Copyright 2001, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 2001 SPE Annual Technical Conference and
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Abstract
The potential for hydrocarbon solid formation and deposition
adversely affecting flow assurance in deepwater production
systems is a key risk factor in assessing deepwater
developments. To reduce this risk, a systematic approach to
defining and understanding the thermodynamic and
hydrodynamic factors impacting flow assurance is required.
The development of experimental and simulation techniques
to provide this information are a current focus of attention in
the reservoir fluid phase behavior community. This paper
provides a case study of the various aspects of a state of the art
laboratory and simulation assessment for a Gulf of Mexico
reservoir crude. The case study illustrates the application of a
systematic approach to characterization of the crude and the
impact of this knowledge on potential production and flow
assurance strategies.
Introduction
Deepwater exploration and development in the Gulf of
Mexico and other deepwater offshore areas around the world
have become key activities for the majority of oil and gas
exploration and production companies. Development
activities in the deepwater face significant challenges.
1
Of
particular concern, are the effects of produced fluid
hydrocarbon solids (i.e. asphaltene, wax, and hydrate) and
their potential to disrupt production due to deposition in the
production system. It is noted that the deposition of inorganic
solids arising from the aqueous phase (i.e. scale) also poses a
serious threat to flow assurance. Scaling issues are beyond the
scope of this paper and have not been considered in this work.
As outlined schematically in Figure 1, hydrocarbon solids
have the potential to deposit anywhere from the near wellbore
Figure 1: Areas of potential solids problems
and perforations, to the wellbore, topside surface facilities and
pipelines. Viewing this in another way, Figure 2
schematically demonstrates the superimposed thermodynamic
phase boundaries for the potential hydrocarbon solid
phenomenon. Also shown is the potential production P-T
pathway that would obviously be dependent on the specific
hydrodynamic and heat transfer characteristics of a given
SPE 71546
A Systematic Approach in Deepwater Flow Assurance Fluid Characterization
A.K.M. Jamaluddin, SPE, J. Nighswander, SPE, N. Joshi, SPE; Oilphase, A Schlumberger Company
2 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
completion and facilities system. As can be seen, the pressure
and temperature PT pathway of the production circuit can
intersect one or all three elements of hydrocarbon solid
formation, and consequently result in potential flow assurance
problems wherever these boundaries are crossed. It is noted
that crossing the thermodynamic conditions for the formation
of hydrocarbon solids does not necessarily imply that a flow
assurance problem will be encountered. In other words, if
hydrocarbon solids form but do not deposit, they are not a
problem. Current techniques to assess the deposition tendancy
of the hydrocarbon solids and the factors affecting the
deposition of solids are not currently well understood and are
Figure 2: Schematic representation of the
thermodynamic conditions of the flow assurance
elements
not addressed in this work. Until such capabilities are
available, experimental and simulation work to define the
phase boundaries and production P-T pathway for real fluids
are the key to providing an understanding of the potential for
hydrocarbon solid deposition and the subsequent impact of
these solids on a given fluid/production system.
As background, a brief discussion of the individual phase
behavior of the various hydrocarbon solid elements are
presented below.
Asphaltenes are defined as high molecular weight aromatic
organic substances that are soluble in toluene but are
precipitated by alkanes (n-heptane/n-pentane). Generally,
asphaltenes tend to remain in solution or in colloidal
suspension under reservoir temperature and pressure
conditions. They may start to precipitate once the stability of
the colloidal suspension is destabilized, which is caused by the
changes in temperature and/or pressure during primary
depletion.
2
On the other hand, asphaltenes have been reported
to become unstable as a result of fluid blending (co-mingling)
of fluid streams
3
as well as by gas injection during Improved
Oil Recovery (IOR) operations.
4-7
It is important to note that
the asphaltenes produced by pressure drop in a reservoir
production system are different than the asphaltenes produced
by solubility criteria as defined above. The reservoir
asphaltene includes some additional components such as
resins.
Waxes are also high molecular weight, highly saturated
organic substances. The formation of wax crystals depends
significantly on temperature change. Pressure and composition
also affect their formation but not to a significant extent.
8
Gas hydrates are defined as the Clathrate inclusion
compounds. They are formed by the contact of hydrate
forming gases (primarily methane, ethane, propane, carbon
dioxide, and hydrogen sulfide) and liquid water at low
temperature (0-40
o
C) and high-pressure conditions
9
. Two
types of gas hydrates are classified in the literature and they
are Structure I and Structure II.
10
Each hydrate building block
has a central cavity to encapsulate molecules of hydrate
forming gases.
Hydrocarbon Solid Characterization Process Case
Study
As noted in the introduction, a systematic approach to defining
the thermodynamic and hydrodynamic characteristics of a
particular development is essential to assess the risk of
hydrocarbon solid formation and deposition. This approach
generally consists of the following steps;
1. Fluid Sampling and Transport
2. Fluid Compositional Characterization
3. Preliminary Screening for Solids
4. Experimental Measurements
a. Asphaltene
b. Wax
c. Hydrate
5. Thermodynamic Model Tuning and Adjustment
6. Hydrodynamic Modeling
7. Conclusions
In the following, a case study is presented where this process
was followed for a Gulf of Mexico reservoir fluid. The
equipment and procedures for each of the key steps are
described along with the results obtained for the case study.
Fluid Sampling and Transport. The first step in assessing
the potential hydrocarbon solid formation characteristics of a
reservoir fluid involves the collection of a suitable reservoir
fluid sample. It is essential to take appropriate care to insure
that no irreversible phase changes occur during the sample
collection, sample transfer (both in the field and the lab), and
sample transportation processes. This is important because of
the uncertainties in the reversibility of asphaltene
precipitation. To insure valid samples for asphaltene
measurements without having to face the reversibility issues, a
single-phase reservoir sample is highly desirable.
SPE 71546 A SYSTEMATIC APPROACH IN DEEPWATER FLOW ASSURANCE FLUID CHARACTERIZATION 3
During open hole Modular Formation Dynamics Testing
(MDT), Single-Phase Multi-Chamber (SPMC) module is
normally used in collecting single-phase reservoir fluid
samples for asphaltene analysis. In the SPMC module, the
fluid pressure is maintained above the reservoir pressure while
the sample is retrieved to the surface by having a pre-charge
nitrogen cushion in the sample chamber. Thus, making the
SPMC suitable for asphaltene precipitation testing. Details of
the equipment and procedural issues surrounding these
operations can be found in reference 11. In the MDT module
other conventional chambers that are not pressure
compensated are also used to collect the reservoir fluid
samples. In these conventional sample modules, fluid may
undergo phase change phenomenon, and hence, render the
sample invalid for asphaltene analysis.
For the present case study, the SPMC samples were not
available, and hence, a sub-sample from the one-gallon
chamber was used.
Fluid Compositional Characterization. Upon arrival of fluid
samples in the laboratory, the sample chambers are first
validated by determining the opening pressure. Subsequently,
a sample is chosen for study and the sample is heated to the
reservoir temperature using a custom made heating jacket. The
sample bottle is then placed into a rocking stand and agitated
for a minimum of 5 days to insure homogenization of the
reservoir fluid. After stabilization, a small portion of the
single-phase reservoir fluid is subjected to a single stage flash
experiment to determine the Gas-Oil-Ratio (GOR), C36+
composition, density at sample pressure and temperature, and
stock oil density (API gravity). The flash is conducted from a
pressure slightly above the bubble point at reservoir
temperature down to ambient conditions. The resulting mass
and volumes of gas and liquid is recorded and the flashed
fluids (gas and liquid) are then analyzed using gas
chromatography
13
. The live oil composition is then calculated
based on the measured gas and liquid compositions and GOR
values. Finally, if the samples were obtained by open-hole
sampling (as was the case in this work), the level of OBM
contamination in the stock tank oil needs to be determined.
This is completed by a subtraction method taking into account
the OBM filtrate composition and the contaminated stock tank
oil composition
14
.
In addition to the grouped carbon number analysis
provided for above, a portion of stock tank liquid is also
prepared for Saturate-Aromatic-Resin(Polars)-Asphaltene
(SAR(P)A) analysis. In this technique, a spinning band
distillation is carried out on the sample to establish two
fractions. The initial boiling point fraction (up to 300
o
C) is
then analyzed using a supercritical fluid chromatographic
(ASTM 5186-91) method to determine saturates and aromatics
content. The greater than 300
o
C fraction is subjected to a
gravimetric analysis to determine the heptane insoluble
content (asphaltenes). This method dissolves the fraction in an
equal weight of toluene then 40 volumes of heptane are added
to precipitate the insoluble portion of the sample. The
precipitate is filtered, dried and weighed. The solvent is
removed from the soluble portion of the sample, which is
referred to as the maltenes. The maltenes are then re-dissolved
in pentane and are chromatographically separated into
saturates, aromatics and resins (polars) fraction by elution
from a column filled with activated alumina, using various
solvents and solvent mixtures. The solvents are then removed
from each fraction and the amount of material weighed. The
data from the three methods are combined to determine the
amount of each component type in the original sample. Mass
balances are calculated throughout the procedure to assure
accurate data.
For the case study considered in this work, the fluid
characterization data determined using the techniques
described above are summarized in Tables 1- 3. This fluid
was noteworthy as it had quite a low GOR (1037 SCF/STB)
for the bubble point of 6267 psia and a relatively high stock
tank oil density of 0.898 g/cm
3
(26
o
API). It is also noted from
the SAR(P)A analysis that the asphaltene (0.67 wt%) and wax
(0.86 wt%) contents of the crude oil are quite low.
Table 1: Preliminary Fluid Properties
Parameters Units Description
Reservoir Pressure - Pi psia 7393
Reservoir Temperature
o
F 152
Flash Gas-Oil Ratio SCF/STB 1037
Bubblepoint Pressure (Pb) at Tres psia 6267
Density of Stock-Tank Oil (STO) g/cc 0.898
Density of Reservoir Fluid at Pb g/cc 0.801
Density of Reservoir Fluid at Pi g/cc 0.819
OBM Contamination in STO % (w/w) 0.845
OBM Contamination in Reservoir Fluid % (w/w) 0.717
Preliminary Screening For Solids. After completion of the
fluid compositional characterization, a series of screening
criteria and simulation are used to evaluate the potential of the
crude oil under consideration to exhibit solid formation
problems. For asphaltenes in particular, the first screening test
is called the De Boer plot (Figure 3a) was developed based on
field observations by Shell
2
. Using the data from the case
study considered here, the plot indicates that the sample under
consideration would not be expected to exhibit any problems
in the field. The second screening criteria is the asphaltene to
resin ratio
15
. As can be seen in Figure 3b, this criteria also
indicated that there should be no solid formation problems for
the case study crude oil considered in this work. The third
screening criteria used was the colloidal instability index
suggested by Baker-Petrolite
15
. Referring to Figure 3c, it can
be seen that according to this criteria, there is potential for
asphaltene formation in this crude. Finally, an asphaltene
stability index criteria developed by Oilphase-Schlumberger is
4 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
shown in Figure 3d. By these criteria, the case study fluid is
on the border between stable and unstable with respect to
asphaltene formation. Predictive techniques for asphaltene
formation are not well developed at the current time, and it is
felt that the screening criteria adequately serve this purpose.
Based on the results presented in Figure 3a-d, it was felt that
there was a probability of asphaltene formation, thus justifying
further lab testing to clarify this potential.
Preliminary screening for wax formation generally
involves consideration of the stock tank oil wax content (UOP
Procedure
16
), the Cross Polar Microscopy (see below) wax
appearance temperature and preliminary thermodynamic
modeling. If wax content is greater than 2 wt% and the
measured or predicted STO wax appearance temperature is in
excess of 120
o
F, this may indicate a significant concern.
Table 2: Reservoir Fluid Composition
Components
Flashed
Liquid
Flashed
Gas
Reservoir
Fluid
% mole

Nitrogen 0.00 0.10 0.07
Carbon Dioxide 0.00 0.14 0.10
Hydrogen Sulfide 0.00 0.00 0.00
Methane 0.00 84.92 60.99
Ethane 0.00 6.08 4.37
Propane 0.00 3.45 2.48
I - Butane 0.00 0.76 0.54
N - Butane 0.01 1.54 1.11
I - Pentane 0.04 0.96 0.70
N - Pentane 0.09 0.65 0.49
pseudo C6H14 1.65 0.74 1.00
pseudo C7+ 98.21 0.67 28.15

Total 100 100 100
MW 293.42 20.85 97.66

Mole %
C7+ 98.21 0.67 28.15
C12+ 71.29 0.00 20.09
C20+ 35.80 - 10.09

Molar Mass
C7+ 297.27 100.31 293.90
C12+ 362.94 165.43 362.94
C20+ 515.90 - 515.90

Density (g/cc)
C7+ 0.899 - -
C12+ 0.920 - 0.920
C20+ 0.959 - 0.959
Fluid at 60
o
F 0.898 - -

MOLE RATIO 0.2818 0.7182
Table 3: SARA Analysis of Stock-Tank Oil
Cylinder Saturates Aromatics Resins Asphaltenes Wax
(n-heptane
Insolubles)
% (w/w)

Sample 1 49.53 31.70 18.10 0.67 0.86
Figure 3a: de Boer Plot
Figure 3b: Asphaltene Resin Ratio
For hydrate screening, it is generally felt that commercial
thermodynamic models provide reasonable initial estimates of
hydrate forming conditions. If the models predict hydrate
formation at temperature above those anticipated during
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.0 10.0 15.0 20.0
Resins % (w/w)
A
s
p
h
a
l
t
e
n
e
s

%

(
w
/
w
)
Stable
Unstable
Sample 1
0
2000
4000
6000
8000
10000
12000
0.50 0.60 0.70 0.80 0.90
In situ density (g/cc)
U
n
d
e
r
s
a
t
u
r
a
t
i
o
n

(
p
s
i
a
)
No
Problems
Uncertain
Severe
Problems
Sample 1
SPE 71546 A SYSTEMATIC APPROACH IN DEEPWATER FLOW ASSURANCE FLUID CHARACTERIZATION 5
production, it is advisable to complete experiments to quantify
the actual hydrate formation conditions. For the case study
completed here, although the general criteria did not indicate
significant potential for wax or hydrate problems, it was
nonetheless anticipated from production profile estimations
that the produced fluids would exhibit quite cold temperature
(as low as 40
o
F) and hence it would be advisable to complete a
series of wax and hydrate experimental measurements.
Figure 3c: Colloidal Instability Index
Figure 3d: Asphaltene Stability Index
Experimental Measurements. After establishing the
potential for solid formation through preliminary analysis and
screening criteria, the decision can be taken with regard to the
scope and nature of more detailed fluid behavior
measurements. Typically, the experimental identification of
the thermodynamic phase boundaries for the individual solid
hydrocarbon elements is the first step in this process. Various
laboratory techniques such as fluorescence spectroscopy
17
,
conductive measurements,
18
acoustic resonance,
19
gravimetric,
20
and light-scattering technique (LST)
8, 21-23
have
been used in determining the onset of solids formation
conditions. A general summary of the various techniques for
asphaltene formation can be found in reference 24. Reference
8, presents techniques to define the thermodynamic conditions
of wax appearance temperature (WAT). Various literatures
present the measurements of hydrate formation conditions and
they are primarily based on visual technique.
25
In the case study considered here, a variety of tests were
chosen to further characterize the solid formation
characteristics of the crude oil. The chosen tests are
summarized below:
Isothermal Depressurization for the Onset of
Asphaltene Precipitation
High-Temperature High Pressure Filtration for
Bulk Precipitation of Asphaltene
Cross Polar Microscope (CPM) for Wax
Appearance Temperature of STO
Isobaric Cooling for Wax Appearance
Temperature of Reservoir Fluid
Live and dead oil viscosity measurements for
Wax Appearance Temperature
Isobaric Cooling for Hydrate Formation
Temperature
Experimental Equipment. The experimental equipment
utilized for the measurements completed in this work is
described below.
Measurements such as isothermal depressurization for
onset of asphaltene, isobaric cooling for wax appearance
temperature and hydrate formation temperature were done
using the JEFRI pressure-volume-temperature (PVT)
apparatus. The equipment details can be found in Reference
24. The JEFRI PVT cell is equipped with fiber optic light
transmittance probes to measure the thermodynamic
conditions for the formation of hydrocarbon solids due to
changes in the temperature, pressure and/or composition. The
fiber optic probes are mounted across the windows of the
visual cell. The principle behind the measurement is based on
the transmittance of a near infra red (NIR) light through the
test fluid undergoing temperature, pressure or the fluid
composition changes. A computerized pump is used to either
maintain the system pressure during temperature sweeps (for
wax nucleation identification) or at a pre-set constant rate for
isothermal pressure drop and/or injections of precipitating
solvents (for asphaltene precipitation studies). The process
variables (i.e., temperature, pressure, solvent volume, time and
transmitted light power level) are recorded and displayed
25.0
35.0
45.0
55.0
65.0
75.0
0.0 20.0 40.0 60.0 80.0
Aromatics + Resins
A
s
p
h
a
l
t
e
n
e
s

+

S
a
t
u
r
a
t
e
s
Reference: Baker Petrolite
Unstable
Stable
Uncertain
Sample 1
-1.0
0.0
1.0
2.0
0.001 0.010 0.100 1.000
Density Undersaturation ( at Pr - at Pb)
S
t
a
b
i
l
i
t
y
Reference: Oilphase Database
Unstable
Stable
Sample 1
6 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
continuously during the course of a test. For consistency, the
fiber optic light transmittance system referred to here is
termed as the light scattering system (LSS).
The viscosity of the reservoir fluid is measured at the
reservoir temperature and pressure conditions using a
Cambridge SPL440 electromagnetic viscometer. The
viscometer consists of one cylindrical cell containing the fluid
sample and a piston located inside the cylinder. The piston is
moved back and forth through the fluid by imparting an
electromagnetic force on the piston. Viscosity is measured by
monitoring the time for the piston to traverse the cell under a
known force. The reported accuracy of the viscometer is
1.5% of full scale. The viscosity of stock-tank oil is
measured using a capillary tube technique. The assembly of an
oil reservoir attached to a capillary tube is maintained at the
required temperature. Subsequently, the oil is allowed to flow
under gravity between two marked levels in the capillary tube.
The time taken to pass through the marked level is then
converted to viscosity.
In addition to the PVT equipment, LSS, and viscosity,
high-pressure filters are also used during the asphaltene
precipitation study to quantify the amount of asphaltene in the
fluid at the specified conditions. The filter assembly consists
of two plates screwed together with the hydrophobic filter
sandwiched between them. Details of the equipment can be
found in reference 24. Finally, Wax Appearance Temperature
(WAT) of the stock-tank oil (STO) is measured using Cross-
Polar Microscopy (CPM) equipment. The CPM method is
based on the principal that the formation of wax crystals will
rotate the plane of polarization of light passing through the
oil/wax sample. The apparatus for CPM (in serial order)
consist of a light source, an IR-filter, a polarizer, a
temperature-controlled stage, an analyzer, a video camera, and
a PC. This setup is designed to detect any rotation of the
plane of polarization due to crystal formation.
Experimental Procedure
Isothermal Depressurization for the Onset of Asphaltene
Precipitation. Onset of asphaltene precipitation (OAP)
measurements using the light scattering system (LSS) involves
charging a known volume of the test fluid at reservoir (or
specified) temperature and pressure to the JEFRI PVT cell.
The LSS components are then mounted across the windows of
the PVT cell. The cell contents are then homogenized at a
maximum mixer speed of 1400 rpm for about 30 minutes.
Subsequently, a light transmittance scan is conducted to
establish a reference baseline. The depressurization
experiment is then started with simultaneous measurement of
light transmittance power. The maximum depressurization
rate used in this system is in the order of 40 psi/min.
The average transmitted light power and the corresponding
pressure are recorded every minute and the experiment is
stopped after reaching a certain pre-defined lower pressure.
During the depressurization run, any change in the light
transmittance characteristics is a reflection of various fluid
property and phase change phenomenon (ie. appearance of
solids and/or gas bubbles) that may occur. Visual observation
of the cell contents are also made and recorded during the
course of the experiment. At the end of the experiment, the
PVT cell is depleted and then rinsed with toluene to measure
the amount of any residual asphaltenes that may remain in the
cell. The quantity obtained provides a qualitative indication of
the percentage of total asphaltenes that may precipitate during
production whereas the rest tend to flow with the oil.
High-Temperature High Pressure Filtration for Bulk
Precipitation of Asphaltene. The high pressure high
temperature filtration test is conducted to quantify the amount
of asphaltenes that may flow at a given pressure.
Conventional theory suggests maximum amount of
asphaltenes are precipitated at the bubblepoint pressure
24
.
Hence, to quantify the maximum amount of asphaltenes that
may precipitate during production, filtration at bubblepoint
pressure is normally conducted. For the case study considered
here, asphaltenes were detected to be present at the reservoir
conditions and hence, an additional filtration at the reservoir
temperature and pressure was conducted to quantify the
amount of asphaltene that are present in the initial reservoir
fluid.
The filtration tests are conducted with a 0.22m filter
paper size. To prevent flashing of the reservoir fluid as it
passes through the filter, high-pressure helium is used to
maintain a backpressure on the downstream side of the filter.
As a result, the filtration process is very close to an isobaric
transfer. After displacement of the test fluid through the filter,
the volume of filtrate is measured and the asphaltene content
on the filter paper and the filtrate is determined.
Cross Polar Microscope (CPM) for Wax Appearance
Temperature of STO. The STO oil sample is homogenized at
the reservoir temperature and then a drop is mounted on a
slide and a cover slip is placed on top of it. The slide is placed
on the stage of a microscope to visually observe the WAT
with simultaneous recording of the process using a video
camera. The rate of cooling of the stage is controlled at
1.5
o
F/min. The slide is brought under focus for visual
observation and the sample is cooled from an initial
temperature of 150
o
F. The WAT is identified off-line at
which the first detectable bright spots are visible.
Live and dead oil viscosity measurements for Wax
Appearance Temperature. Prior to measuring the viscosity, a
suitable size piston is selected with the proper viscosity range
and the electromagnetic viscometer is calibrated using a fluid
with known viscosity. A portion of the reservoir fluid is then
transferred into a high-pressure high-temperature
electromagnetic viscometer. The viscometer is initially
evacuated and its temperature is controlled at the desired
temperature. During the transfer of reservoir fluid to the
evacuated viscometer, flashing of oil takes place, and hence,
the viscometer system is flushed with two viscometer volumes
of reservoir fluid to ensure that a representative oil sample is
taken. Subsequent to transfer of reservoir fluid into the
SPE 71546 A SYSTEMATIC APPROACH IN DEEPWATER FLOW ASSURANCE FLUID CHARACTERIZATION 7
viscometer, the fluid system is allowed to achieve thermal and
pressure equilibration. Then, the viscosity reading is taken.
For wax appearance temperature testing as considered in this
work, the temperature is then reduced while maintaining
pressure at the desired level. After thermal stabilization,
another viscosity reading is completed. This is repeated for a
pre-defined series of test temperatures.
Isobaric Cooling for Wax Appearance Temperature of
Reservoir Fluid. The isobaric cooling experiments using LSS
are conducted to measure the onset of wax appearance
temperature (WAT) of the reservoir fluid. In these
experiments, a known volume of the test fluid is charged into
the PVT apparatus at the reservoir temperature and pressure
conditions. The LSS components are then mounted across the
windows of the PVT cell. The cell content is then
homogenized at a maximum mixer speed of 1400 rpm for
about 30 minutes. The fluid is then isothermally flashed and
equilibrated at the designed experimental pressure.
Subsequently, the formed vapor phase is displaced from the
PVT cell to ensure constant liquid composition during the
isobaric cooling. Following gas displacement, a light
transmittance scan is conducted to establish the reference
baseline. The isobaric cooling experiment is then started with
simultaneous measurement of light transmittance power and
temperature. A maximum cooling rate of 1
o
F/minute is used
for this system.
Isobaric Cooling for Hydrate Formation Temperature. A
small volume of the homogenized single-phase fluid is
transferred into JEFRI PVT cell at reservoir temperature and
pressure conditions. After stabilization, the system pressure is
reduced to the experimental pressure below the bubblepoint
pressure. This generates a gas phase. Subsequently, a
sufficient amount of water is charged to the PVT cell to make
sure that the Oil System has excess free water. The system is
then equilibrated at the specified pressure. After stabilization,
an isobaric cooling experiment is conducted to determine the
temperature at which hydrates start to form. For gas-water
system, isobaric cooling with NIR provides good signature of
hydrate formation. However, for gas-water-oil system, NIR is
not adequate, hence, Oilphase developed a volume-
temperature (V-T) measurement techniques as described
below.
During the isobaric cooling experiment, the system volume
is monitored and recorded. During this isobaric cooling, the
system volume keeps decreasing as a result of cooling. At the
onset of gas hydrate formation, a larger volume of gas enters
the hydrate cavity. Consequently, a large decrease in volume
is detected during the hydrate formation. This volume change
provides a distinct signature of hydrate formation. Therefore,
VT measurements are used along with the visual confirmation
to determine the hydrate formation conditions.
Subsequently, the fluid system is heated and the volume is
again continuously measured. The volume measured during
the heating indicates when total hydrate decomposition occurs.
The formation and decomposition points are not the same due
to transient hysteresis.
Experimental Results
Isothermal Depressurization for the Onset of Asphaltene
Precipitation. Following the procedures outlined previously,
the reservoir fluid sample was stabilized for a period of 5 days
at reservoir temperature (152
o
F) and a pressure of 14,000 psig.
The stabilized sample was then transferred to the JEFRI PVT
cell at these conditions and the LSS test initiated. The LSS
data for this test is provided in Figure 4. As can be seen, the
fluid light transmittance initialy increases as expected and then
begins to fall at approximately 13,000 psia indicating the
formation of asphaltenes. This occurrence was surprising in
so much as the asphaltene onset occured well above reservoir
pressure of 7393 psia. Such a phenomenon could be attributed
to two factors:
1) The sample under consideration was not valid
because it was a sub-sample from a one-gallon
sample chamber and went through phase separation
during sample retrival from the wellbore.
2) The sample behavior deviated from the conventional
thinking that the aggregated asphaltenes cannot exist
at reservoir conditions.
Subsequently, to establish any temperature dependency on the
asphaltene onset pressure, it was decided to complete an
additional asphaltene onset screening test at 130 F. This test
was completed in the same manner as described above and the
LSS data for this test are provided as Figure 5. In this case, an
asphaltene onset pressure of 7600 psia was identified. This
indicated very significant effect of temperature on the
asphaltene stability for this crude oil.
Figure 4: Isothermal Depressurization: Onset of
Asphaltene Precipitation at 152
o
F
With the given measurements of asphaltene instability above
the reservoir pressure at both temperatures and uncertainty
0
200
400
600
800
1000
0 5000 10000 15000
Pressure (psia)
L
i
g
h
t

T
r
a
n
s
m
i
t
t
a
n
c
e

(
n
W
)
Poap = 13000 psia
Pi = 7393 psia
8 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
about the sample validity, the data interpretation is in the
realm of possibilities and ambiguous conclusions. Hence, no
further asphaltene characterization was deemed appropriate.
Figure 5: Isothermal Depressurization: Onset of
Asphaltene Precipitation at 130
o
F
Bulk Precipitation of Asphaltene. To establish the
presence of significant asphaltene aggregates in the reservoir
fluid at reservoir temperature and pressure, a bulk filtration
was completed at reservoir conditions. In addition, a bulk
filtration was completed near bubble point pressure to
establish the process of asphaltene particle aggregation.
Results of these measurements are presented in Table 4 in the
percentage units of mass of asphaltene filtered in 0.22m filter
paper per total mass of asphaltenes in the sample. As can be
seen, 13.9% of the asphaltenes in the oil are greater than
0.22m in size at reservoir pressure, whereas, 22.3% are
greater than this size at bubble point pressure. This provides
further evidence of asphaltene aggregates growing in size in
the reservoir fluid as pressure conditions are changed.
Table 4: High Pressure High Temperature Filtration
Results
Filtration Step
% of the total oil asphaltene content

Filter Filtrate Toluene Total

Paper Rinse
Filtration at
7400 psia &
153
o
F 13.97 74.49 n/a 88.5
Filtration at Pb
& 153
o
F 22.35 64.26 5.59 92.2


Cross Polar Microscope (CPM) for Wax Appearance
Temperature (WAT) of STO. As mentioned previously CPM
for determining the WAT of the stock tank oil is a general
screening parameter for potential wax formation issues. The
CPM data for the crude oil considered in this work is provide
as Figure 6. As can be seen, the first crystals of wax can be
identified forming in the STO at approximately 104
o
F.
Figure 6a: Stock-Tank Oil at 152
o
F
Figure 6b: Stock-Tank Oil at 103.6
o
F
Figure 6c: Stock-Tank Oil at 70
o
F
Live and dead oil viscosity measurements for Wax
Appearance Temperature. In the past, fluid rheology behavior
was conventionally used to define wax appearance
temperature (WAT). The viscosity measurements conducted in
these tests are for fluid rheology measurements only. The data
obtained are presented in Figure 7. As can be seen, the stock
tank oil WAT was found to be approximately 102
o
F and the
reservoir fluid WAT at 7000 psia was 108
o
F. This provided
reasonable confirmation of the CPM value, however, it is
generally expected that WAT will decrease with the addition
0
400
800
1200
1600
0 3000 6000 9000 12000 15000
Pressure (psia)
L
i
g
h
t

T
r
a
n
s
m
i
t
t
a
n
c
e

(
n
W
)
Poap = 7600 psia
Wax Crystal at
initiation
SPE 71546 A SYSTEMATIC APPROACH IN DEEPWATER FLOW ASSURANCE FLUID CHARACTERIZATION 9
of solution gas below the fluid saturation pressure and will
show a slight increase with pressure above the saturation
pressure. The 108
0
F measurement for the reservoir fluid in
this case was attributed to the relative uncertainty of the
viscometry technique for WAT determination, which is
estimated to be +/- 10
o
F. It is noted that the viscometry
technique is predominately done for fluid rheology
determination and not for WAT determination.
Figure 7: Viscosity Measurements
Isobaric Cooling for Wax Appearance Temperature of
Reservoir Fluid. It was decided that attempting to confirm the
WAT at reservoir conditions using the LSS may be
inconclusive due to the previously observed asphaltene
behavior at reservoir conditions. In other words, the wax and
asphaltene onset curves were very close at reservoir conditions
and would not be possible to distinguish between an
asphaltene onset and a wax appearance condition. As a result,
it was felt it would be more informative to have data at a lower
pressure condition, as this was more representative of the
anticipated production P-T pathway condition where wax
formation may become an issue. As a result, the WAT was
measured using LSS at a pressure condition of 2000 psia. The
results are presented in Figure 8 and indicate a WAT of 93
o
F.
This value was more consistent with expectation and shows
the effect of solution gas content in reducing the WAT.
Isobaric Cooling for Hydrate Formation Temperature.
The final test conducted on the reservoir fluid sample was for
the identification of the hydrate formation temperature. For
the same reasons as for the wax measurement, the hydrate
measurement was completed at a pressure of 2000 psi. The
results of the tests are presented as Figure 9. As shown, the
hydrate formation temperature on cooling was 47
o
F, whereas
the hydrate dissolution temperature upon re-heating was 52
o
F.
It is noted that wax will have formed at these conditions;
however, this will not affect the hydrate forming condition, as
Figure 8: Isobaric Cooling: Wax Appearance
Temperature at 2000 psia
Figure 9: Isobaric Cooling: V-T relationship for
Hydrate Measurements at 2000 psia
hydrate formation is dependent on the gse phase contact with
the free aqueous phase.
Modeling
Thermodynamic Model Tuning and Adjustment. To help
understand the expected solid formation behavior over a wide
range of potential operating conditions, the measured
properties of the reservoir fluid were used to tune an equation
of state (EOS) model for Vapour-Liquid behavior as well as
wax and hydrate formation conditions. The input parameters
for the model were the measured reservoir fluid composition,
0.1
1.0
10.0
100.0
60 80 100 120 140 160
Temperature (F)
V
i
s
c
o
s
i
t
y

(
c
P
)
STO Viscosity Viscosity at 7000 psia
0
50
100
150
200
250
300
0 30 60 90 120 150 180
Temperature (F)
L
i
g
h
t

T
r
a
n
s
m
i
t
t
a
n
c
e

(
n
W
)
WAT = 93
o
F
70.0
72.0
74.0
76.0
78.0
80.0
82.0
84.0
86.0
30 60 90 120
Temperature (F)
V
o
l
u
m
e

(
c
c
)
Cooling Heating
Complete
Hydrate
Decomposition
= 85
o
F
Hydrate
Decomposition =
52
o
F
Hydrate Formation
while cooling =
47
o
F
10 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
the molecular weight of the fluid, and the measured fluid
saturation pressures, WATs, and Hydrate formation
conditions. All tuning and predictions were completed using a
commercially available software package (PVTsim).
After tuning, the model was first used to predict the vapor-
liquid equilibrium curve as shown in Figure 11. However, the
software did not provide a direct tuning capability for Hydrate
formation. The un-tuned hydrate prediction at 2000 psia was
11
o
F above the measured decomposition temperature of 52
o
F.
Hence, the predicted curve was horizontally shifted to match
the measured data as shown in Figure 10. Although this
approach is not strictly rigorous, it was felt that it was an
acceptable estimation given the desired use of the predictive
model. The wax deposition phase envelope (Figure 11) was
predicted after tuning the compositional model with the wax
appearance temperature of 103.6
o
F for the stock-tank oil. The
tuned model predicted the wax appearance temperature of
93
o
F at 2000 psia without the need for additional tuning.
It is noted that asphaltene formation modeling was not
successful or meaningful given the experimental observation
that asphaltenes are present in a range of aggregated states
throughout a large range of the anticipated production
conditions. For this reason, no asphaltene model results were
completed.
Table 5: Hydrodynamic Calculation Assumptions
Parameters Values Units

Production tubing diameter 5 inches
Flow Rate 13000 - 8000 barrels per day
Tubing Insulated
Completion Subsea
Hydrodynamic Modeling. To estimate the potential
production P-T pathways for the reservoir under
consideration, a commercially available software package
(Olga) was used to simulate the hydrodynamic behavior of the
reservoir fluid. For the calculations, it was assumed that an
initial fluid flow rate of 13000 barrels per day would be
achieved and that this would reduce to 8000 barrels per day
after 5 years. The hydrodynamic calculations at 13000 bpd are
represented as Curve A in Figure 11 whereas that as 8000 bpd
are presented as Curve B. The input parameters for the
simulations are summarized in Table 5. The simulations here
obviously involve gross assumptions regarding the
hydrodynamic behavior of the produced fluid over time,
however they were felt to provide a reasonable bound for the
range of expected production conditions to be encountered by
the reservoir fluid.
Discussions. The experimental results and the theoretically
predicted phase envelopes were combined with the
hydrodynamic simulations to represent the overall
thermodynamic and hydrodynamic behavior of the reservoir
fluid. This information is summarized in Figure 11. As can be
seen, the pressure-temperature profile during production at
13000 bpd (Curve A) is at least 25
o
F higher than wax/hydrate
precipitation at any pressure. Thus, the reservoir fluid is not
believed to encounter wax/hydrate deposition problems during
early production. However, as the production rate decreases to
8000 bpd after five years, the heat transfer characteristics
change as indicated by Curve B in Figure 11. The path for
curve B crosses the conditions conducive for wax and hydrate
formation. Hence, wax and hydrate deposition problems are
expected during production at later times when production
rates begin to decline.
Finally, as determined during experimental measurements,
asphaltene instability could not be established with the given
uncertainties. Hence, effort to establish the asphaltene
precipitation phase behavior was abandoned.
Figure 10: Hydrate Phase Envelope
0
2000
4000
6000
8000
10000
0 20 40 60 80 100
Temperature (F)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
V-L-E Phase Envelope
Measured Hydrate Decomposition
Simulated Hydrate Envelope
Adjusted Hydrate Envelope
SPE 71546 A SYSTEMATIC APPROACH IN DEEPWATER FLOW ASSURANCE FLUID CHARACTERIZATION 11
Figure 11: Overall Phase Envelope
Conclusions
A systematic approach to the characterization of reservoir
fluids for potential hydrocarbon solid formation has been
presented. A case study following this systematic approach
has been used to demonstrate the practical application of this
technique. It can be concluded that although the general
approach presented provides some structure to the
hydrocarbon solid formation issues, specialist interpretation of
the scope of experiment and fluid property simulation is
necessary during intermediate stages of the process. This
results from the diverse nature of fluid phase behavior,
particulary hydrocarbon solid phase behavior.
It is noted that the asphaltene analysis has been
inconclusive because of the uncertainties with regards to the
sample validity resulting from phase change phenomenon
during the sample retrieval. To avoid uncertainties in the
asphaltene measurements, single-phase samples are highly
desired.
It is also noted that fluid characterization following the
approach presented should not be viewed as providing
definitive answers with regard to the extent of a potential flow
assurance problem. However, the data in insights gained
through the process are invaluable in assessing the risk
associated with flow assurance issues when considering a
particular field for development. The risk of flow assurance
problems arising from hydrocarbon solid deposition will have
considerable impact on all aspects of a field economic
assessment as control and remediation techniques for dealing
with these issues significantly effect the OPEX and CAPEX
contingencies in any field development.
As such, future work to establish techniques to quantify
the deposition tendancy of the various hydrocarbon solids as
well as the need to develope an understanding of the
interrelated aspects of their individual phase behavior
phenomenon will be very important in further reducing the
risks associated with deepwater production.
Acknowledgements
Authors wish to thank Murphy Oil and Oilphase for the
permission to publish the case study. Special thanks to Jim
Hunter of Murphy Oil for his contributions in designing some
of these tests.
References
1. C. Alexander: Technology Opens Deepwater
Opportunities, SPE Oil & Gas Executive Report, 4 (1),
2001, 36.
2. De Boer, R.B, & Leeriooyer K.: Screening of Crude Oils
for Asphalt Precipitation: Theory, Practice, and Selection
of Inhibitors, paper SPE 24987 presented at the European
Petroleum Conference held in Cannes, France, 16-18
November 1992.
3. Catalan, L.L., Jamaluddin, A.K.M., Stephanic, D.W.,
McNichol, P.A.: Solids Problem at the Ring Border Gas
Plant, JCPT, 37 (12), December 1998, 48
4. Koch, H.A. Jr.: High Pressure Gas Injection Is A
Success, World Oil, 143, (Oct 1956), 260.
5. Thomas,. F.B.: Proposed Screening Criteria for Gas
Injection Evaluation, JCPT, 37 (11), (November 1998),
14.
6. Burke, N.E., Hobbs, R.E., and Kashou, S.F.: Measurement
and Modeling of Asphaltene Precipitation, JPT
(November 1990), 1440.
7. Leontaritis, K.J. and Mansoori, G.A.: Asphaltene
Deposition: A Survey of Field Experiences and Research
Approaches, J. Pet. Sci. Eng. 1 (1988) 229.
8. Hammami, A. and Raines, M.: Paraffin Deposition from
Crude Oils: Comparison of Laboratory Results to Field
Data, paper SPE 38776 presented at the 1997 SPE Annual
Technical Conference and Exhibition, San Antonio, TX,
October 5-6.
9. Jamaluddin, A.K.M., Kalogerakis, N., and Bishnoi, P.R.:
Hydrate Plugging Problems in Natural Gas Pipelines
Under Shutdown Conditions, J. of Pete. Sci. and Engg., 5,
1991, 323.
10. Makogon, I.U.F.: Hydrates of Natural Gas, PennWell
Books, Tulsa, Oklahoma, 1981.
11. Nighswander, J. and Kurkjian, A., Sampling Hydrocarbon
Reservoir Fluids, IUPAC Experimental Thermodynamics,
Vol VI. Measurement of the Thermodynamic Properties of
Single Phases. (In Print)
12. Jamaluddin, A.K.M., Ross, B., and Hashem, M.: Single-
phase Reservoir Sampling: Is it Necessity or Luxury,
paper CIM 99-36 presented at the 1999 CSPG and
Petroleum Society Joint Convention, Calgary, Alberta, June
14-18, 1999.
0
2000
4000
6000
8000
10000
0 50 100 150 200 250 300
Temperature (F)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
V-L-E Phase Envelope
Measured Pb
Measured WAT by CPM
Measured WAT by NIR
Simulated WAT
Measured Hydrate
Simulated Hydrate
Reservoir Conditions
P-T at 13000 bpd
P-T at 8000 bpd
Curve A
Curve B
12 A.K.M. JAMALUDDIN, J. NIGHSWANDER AND N. JOSHI SPE 71546
13. Jamaluddin, A.K.M., Ye, S., Thomas, J., DCruz, D.,
Nighswander, J.: Experimental and Theoretical
Assessment of Using Propane to Remediate Liquid Buildup
in Condensate Reservoirs paper SPE 71526 to be
presented at the 2001 Annual Technical Conference and
Exhibition held in New Orleans, Louisiana, 30 September
3 October, 2001.
14. Gozalpour, F., Danesh, A., Tehrani, D.H., Todd, A.C., and
Tohidi, B.: Predicting Reservoir Fluid Phase and
Volumetric Behavior from Samples Contaminated with
Oil-Based Mud paper SPE 56747 presented at the 1999
SPE Annual Technical Conference and Exhibition held in
Houston, 3-6 October 1999.
15. Yen, A., Yin, Y.R., and Asomaning, S.: Evaluating
Asphaltene Inhibitors: Laboratory Tests and Field Studies
paper 65376 presented at the 2001 SPE International
Symposium on Oilfield Chemistry held in Houston, Texas,
13-16 February 2001.
16. UOP Method 46-64, UOP Reference Manual.
17. Wehry, E.L. and Rogers, L.B.: Fluorescence and
Phosphorescence of Organic Molecules, Fluorescence and
Phosphorescence Analysis, D.M. Hercules (ed.),
Interscience Publications, New York (1966) 81.
18. Fotland, P., et al.: Detection of Asphaltene Precipitation
and Amounts Precipitated by Measurement of Electrical
Conductivity, Fluid Phase Equilibria, 82 (1993) 157.
19. Jamaluddin, A.K.M., et al.: A Proactive Approach to
Address Solids (Wax and Asphaltene) Precipitation During
Hydrocarbon Production, paper SPE 49465 presented at
the 8
th
Abu Dhabi Petroleum Exhibition and Conference,
Abu Dhabi, U.A.E., 11-14 October 1998.
20. Kabir, C.S., and Jamaluddin, A.K.M.: Asphaltene
Characterization and Mitigation in South Kuwait's Marrat
Reservoir, paper SPE 53155 presented at the 1999 SPE
Middle East Oil Show held in Bahrain, 2023 February
1999.
21. Nighswander, J.A., et al.: Effect of Low Molecular
Weight Hydrocarbons on the Onset Concentration and Bulk
Properties of Asphaltene at In-Situ Temperature and
Pressure Conditions, paper 55E presented at the AIChE
meeting, March 28-April 1, 1993.
22. Fuhr, B.J., et al.: Properties of Asphaltene From Waxy
Crude, Fuel, 70 (1991) 1293.
23. Jamaluddin, A.K.M., et al.: De-Asphalted Oil: A Natural
Asphaltene Solvent, SPEPF (Aug. 1996) 161.
24. Jamaluddin, A.K.M., Creek, J., Kabir, C.S., McFadden,
J.D., DCruz, D., Thomas, J., Joshi, N., Ross, B.: A
Comparison of Various Laboratory Techniques to Measure
Thermodynamic Asphaltene Instability paper SPE 72154
to be presented at the SPE Asia Pacific improved Oil
Recovery Conference held in Kuala Lumpur, Malaysia, 8-9
October 2001.
25. Bishnoi, P. R.: Formation and Decomposition of Gas
Hydrates, Fluid Phase Equilibria, 117 (1996) 168.