetically sealed and kept in the dark for 30 days at 32 °C.
Asphaltene stability was assessed at intervals of 5 days. In the
case of COL2, dilutions were storage at the same conditions,
but only for 28 days. In this case, asphaltene stability was
assessed at 3-day intervals during the first 7 days, and then at
Figure 2. Detection of the asphaltenes’ flocculation onset by 7-day intervals.
optical microscopy (100× magnification). (A) Before
flocculation onset. (B) At the flocculation onset. (C) After the
flocculation onset. Table 2. Properties of the Natural Gas Condensates used as
diluent.
Two Colombian heavy oils (COL1 and COL2) from Los
Llanos Basin were used to prepare the dilutions. Table 1 Parameter Value
summarizes their composition and some rheological properties
Paraffins 36.136 wt%
of interest. Stability indicators such as resins to asphaltenes
ratio (R/A), the Gaestel’s colloidal instability index CII Iso-paraffins 45.295 mass%
(Gaestel et al., 1971), and the Heithaus’ stability parameters Olefins 0.029 mass%
(FRmax; Pa, Po, and P) are also included in this table. Naphtenes 15.390 mass%
Aromatics 3.114 mass%
Table 1. Properties of Colombian heavy oils used in this
Unidentified 0.036 mass%
research.
API Gravity 80.4 °API
COL1 COL2 Reid vapor pressure (RVP) 91.0 kPa
Saturates 38.6 19.1 Kinematic viscosity (mm2/s)
50 °F 0.480
Aromatics 30.3 41.9
68 °F 0.440
Resins 16.7 29.5 86 °F 0.409
Asphaltenes 14.4 9.5
Acid number 0.45 1.230
SARA fractionation of the heavy oils was performed as
Sulfur (mass %) 1.34 2.1
follows: Asphaltenes were precipitated by n-heptane excess
API Gravity (° API) 13.3 10.8
(40:1) following ASTM D3279 protocol. Maltenes were
Reid vapor pressure, kPa 0 0
recovered and further fractionated by liquid chromatography
in a glass column packed with silica. Saturated fraction was
Kinematic Viscosity (mm2/s)
eluted with n-hexane. Aromatics were eluted with a solvent
86 °F 4706 8508
mixture composed of n-hexane and toluene 70/30 v:v, and
122 °F 708.7 2955
resins with a mixture of dichloromethane/methanol 90/10 v:v.
140 °F 303.3 276.3 All fractions were quantified gravimetrically.

R/A 1.14 3.10

The distribution of paraffins, olefins, naphtenes and aromatics
(PONA) in the NGC was determined in accordance to ASTM
CII (*) 1.13 0,40
D6729. SARA distributions of dilutions were calculated from
FRmáx. 0.53 0.31 the PONA and SARA distributions considering the mass ratio
Pa 0.47 0.69 of mixing NGC with the heavy oils.
Po 0.89 0.82
Acid number, sulfur content, API gravity, Reid vapor pressure
PHeithaus 1.68 2.65 and kinematic viscosity at 50, 68, 70, 86, 122, and 140 °F
(*) CII =(Saturates + Asphaltenes)/(Resins + Aromatics) (10.0, 20.0, 21.1, 30.0, 50.0, and 60.0 °C respectively) were
determined in accordance to ASTM D664, ASTM D7691,
ASTM D 1298, ASTM D323, and ASTM D445 respectively.
Table 2 shows the composition and rheological properties of
the natural gas condensate (NGC) sample used as solvent.
Dilutions of the heavy oil COL1 were prepared volumetrically
at concentrations of 15, 17.5, 20.0, 22.5, 25.0, and 30.0 vol%
NGC. Dilutions of the heavy oil COL2 were prepared in the

Heavy Oil Latin America 2015 Full Paper Template Page | 4

RESULTS Table 4. Properties of COL2 heavy oil dilutions

The rheological and compositional properties of dilutions Dilutions

obtained from COL1 and COL2 are listed in Tables 3 and 4 Property
1 2 3 4 5
respectively. The resins to asphaltenes (R/A) ratio, the
Gaestel’s colloidal instability index (CII) and the Heithaus’ NGC vol% 14.0 18.0 22.0 28.0 35.0
parameters are also included.
RVP (kPa) 29.5 35.75 40.5 43.5 46.75

As shown in Table3, all dilutions made with COL1 are API 16.6 19.0 20.7 23.4 27.2
eligible to be transported through pipelines at an average Kinematic
temperature of 86 °F (30 °C). They show API gravities higher viscosity
(mm2/s)
than 18 °API, kinematic viscosities lower than 350 mm2/s,
RVP values lower than 99.97 kPa, and acceptable asphaltene 70 ºF 1168.1 581.8 278.5 87.81 29.29
stabilities (Heithaus P values higher than 1.0). For economy 86 ºF 623.5 319.8 169.3 63.78 24.78
reasons, only those dilutions prepared with the minor amounts 100 ºF 381.7 200.8 114.7 49.42 21.62
of diluent (dilutions 1, 2 and 3) are the best candidates for
pipeline transportation. In the case of COL2, only dilutions 2 122 ºF 198.7 105.3 66.74 34.43 17.74
and 3 appear to be the most appropriate (Table 4).
S mass% 26.71 29.04 31.39 35.01 39.48
Table 3. Properties of COL1 heavy oil dilutions
A mass% 38.10 36.94 35.77 33.96 31.73
Dilutions R mass% 26.62 25.73 24.84 23.47 21.78
Property A mass%
1 2 3 4 5 6 8.57 8.29 8.00 7.56 7.01
R/A 3.1 3.1 3.1 3.1 3.1
NGC vol% 15.0 17.5 20.0 22.5 25.0 30.0
CII (*) 0.55 0.60 0.65 0.74 0.87
RVP (kPa) 29.5 35.75 40.5 43.5 46.75 52.5
FRmax 0.33 0.34 0.34 0.34 0.32
API 19.6 20.6 21.8 24.3 25.8 29.4
Pa 0.67 0.66 0.66 0.66 0.68
Kinematic
viscosity Po 0.80 0.78 0.78 0.76 0.64
(mm2/s)
P 2.44 2.32 2.28 2.23 2.02
70 ºF 432.4 320.0 203.0 102.0 69.5 31.8
(*) CII =(Saturates + Asphaltenes)/(Resins + Aromatics)
86 ºF 248.2 180.6 121.0 66.4 46.3 22.8
100 ºF 160.2 115.4 80.8 47.4 33.6 17.5
122 ºF 89.8 64.2 50.1 31.3 18.4 12.6
Tables 5 and 6 list the results of the Heithaus parameters
(FRmax, Pa, Po, and P) obtained after monitoring the dilutions
during 30 days of storage. The patterns described by the
S mass% 44.8 45.88 47.03 48.24 49.37 51.82 parameter P over time are of special interest for this study,
A mass% 27.41 26.9 26.36 25.8 25.27 24.13
since they represent the overall stability of the samples. Such
patterns are further discussed in the following section.
R mass% 14.93 14.62 14.29 13.94 13.62 12.92
A mass% 12.87 12.6 12.32 12.02 11.74 11.13
R/A 1.16 1.16 1.16 1.16 1.16 1.16 DISCUSSION
CII (*) 1.36 1.41 1.46 1.52 1.57 1.70 The main effect of adding a light solvent to a heavy crude oil
FRmax 0.56 0.57 0.59 0.57 0.56 0.55 is the viscosity reduction produced on the later. Guevara et al.
(1998) have claimed that the reduction of the heavy oil’s
Pa 0.44 0.43 0.42 0.43 0.44 0.45
viscosity is exponential at low dilution ratios and then it
Po 0.94 0.93 0.94 0.89 0.84 0.81 reaches a linear behavior at higher diluent concentrations.
P 1.68 1.64 1.61 1.56 1.50 1.47 Pierre et al. (2004) have shown that this viscosity behavior
(*) CII =(Saturates + Asphaltenes)/(Resins + Aromatics) is intimately related to the decrease of the asphaltene
concentration in the oil, and that it obeys to a transition
from a non-Newtonian (viscoelastic) fluid to a Newtonian
fluid.

Heavy Oil Latin America 2015 Full Paper Template Page | 5

Table 5. Assessment of Heithaus stability parameters over Table 6. Assessment of Heithaus stability parameters over
storage time of dilutions prepared by mixing COL1 heavy oil storage time of dilutions prepared by mixing COL2 heavy oil
with increasing amounts of a natural gas condensate (NGC) with increasing amounts of a natural gas condensate (NGC)
sample. sample.

NGC Storage Time (days) NGC Storage Time (days)

(Vol%) 0 5 10 15 20 25 30 (Vol%)
0 3 5 7 14 21 28
15.0 FRmax 0.56 0.55 0.53 0.53 0.56 0.55 0.55 14.0 FRmax 0.33 0.33 0.34 0.33 0.33 0.33 0.36
Pa 0.44 0.45 0.47 0.47 0.44 0.45 0.45 Pa 0.67 0.67 0.66 0.67 0.67 0.67 0.64
Po 0.94 0.88 0.81 0.82 0.85 0.86 0.87 Po 0.80 0.82 0.84 0.82 0.82 0.83 0.90
P 1.68 1.6 1.53 1.54 1.55 1.55 1.57 P 2.44 2.45 2.45 2.47 2.48 2.49 2.50

17.5 FRmax 0.57 0.53 0.52 0.53 0.53 0.53 0.54 18.0 FRmax 0.34 0.34 0.35 0.36 0.35 0.34 0.36
Pa 0.43 0.48 0.48 0.47 0.47 0.47 0.46 Pa 0.66 0.66 0.65 0.64 0.65 0.66 0.64
Po 0.93 0.79 0.79 0.8 0.81 0.81 0.83 Po 0.78 0.82 0.83 0.88 0.83 0.83 0.87
P 1.64 1.50 1.50 1.51 1.52 1.51 1.53 P 2.32 2.37 2.39 2.41 2.40 2.40 2.40

20.0 FRmax 0.59 0.56 0.54 0.56 0.56 0.56 0.57 22.0 FRmax 0.34 0.34 0.35 0.37 0.35 0.33 0.34
Pa 0.42 0.44 0.46 0.44 0.44 0.44 0.43 Pa 0.66 0.66 0.65 0.63 0.65 0.67 0.66
Po 0.94 0.84 0.85 0.87 0.88 0.88 0.9 Po 0.78 0.78 0.8 0.86 0.81 0.76 0.77
P 1.61 1.5 1.56 1.56 1.56 1.58 1.6 P 2.28 2.29 2.30 2.32 2.31 2.27 2.24

22.5 FRmax 0.57 0.54 0.53 0.53 0.53 0.55 0.56 28.0 FRmax 0.34 0.34 0.34 0.34 0.34 0.34 0.35
Pa 0.43 0.46 0.47 0.47 0.47 0.45 0.44 Pa 0.66 0.66 0.66 0.66 0.66 0.66 0.65
Po 0.89 0.8 0.79 0.79 0.79 0.84 0.84 Po 0.76 0.73 0.74 0.76 0.76 0.74 0.74
P 1.56 1.48 1.49 1.49 1.49 1.52 1.50 P 2.23 2.14 2.15 2.21 2.21 2.18 2.11

25.0 FRmax 0.56 0.55 0.54 0.56 0.56 0.56 0.56 35.0 FRmax 0.32 0.33 0.36 0.36 0.36 0.33 0.33
Pa 0.44 0.45 0.46 0.44 0.44 0.44 0.44 Pa 0.68 0.67 0.64 0.64 0.64 0.67 0.67
Po 0.84 0.81 0.79 0.82 0.85 0.84 0.84 Po 0.64 0.67 0.72 0.74 0.74 0.67 0.67
P 1.50 1.47 1.46 1.48 1.51 1.50 1.50 2.02 2.02 1.97 2.05 2.05 2.02 2.02
P

30.0 FRmax 0.55 0.53 0.53 0.53 0.55 0.55 0.56

Pa 0.45 0.47 0.47 0.47 0.45 0.45 0.44

Po 0.81 0.74 0.75 0.77 0.82 0.81 0.83 When a light solvent with a high aliphatic character is
P 1.47 1.4 1.41 1.45 1.48 1.47 1.48 added to the viscous heavy oil, it produces the partial
destruction of the viscoelastic network, which in turn is
reflected as a reduction of the viscosity. If conditions are
According to Akbarzadeh et al., (2004), asphaltenes exist in given, asphaltene particles try to reestablish equilibrium by
heavy crude oils as aggregated particles that attract each other restoring the viscoelastic network; otherwise they
to form a viscoelastic network. This network is the responsible flocculate and precipitate (Akbarzadeh et al., 2004). This
for the high viscosity of the oil and it is kept stabilized by the process takes place after every addition of the diluent, so
action of surrounding resins and aromatic hydrocarbons. that the non-Newtonian-to-Newtonian transition occurs in a
progressive way. If dilution is carried out in an extent
The non-Newtonian-to-Newtonian transition has been related beyond the flocculation onset, the restoration process is
by Pierre et al. (2004) to the perturbing effects that the light completely inhibited and asphaltene precipitation takes
diluent produces on the asphaltenic viscoelastic network. place (Akbarzadeh et al., 2004).

Heavy Oil Latin America 2015 Full Paper Template Page | 6

Crude oils COL1 and COL2 derive from the same field but
they are substantially different as can be seen in Table 1.
Crude COL2 is heavier than COL1. It has higher contents
of aromatics and resins and lower contents of saturate
compounds and asphaltenes compared to COL1. These
SARA patterns obviously affect the overall stability of
asphaltenes in each sample, which in turn is reflected on
the corresponding CII and Heithaus P values (Table 1). For
these reasons, more stable dilutions are expected from
COL2 crude oil.
Initial stability of heavy oil dilutions. Figure 3 confirms
that COL2 produces more stable dilutions in terms of the
peptization state of asphaltenes. The characteristic
reduction of the initial Heithaus P parameter as a
consequence of the addition of the solvent is also observed
in Figure 3. Even though the Heithaus P parameter
decreases, it is noticed that none of the prepared dilution
crossed the limiting value. As a result, all mixtures were
declared stable at the moment of preparation.
Figure 3. Initial Heithaus P parameter of dilutions prepared
from COL1 and COL2 crude oils and natural gas condensates
(NGC).
Figure 4 depicts the dependence of kinematic viscosity at 86
°F (30 °C) with the added amount of NGC. The figures
signaling experimental points correspond to the concentration
of asphaltenes in the respective mixture. It is observed that
kinematic viscosity decays exponentially in both sets of
dilutions until reaching a point from which it behaves linearly.
This point, according to Pierre et al. (2004), represents the
onset of the non-Newtonian-to-Newtonian fluid transition. It
is interesting to note that the transition point appears in COL1
at a lower diluent concentration in comparison to the case of
COL2. In other words, COL1 reaches a Newtonian behavior
faster than COL2 when it is diluted. This observation strongly
suggests that the asphaltene viscoelastic network existing in
COL1 is more prone to destabilization compared to the one
existing in COL2. Even though this result is not surprising
(given the difference in Heithaus P values between both crude
oils (Table 1)); it calls the attention because it is a reflect of
Heavy Oil Latin America 2015 Full Paper Template
the asphaltene stabilization-destabilization dynamics that
might exist in complex colloidal systems such as the ones
represented by diluted heavy crude oils.
It is important to keep in mind that the Heithaus method −as
any other titration method intended for evaluating asphaltene
stability/compatibility− only provides instantaneous informa-
tion about the peptization state of asphaltenes, giving no clues
about the entire process of perturbation-restoration undergone
by the viscoelastic network. In this regard, it is important to
know how the restoration process is carried out and how long
it takes to be completed.
Figure 4. Kinematic viscosity at 86 °F (30°C) of diluted
heavy oils as a function of diluent concentration. The figures
signaling experimental data points correspond to the
concentration of asphaltenes in the respective mixture.
.
Effects of storage time on the peptization state of
asphaltenes in heavy oil dilutions. A practical option to get
some insights about the perturbation-restoration process of the
asphaltene viscoelastic network consists in evaluating the
peptization state of asphaltenes at equal time intervals during a
large time-spam. In this regard, Heithaus titration method
resulted appropriate, since it provides a complete picture of
asphaltene stability conditions at a given time. Figure 5 shows
the evolution of the Heithaus P parameter in COL1 and COL2
dilutions with storage time.
Page | 7

Figure 5. Evolution of the Heithaus P parameter in COL1 and
COL2 dilutions with storage time.
Trends clearly indicate that the entire set of COL1 dilutions
transit through a minimum of the Heithaus P parameter. In the
case of COL2, only the most diluted mixtures (28.0 and 35.0
vol% NGC) showed a similar trend. It is also observed in
Figure 5 that, after few days, the Heithaus P parameter reaches
a plateau. The time elapsed from the preparation of dilutions
until the appearance of the minimum can be interpreted as the
duration time of the perturbing effects caused by the diluent
on the viscoelastic network. Likewise, the time measured from
the minimum point to the moment at which the curves reach
the plateau can be understood as the time required for
individual asphaltene particles to restore the network. The
fluctuation patterns describe time-windows in which the
peptization state of asphaltenes decreases before it reaches
equilibrium. We have named these time-windows as the
“destabilization windows” and their limits vary from 0 to10
days in COL1 dilutions with diluent concentrations ranging
from 15.0 to 22.5 vol% and from 0 to 15 days in mixtures with
more than 25.0 vol% of diluent (Figure 5). In the case of
COL2, the destabilization window is only observed in
dilutions with more than 28.0 vol% of diluent during the first
seven days of storage.
Apparently, the faster dilutions cross the non-Newtonian-to-
Newtonian boundary, the wider the destabilization window
Heavy Oil Latin America 2015 Full Paper Template
becomes. That is, the process undergone by the viscoelastic
network takes longer times in less stable mixtures.
The evolution of the kinematic viscosity with the storage time
is also consistent with the behavior of the Heithaus P
parameter. The kinematic viscosity of COL1 diluted with 20.0
vol% NGC (dilution # 3) was measured in the fluids collected
near the top and near the bottom of the sample container after
5, 15, and 30 days of being prepared (Figure 6). Results
clearly showed a great difference between top and bottom
viscosities after 5 days of storage and non-significant
differences after 30 days. The occurrence of the highest
viscosity difference coincided with the appearance of the
minimum point in the curve of the Heithaus P parameter
(Figure 5), whereas the observation of similar viscosities at
day 30 implies that the system reached an equilibrium
condition.
300
Kinematic viscosity mm2/s Bottom
250
200
Top
150
100
0 5 10 15 20 25 30
Storage time (days)
Figure 6. Evolution of the kinematic viscosity at 86 °F of
crude oil COL1 diluted with 20.0 vol% of NGC.
Measurements were made on the fluid near the top and near
the bottom of the sample container after 5, 15 and 30 days of
dilution preparation.
All, the information collected in this research indicates that
both the perturbation and the restoration of the viscoelastic
network is a kinetic phenomenon. Maqbool et al., (2009)
have obtained interesting results, in this regard, by monitoring
the stability of mixtures prepared by diluting heavy oils with
solvents composed of toluene and n-heptane (heptol). By
increasing the amounts of n-heptane in the heptol solvent,
these authors found that heavy oil dilutions that appeared to be
stable at the moment of preparation showed an evident
formation of asphaltene precipitates after a long time of
storage. The time at which asphaltene precipitation occurred
(the onset time) varied from few minutes to several months,
depending upon the concentration of n-heptane in the solvent
(Maqbool et al., 2009).
It is important to emphasize that we did not observed the
formation of asphaltenic precipitates in any of the evaluated
Page | 8
mixtures, even after 30 days of storage. The corresponding
Heithaus P values were always greater than the limit value (P
> 1) despite the observed fluctuations of the peptization state
of asphaltenes. In our personal opinion, and putting the
results of Maqbool et al. in the context described by our
research, precipitation of asphaltenes occurred in heptol
solvents because the minimum that appears in the curve of the
Heithaus P parameter vs. storage time may have crossed the
limit value of stability. In other words, during the
development of the destabilization window, the Heithaus P
parameter may have reached a value lower than 1.0 (P ≤ 1), so
that the restoration of the viscoelastic network may have been
completely inhibited in these mixtures. This means that the
extent of the perturbation provoked by the addition of a
solvent can lead the destabilization window towards the
restoration of the viscoelastic network (the establishment of a
new stability condition) or towards its total collapse
(asphaltene precipitation).
The interpretation of our findings together with those reported
by Maqbool et al. indicate that the appearance of asphaltene
precipitates in heavy oil dilutions that were declared stable at
an initial stage, depends on both the dynamics associated to
the development of the destabilization window and the
ultimate minimal value reached by the Heithaus P parameter
in such window. Even though oil and diluent compositions, as
well as the structural features of saturates, aromatics, resins,
and asphaltenes are also considered key factors, further
attempts are required to fully understand this phenomenon.
From a strategic point of view, the kinetic phenomenon that
controls fluctuations of the peptization state of asphaltenes in
stable heavy oil dilutions represents a potential risk of fouling
during pipeline transportation (Ramirez-Jaramillo et al.,
2006). The situation could get worse if the fluid has to travel
long distances over terrains of complex topography where
some segments of the pipeline have to change their inclination
due to the presence of steep slopes.
Changes in inclination from a horizontal to a vertical or almost
vertical position produces pressure drops and changes in the
flow pattern of the fluid transmitted by the pipeline (Guo et
al., 2014). In heavy oils diluted with natural gas condensates
there is a high probability of developing a slug flow pattern if
lighter components of the diluent leave the liquid phase in the
form of big gas bubbles (Guo et al., 2014). The expansion of
these light components produces variations in the average
solubility parameter of the liquid phase and the concomitant
precipitation of asphaltenes (Rivas, 1995). If the fluid is
delivered during the development of the destabilization
window, the perturbation produced by this situation might
contribute to inhibit the restoration of the viscoelastic
network, so the scenario could turn from one risky to one
catastrophic.
Heavy Oil Latin America 2015 Full Paper Template
This means that declaring stable a heavy oil dilution that
fulfilled rheological specifications for pipeline transportation
is not a guarantee to ensure a safety operation if the dynamics
of the peptization state of asphaltenes has not been properly
assessed. Any decision based on incomplete information may
lead to disastrous outcomes. It is important to keep in mind
that the removal of asphaltenic deposits adds costs to the
economic balance of the oil transport operation. The ability to
predict them and prevent their formation should be preferred
to their cleanup after they have already formed.
CONCLUSION
Fluctuations of the peptization state of asphaltenes have been
detected in stable dilution prepared by mixing natural with gas
condensates with heavy crude oils. Such fluctuations occur in
a time-spam of about 5-15 days counted from the preparation
of the mixtures. The limits of the time-spam define a
destabilization window in the curve of the Heithaus P
parameter vs. storage time, which is characterized by the
appearance of a local minimum of stability. The
destabilization window comprises the time required by the
diluent’s components to disturb the structure of the
asphaltenic viscoelastic network and the time required by the
asphaltene particles to restore the network. These findings can
contribute to improve predictive models intended for
transportation of diluted heavy oils.
ACKNOWLEDGMENT
We thank E. Diaz, O. Diaz, N. Torres, and M. Lattanzio, for
the analytical support provided. The authors also thank Pacific
Rubiales Energy− Colombia for allowing publication of the
present work.
NOMENCLATURE
BS&W Bottom sediments and water.
CII Gaestel’s Colloidal Instability Index, adimensional
Cmin Minimum concentration of oil, determined by
Heithaus titration, that can be present in a specific
titrant concentration without forming asphaltene
precipitates, g/mL
FRmax Solvent-titrant ratio, determined by Heithaus
titration, at which the oil is soluble in all its
concentrations.
NGC Natural gas condensates
P Overall peptizability parameter determined by
Heithaus titration
Pa Asphaltene peptizability parameter determined by
Heithaus titration
Po Peptizing power of the maltenes determined by
Heithaus titration
PONA Paraffins, Olefins, Naphtenes, and Aromatic
compounds, wt %
R/A Resins to asphaltenes ratio
Page | 9
RVP Reid vapor pressure, kPa.
SARA Saturates, Aromatics, Resins, and Asphaltenes, wt %
VS Solvent volume required to dissolve an amount of
sample during Heithaus titration procedure, mL.
VT Volume of titrant required to induce asphaltene
flocculation during Heithaus titration procedure, mL
W Mass of sample, g.
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