Awari Yusuf Ibrahim, Measurement of Crude Oil Interfacial Tension To Determine Minimum Miscibility in Carbon Dioxide and Nitrogen

MEASUREMENT OF CRUDE OIL INTERFACIAL TENSION TO
DETERMINE MINIMUM MISCIBILITY IN CARBON DIOXIDE

AND NITROGEN
by
Ibrahim O. Awari-Yusuf
Submitted in partial fulfilment of the requirements

for the degree of Master of Engineering
at
Dalhousie University
Halifax, Nova Scotia
August 2013
Copyright by Ibrahim O. Awari-Yusuf, 2013

DALHOUSIE UNIVERSITY
PETROLEUM ENGINEERING
The undersigned hereby certify that they have read and recommend to the Faculty of
Graduate Studies for acceptance a thesis entitled MEASUREMENT OF CRUDE OIL
INTERFACIAL TENSION TO DETERMINE MINIMUM MISCIBILITY IN CARBON
DIOXIDE AND NITROGEN by Ibrahim O. Awari-Yusuf in partial fulfilment of the
requirements for the degree of Master of Engineering.
Dated: August 19, 2013
Supervisor: _________________________________
Reader: _________________________________
ii
DALHOUSIE UNIVERSITY
DATE: August 19, 2013
AUTHOR: Ibrahim O. Awari-Yusuf
TITLE: MEASUREMENT OF CRUDE OIL INTERFACIAL TENSION TO

DETERMINE MINIMUM MISCIBILITY IN CARBON DIOXIDE AND
NITROGEN
DEPARTMENT OR SCHOOL: Petroleum Engineering
DEGREE: MEng. CONVOCATION: October YEAR: 2013
Permission is herewith granted to Dalhousie University to circulate and to have copied

for non-commercial purposes, at its discretion, the above title upon the request of
individuals or institutions.
_______________________________
Signature of Author
The author reserves other publication rights, and neither the thesis nor extensive extracts
from it may be printed or otherwise reproduced without the authors written permission.
The author attests that permission has been obtained for the use of any copyrighted
material appearing in the thesis (other than the brief excerpts requiring only proper
acknowledgement in scholarly writing), and that all such use is clearly acknowledged.
iii
DEDICATION
I dedicate this work to the two father figures in my life, Mr Ismaila Awari-Yusuf and Mr
Yusuf Yusuf Awari, to Mrs Taibat Awari-Yusuf and to all my family and friends who
have supported me through the course of my studies.
iv
TABLE OF CONTENTS
LIST OF TABLES ................................................................................................................... vii

LIST OF FIGURES................................................................................................................ viii
ABSTRACT......................................................................................................................................... x
LIST OF ABREVIATIONS AND SYMBOLS ........................................................................................... xi
ACKNOWLEDGEMENTS ..................................................................................................................xiii
CHAPTER 1 INTRODUCTION ............................................................................................. 1
1.1. Background ...................................................................................................................... 1
1.2. Objective ............................................................................................................................... 3
CHAPTER 2 LITERATURE REVIEW ................................................................................... 4
2.1. Miscibility .............................................................................................................................. 4
2.2. Miscible flooding ................................................................................................................... 4
2.3. Carbon dioxide flooding ........................................................................................................ 5
2.3.1. Properties of carbon dioxide ............................................................................................. 5
2.4. Nitrogen flooding .................................................................................................................. 6
2.4.1. Nitrogen properties ........................................................................................................... 7
2.5. Miscible flooding mechanism ............................................................................................... 7
2.6. Interfacial tension ................................................................................................................. 8
2.7. Minimum miscibility pressure............................................................................................... 8
2.8. Experimental methods for determining minimum miscibility pressure ............................... 9
2.9. Crude oil density ................................................................................................................. 10
CHAPTER 3 EXPERIMENTAL............................................................................................. 11
3.1. The theory behind the pendant drop technique ................................................................ 11
3.2. Apparatus ............................................................................................................................ 13
3.3. Accuracy and reproducibility .............................................................................................. 16
3.4. Materials ............................................................................................................................. 17
3.5. Requirement of the drop shape analysis ............................................................................ 17
3.5.1. Crude oil density measurement....................................................................................... 17
3.5.2. Carbon dioxide Density .................................................................................................... 18
3.5.3 Nitrogen Density ............................................................................................................... 20
v
3.6 DSA Measurement ............................................................................................................... 22
CHAPTER 4 RESULTS AND DISCUSSION ................................................................... 24
4.1. Crude oil and carbon dioxide systems at 220C.................................................................... 26
4.2. Crude oil and nitrogen systems at 220C .............................................................................. 35
4.3 Gullfaks C using carbon dioxide at 600C............................................................................... 44
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS........................................ 47
1.1 Conclusions .................................................................................................................... 47
5.2 Recommendations ............................................................................................................... 48
REFERENCES ................................................................................................................................... 49
vi
LIST OF TABLES
Table 3.1: Calibration data .................................................................................................16

Table 3.2: Crude oil density data ...................................................................................... 18
Table 3.3: Carbon dioxide density data .............................................................................19
Table 3.4: Variation of nitrogen density with pressure..................................................... 20
Table 4.1: DSA measurement for Arab AH-50 using carbon dioxide.............................. 25
Table 4.2: DSA measurement of Gullfaks C using carbon dioxide.................................. 27
Table 4.3: DSA measurement of West Texas Intermediate using carbon dioxide ........... 27
Table 4.4: DSA measurement of Arab AH-50 using nitrogen.......................................... 35
Table 4.5: DSA measurement of Gullfaks C using nitrogen ............................................ 36
Table 4.6: DSA measurement of West Texas intermediate using nitrogen ...................... 37
Table 4.7: DSA measurement of Gullfaks C using carbon dioxide at reservoir
temperature ....................................................................................................................... 44
vii
LIST OF FIGURES
Figure 2.1: Pure carbon dioxide phase diagram ................................................................ 5

Figure 2.2: Carbon dioxide density as a function of pressure at 600C ............................... 6
Figure 3.1: Schematic of a pendant drop ........................................................................ 17
Figure 3.2: Drop shape analysis (DSA 100 V 1.9) and high pressure pendant drop (PD-E
1700) ................................................................................................................................. 18
Figure 3.3: Schematic of the axisymmetric drop shape analysis (ADSA) ...................... 19
Figure 3.4: Variation of carbon dioxide density with Temperature................................. 22
Figure 3.5: Variation of Gullfaks C density with pressure .............................................. 24
Figure 3.6: Flow sheet of the PD-E1700 ....22
Figure 4.1: Variation of Arab AH-50 drop volume with pressure using carbon dioxide at
220C................................................................................................................................... 31
Figure 4.2: Variation of Gullfaks C drop volume with pressure using carbon dioxide at
220C................................................................................................................................... 31
Figure 4.3: Variation of West Texas intermediate drop volume with pressure using
carbon dioxide at 220C ...................................................................................................... 32
Figure 4.4: Variation of Arab AH-50 drop surface area with pressure using carbon
dioxide at 220C.................................................................................................................. 33
Figure 4.5: Variation of Gullfaks C drop surface area with pressure using carbon dioxide
at 220C............................................................................................................................... 33
Figure 4.6: Variation of West Texas intermediate drop surface area with pressure using
Figure 4.7: Variation of Arab AH-50 interfacial tension with pressure using carbon
dioxide at 220C.................................................................................................................. 35
Figure 4.8: Variation of Gullfaks C interfacial tension with pressure using carbon
dioxide at 220C.................................................................................................................. 35
Figure 4.9: Variation of West Texas intermediate interfacial tension with pressure using
Figure 4.10: Variation of Arab AH-50 drop volume with pressure using nitrogen at 220C
........................................................................................................................................... 40
Figure 4.11: Variation of Gullfaks C drop volume with pressure using nitrogen at 220C
.......................................................................................................................................... .40
Figure 4.12: Variation of West Texas intermediate drop volume with Pressure using
nitrogen at 220C ................................................................................................................ 41
Figure 4.13: Variation of Arab AH-50 drop surface area with pressure using nitrogen at
220C................................................................................................................................... 42
Figure 4.14: Variation of Gullfaks C drop surface area with pressure using nitrogen at
220C................................................................................................................................... 42
Figure 4.15: Variation of West Texas intermediate drop surface area with pressure using
nitrogen at 220C ................................................................................................................ 43
Figure 4.16: Variation of drop interfacial tension With pressure Using nitrogen at 220C
........................................................................................................................................... 44
Figure 4.17: Variation of Gullfaks C Drop IFT With Pressure Using nitrogen at 220C.. 44
Figure 4.18: Variation of West Texas intermediate drop interfacial tension with pressure
using nitrogen at 220C ....................................................................................................... 45
viii
Figure 4.19: Variation of Gullfaks Cs interfacial tension with pressure using carbon
dioxide At 600C................................................................................................................. 47
Figure 4.20: Variation Of Gullfaks Cs interfacial tension With temperature ................ 47
ix
ABSTRACT
Gas injection has been used to enhance oil recovery due to its ability to maintain
reservoir pressure, reduce oil viscosity, reduce oil interfacial tension, displace residual oil
and induce oil swelling effect.
However the type of gas used would have a considerable impact on oil recovery and the
cost incurred during injection thereby determining the economics of the process.
In this study, the axisymmetric drop shape analysis (ADSA) technique is used to assess
the impact of pressure change, injection gas type and crude oil type on the pendant drop
volume, surface area and interfacial tension. The ADSA technique is used to measure the
pendant drop parameters of the Arab AH-50, the Gullfaks C and the West Texas
intermediate crude oil pendant drops in carbon dioxide and nitrogen. It is found that in
each test, the pendant drop volume, surface area and IFT reduce linearly with pressure
increase. Reduction in the three parameters is more pronounced in the crude oil-carbon
dioxide system. The vanishing interfacial tension (VIT) technique is used to estimate first
contact minimum miscibility pressure of the crude oil-gas systems from the measured
interfacial tension and it was seen that the systems with carbon dioxide required less
pressure to achieve miscibility thereby making carbon dioxide a more favourable gas for
miscible flooding in comparison to nitrogen.
x
LIST OF ABREVIATIONS AND SYMBOLS
= Oil density at reservoir conditions(lb/ft3)
= Fake density used in oil density calculation (lb/ft3)
= Pseudo liquid density (lb/ft3)
= Oil density at reservoir bubblepoint (lb/ft3)
= The difference in density of the two phases (Kg/m3)
= Adjustment of oil density due to pressure (lb/ft3)
= Adjustment of oil density due to temperature (lb/ft3)
Interfacial tension
= Weighted average surface gas specific gravity
= Stock tank oil specific gravity
= Separator gas specific gravity
= Interfacial tension (mN/m)

a = Capillary length
= Constants
B0 = Bond number which represents the ratio of buoyancy force to surface force
(dimensionless)
= Weighted average oil compressibility from bubble point pressure to a higher

pressure of interest, 1/psi
g = Gravitational acceleration (M/s3)
= Pressure (psia)
= Bubblepoint pressure (psia)
= Pressure difference at a reference plane (psia)

r = Characteristic radius (m)
R0 = Radius at the apex of the drop (m)
= Principal radii of curvature
xi
=Solution gas oil ratio at bubblepoint pressure (scf/STB)
mN/m = Mill-Newton per meter
= Temperature (0F)
ADSA = Axisymetric drop shape analysis
EOR = Enhanced oil recovery
IFT = Interfacial tension
MMP = Minimum miscibility pressure
PV = Pore volume
RBA = Rising bubble apparatus
VIT = Vanishing interfacial tension
xii
ACKNOWLEDGEMENTS
I am immensely grateful to all faculty members and staff especially Mr Mumuni Amadu
and Mr. Matt Kujath for their support and motivation during this project. I will also like
to thank my supervisor Dr. Michael Pegg, for the continued assistance, guidance and
support given me through the course of this project. I am also thankful to Dr. Jan
Healssig for his acceptance to serve on the examining committee.
Finally, to my family which has been a constant source of encouragement and support, I
say thank you.
xiii
CHAPTER 1 INTRODUCTION
1.1. Background
As crude oil recovery from conventional reservoirs continues to decrease, enhanced oil recovery
(EOR) is increasingly becoming significant in the petroleum industry. Gas injection has been
used as an EOR process in the petroleum industry for a very long time due to its pressure
maintenance capability, its ability to reduce the viscosity of reservoir fluids, and its efficiency in
displacing reservoir fluids as well as inducing oil swelling effect which is the expansion of the
reservoir oil due to the dissolution of the injected solvent into the reservoir fluid (Sclumberger
Limited, 2013).
Interfacial mass transfer occurs between the injected gas phase and the reservoir fluid during gas
injection until an equilibrium state is achieved. As a result of this phenomenon, the physical and
chemical properties of the reservoir fluid are modified leading to a more efficient displacement
process (Danesh, 1998).
Gas flooding can be classified into miscible, semi miscible and immiscible flooding processes
depending on the temperature, pressure, type of injected gas and reservoir conditions (Ali et al.,
2013). Lake (1989) stated that fluids that mix in all proportions while still existing in a single
homogenous phase are considered to be miscible. The minimum miscibility pressure (MMP) is
defined by Johnson and Pollin as the lowest pressure at which an apparent point of maximum
curvature can be seen as recovery of oil at 1.2 pore volumes (PV) gas injected is plotted against
pressure (Johnson & Pollin, 1981) this can also be said to be the pressure at which the interfacial
tension (IFT) between two phases is zero (Green & Willhite, 1998).
1
2
The classification of gas flooding is based on the MMP (Wang & Gu, 2011). Hence If the
pressure of the reservoir is not maintained above the MMP of the injected gas then the injection
process would become semi miscible or immiscible (Fanchi, 2006).
Determining MMP accurately is a crucial step in the design of an economical miscible injection
program. Numerous analytical and experimental methods have been developed to predict or
estimate MMP. Traditionally, the slim tube method is considered as the standard technique for
MMP measurement in an oil/solvent system (Huang & Dyer, 1993). However, it is very
expensive and time consuming (Gu et al., 2013). High pressure carbon dioxide core flood tests
can also be used to measure MMP in a similar fashion as the slim tube method (Huang, 1992).
The rising-bubble apparatus (RBA) (Christiansen & Haines, 1987) and the vanishing interfacial
tension (VIT) technique (Rao, 1997; Rao & Lee, 2002; Rao & Lee, 2003 ; Gu et al., 2013) are
faster and less expensive methods of which MMP can be experimentally estimated.
It has been shown that IFT reduces in a linear fashion in an isotherrmal system as the pressure
reduces (Adamson & Gast, 1997) and that MMP can be estimated through the extrapolation of
the IFT linear equation till IFT is zero (Rao & Lee , 2003).
The choice of injection gas would depend on the availability of the gas, reservoir conditions and
the economic viability of the gas injection process. Carbon dioxide injection is said to be one of
the most effective methods to improve the efficiency of the oil recovery process (Alvarado &
Manrique, 2010; Farouq & Thomas, 1996).
To test the above stated statements, the axisymmetric drop shape analysis (ADSA) technique is
used to assess the impact of pressure change, injection gas type and crude oil type on the pendant
drop volume, surface area and IFT. In more detail, the ADSA technique is used in this study to
measure the DSA pendant drop parameters of the Arab AH-50, the Gullfaks C and the West
3
Texas intermediate pendant drops in carbon dioxide and nitrogen systems. The VIT technique is
then used to estimate first contact minimum miscibility pressure of the crude oil and gas systems
from the measured IFT at 220C and over a pressure of 100 to 600 psi.
1.2. Objective
This work is being carried out for the following reasons:
1) To understand the principles behind miscible gas injection as an EOR method .
2) To test the accuracy of statements from literature that state that IFT reduces linearly with
pressure increase under isothermal conditions and that carbon dioxide is a more favorable
gas for miscible flooding compared to nitrogen.
3) To generate data that can form the basis of correlations to determine MMP of the used
crude oil samples in carbon dioxide and nitrogen systems.
4) To determine the variation in pendant drop volume and surface area with pressure and
density.
5) To determine if IFT varies linearly with pressure at non reservoir conditions.

CHAPTER 2 LITERATURE REVIEW
2.1. Miscibility
Miscibility between two or more fluids has been defined in numerous ways by different authors
(Rao D. N., 1997; Benham et al., 1965; Lake, 1989). However all definitions acknowledge one
of the following (Mohamed, 2009): (1) Inexistence on an interface between the mixing fluids; (2)
Occurrence of zero IFT between the mixing fluids; (3) All fluid mixtures mix in all proportions
while existing in a single indistinguishable phase.
2.2. Miscible flooding
This is a branch of enhanced oil recovery (EOR) where miscible gases are injected into the
reservoir. These gases maintain the reservoir pressure as well as improve the recovery of the
reservoir fluid due to the reduction in IFT between the injected fluid and the reservoir fluid
(Schlumberger Limited, 2013). Many miscible gasses could be injected into the reservoir to
achieve the same outcome. The choice of the gas would depend on the cost and its availability. A
few gases that are currently being used are liquefied petroleum gas (LPG) such as methane and
propane, light hydrocarbon, nitrogen and carbon dioxide. Carbon dioxide is the most widely used
gas for miscible flooding because it reduces oil viscosity and is less expensive when compared to
LPG (Schlumberger, 2013).
4
5
2.3. Carbon dioxide flooding
Carbon dioxide has been used in oil recovery since 1952 (Stalkup, 1978). Carbon dioxide can be
used for miscible displacement (Rathmel et al., 1971), immiscible displacement (Kumar & Von
Gonten, 1973), reservoir pressure maintenance (Holm & Josendal, 1974), well stimulation
(Stright Jr., Aziz, & Settari, 1977), etc.
2.3.1. Properties of carbon dioxide
Carbon dioxide is a relatively non-toxic, non-flammable fluid (Mohamed, 2009). It has a critical
temperature and pressure of 30.9782 0C and 7.3773 MPa respectively; its triple point is -56.558
0
C and 517.15 MPa (Span & Wagner, 1994). Figure 2.1 illustrates the pressure-temperature
property of carbon dioxide. It can be seen that carbon dioxide would exist in different phases
depending on its temperature and pressure.
Figure 2.1: Pure carbon dioxide phase diagram (Zhang et al., 2012)
6
Figure 2.2 show the variation in density with pressure at 600C. It can also be seen from Figure
2.2 that pressure has a large impact on density. Figure 2.2 was plotted using data from the peace
software thermodynamic data (Peace Software) and the correlation proposed by Ouyang
(Ouyang, 2011).
1.2
Density (kg/m3) at 60 degrees
0.8
density (g/cm3)
0.6
0.4
0.2
0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Pressure (psia)
Figure 2.2: Carbon dioxide density as a function of pressure at 600C (Peace software;
Ouyang, 2011)
2.4. Nitrogen flooding
Nitrogen flooding has been used in EOR successfully for a long time in the oil industry (Koch &
Hutchinson, 1958; Hudgins et al., 1990). It has also been used for other purposes such as gas lift,
pressure maintenance and gas cycling (Clancy et al., 1985). Nitrogen is used as an alternative to
natural gas and carbon dioxide due to its low cost and non corrosive nature and since it can be
7
extracted from atmospheric air via cryogenic processes, its source is largely unlimited (Lindley,
2011).
Nitrogen miscibility is favored in reservoirs that are rich in light and intermediate hydrocarbon
components at a high reservoir pressure (Hudgins et al., 1990). Due to the high injection pressure
that nitrogen flooding requires, the reservoir should be able to withstand this high pressure
without fracturing the formation (Lindley, 2011).
2.4.1. Nitrogen properties
Nitrogen is a nontoxic, non-flammable gas at atmospheric conditions. It has a critical
temperature of -147 C and a critical pressure of 3.3999 MPa and critical density of 314.03
kg/m3. Its triple point is at -210.1 C and 0.01253 MPa. Nitrogen makes up at least 78% of
atmospheric air by volume (Air Liquide, 2013).
2.5. Miscible flooding mechanism
Miscible gases displace reservoir fluid in very similar ways. Lindley (2011) explained that the
injected gas forms a miscible front by vaporizing light components of reservoir oil. The enriched
gas then moves away from the injection well into the reservoir, where it further enriches itself by
contacting with reservoir oil and vaporizing more light components. This enrichment process
continues until the gas becomes miscible with the reservoir fluid and a homogenous phase with
new physicochemical properties is formed. Continuous injection of the gas would push oil via
the miscible front towards the production well. The produced reservoir fluid can be separated for
oil, natural gas and the injected gas (Lindley, 2011).

8
2.6. Interfacial tension
Interfacial tension, commonly expressed in mN/m or dyne/cm, is a property of the interface that
exists between two immiscible phases. It is referred to as interfacial tension when both phases
are liquid and it is called surface tension when one of the phases is atmospheric air. However,
they both refer to the Gibbs free energy present per unit interface area at a particular temperature
and pressure (Schlumberger, 2013).
2.7. Minimum miscibility pressure
The minimum miscibility pressure (MMP) is defined by Johnson and Pollin as the lowest
pressure at which an apparent point of maximum curvature can be seen as recovery of oil at
1.2PV gas injected is plotted against pressure (Johnson & Pollin, 1981). It can also be defined
as the minimum pressure whereby the injected gas phase becomes miscible with the residual oil
in place (ROIP) after a multi-contact process at the existing reservoir temperature. (Stalkup,
1987). MMP is dependent on factors such as the composition of the injected gas, the ROIP and
the reservoir temperature and independent of the velocity of displacement and the condition of
the porous media (Alomair et al, 2011)

9
2.8. Experimental methods for determining minimum miscibility
pressure
A number of experimental methods have been developed to measure MMP. Traditionally, the
slim tube method is considered as the standard technique for MMP measurement in an
oil/solvent system (Huang & Dyer, 1993). This method reproduces the multiphase fluid flow
through a porous medium under reservoir conditions. It is however very expensive and time
consuming (Gu et al., 2013). High pressure carbon dioxide core flood tests can also be used to
measure MMP in a similar fashion as the slim tube method (Huang, 1992).
The expensive and time consuming nature of the above methods led to the development of more
favorable methods that are faster and more cost effective such as the rising-bubble apparatus
(RBA) (Christiansen & Haines, 1987). The use of the RBA to determine MMP is faster and
requires less crude compared to the slim tube method and the core flooding approach; however,
this method could overestimate MMP for some systems (Gu et al., 2013).
The VIT, which is the technique used in this study, has recently been used to measure MMP
(Rao D. N., 1997; Rao & Lee, 2002; Rao & Lee, 2003;Gu et al., 2013). The IFT between crude
oil and carbon dioxde can be accurately measured using ADSA and the MMP can be
extrapolated from IFT data at reservoir conditions.

10
2.9. Crude oil density
There are a number of correlations that can be used to estimate crude oil density. However, in
this work, the use of correlations was not feasible due to the large amount of data needed by the
correlations. Hence the measurement of crude oil density was carried out in the laboratory using
a pycnometer (purchased from VWR International) according to ASTM standard D1217 12.
11
CHAPTER 3 EXPERIMENTAL
3.1. The theory behind the pendant drop technique
The pendant drop technique uses axisymmetric drop shape analysis (ADSA) to determine
interfacial properties through ascertaining the profile of the liquid droplets formed. This
experimental profile is then fitted with the theoretical Laplace equation reported by Cheng,
(1990). Hydrodynamic equilibrium is a requirement for this technique, i.e. the only forces acting
on the drop should be gravity and surface tension (Neumann & Rio, 1997). Figure 3.1 below
shows the schematic of a pendant drop.
Figure 3.1: Schematic of a pendant drop (Mohammed, 2009)

12
Chiquet et al, (2007) reported that Chengs equation can be represented by the following
ordinary differential equations with an arc length of s:
(17)
(18)
(19)
R0 2R0 + (20)
Where:
= angle between the horizontal and the tangent to the drop contour
B0 = Bond number which represents the ratio of buoyancy force to surface force (dimensionless)
r = characteristic radius (m)
= The difference in density of the two phases (kg/m3)
g = Gravitational acceleration
R0 = radius at the apex of the drop (m)

13
The ADSA determines B0 and values that minimizes the difference between the solution to
equation 20 and the digital profile of the drop. Hence, the capillary length a is determined.
Capillary length can be expressed as:

(21)
The IFT can therefore be determined by solving equation 21 after the difference in density
between the two phases has been obtained. Hence:
IFT( ) = (22)
3.2. Apparatus
The high pressure pendant drop apparatus (PD-E 1700) and the drop shape analysis (DSA 100
V1.90.0.14) are used to measure the equilibrium and dynamic IFTs of crude oil/carbon dioxide
systems at different temperatures and pressures. The PD-E 1700 was made by
EUROTECHNICA and the DSA 100V1. 90.0.14 was made by K SS. The equipment is shown
in Figure 3.2.
14
Figure 3.2: Drop shape analysis (DSA 100 v 1.9) and high pressure pendant drop (PD-E 1700)
The major components of the PD-E 1700 are a high temperature and pressure cell with two
windows. 200 0C and 69 MPa are the maximum operating temperature and pressure. The DSA
100 (V1.90.0.14) consists of a light source and a high resolution CCD camera. The high pressure
cell is placed between the camera and the light source to enable illumination through the two
windows.
The IFT is determined by analyzing the shape of a pendant drop and this is considered as the
most powerful method of measuring interfacial properties because of its versatility, accuracy and
simplicity (Cheng & Neumann, 1992; Jennings & Pallas, 1988). The pendant crude oil drop is
formed within the carbon dioxide phase using a needle installed at the top of the high pressure
cell. A digital image of this drop is acquired using a digital image acquisition system.
15
This image is then fitted with the Laplace equation of capillarity and the IFT is automatically
calculated by generating an interfacial profile that best fits the actual drop. Figure 3.3 shows a
schematic of the process.
Image
Image Analysis
Numerical Optimization
Physical Properties
(,g)
( )
Interfacial tension
Figure 3.3: Schematic of the axisymmetric drop shape analysis (ADSA) adapted from
(Hoorfar & Neumann, 2006)

16
3.3. Accuracy and reproducibility
The accuracy of the pendant drop equipment was tested by calibrating with the measurement of
the IFT of deionised pure water /atmospheric air system until the typical value of 70.26 mN/m
was obtained.The calibration data are shown in Table 3.1 below . The standard deviation of the
data was calculated as 0.310289.
Table 3.1 : Calibration data
IFT
Theta(L) Theta(R) Theta(M) Vol Area BD Fit-Er MAG
[mN/ Method Density
[deg] [deg] [deg] [l] [mm*2] [mm] [um] [pix/mm]
m]
70.13 108.4 108.4 108.4 24.18 39.58 1.619 3.43 L-Y 82.06 0.9968
70.71 100.8 100.8 100.8 25.34 41.48 1.533 3.86 L-Y 82.01 0.9968
70.33 107.4 107.4 107.4 24.43 39.95 1.604 3.49 L-Y 82.02 0.9968
70.17 107.1 107.1 107.1 24.45 39.99 1.604 3.61 L-Y 82.04 0.9968
70.2 107 107 107 24.46 40.01 1.603 3.5 L-Y 82.01 0.9968
69.83 106.5 106.5 106.5 24.43 40.02 1.596 3.71 L-Y 82.04 0.9968
69.88 106.3 106.3 106.3 24.47 40.06 1.596 3.67 L-Y 82.01 0.9968
70.28 107 107 107 24.47 40.02 1.6 3.43 L-Y 82.03 0.9968
70.16 106.9 106.9 106.9 24.45 39.99 1.601 3.54 L-Y 82.03 0.9968
70.06 106.7 106.7 106.7 24.46 40.03 1.599 3.52 L-Y 82.05 0.9968
70.03 106.6 106.6 106.6 24.45 40.02 1.597 3.58 L-Y 82.04 0.9968
70.18 106.1 106.1 106.1 24.67 40.31 1.596 3.5 L-Y 81.99 0.9968
70.08 105.8 105.8 105.8 24.66 40.34 1.592 3.3 L-Y 81.99 0.9968
70.08 105.7 105.7 105.7 24.67 40.35 1.59 3.52 L-Y 81.96 0.9968
70.04 105.6 105.6 105.6 24.67 40.34 1.59 3.42 L-Y 81.97 0.9968
69.99 105.5 105.5 105.5 24.68 40.39 1.589 3.27 L-Y 81.96 0.9968
70.01 105.5 105.5 105.5 24.64 40.31 1.587 3.63 L-Y 81.97 0.9968
69.9 105.5 105.5 105.5 24.58 40.24 1.585 3.5 L-Y 82.01 0.9968
69.88 105.4 105.4 105.4 24.65 40.34 1.588 3.29 L-Y 81.99 0.9968
69.93 105.4 105.4 105.4 24.68 40.38 1.588 3.39 L-Y 81.96 0.9968
70.52 107.6 107.6 107.6 24.47 39.96 1.608 3.61 L-Y 82.02 0.9968
70.56 107.6 107.6 107.6 24.5 40 1.61 3.72 L-Y 82.03 0.9968
70.5 107.5 107.5 107.5 24.46 39.95 1.607 3.77 L-Y 82.04 0.9968
70.74 104.7 104.7 104.7 25.04 40.83 1.577 3.37 L-Y 82 0.9968
70.79 104.7 104.7 104.7 25.02 40.82 1.575 3.59 L-Y 81.99 0.9968
70.71 104.7 104.7 104.7 25.02 40.81 1.577 3.54 L-Y 82.01 0.9968
70.71 104.6 104.6 104.6 25.07 40.9 1.578 3.45 L-Y 82.01 0.9968
70.67 104.6 104.6 104.6 25.03 40.86 1.576 3.47 L-Y 82.02 0.9968
70.56 104.3 104.3 104.3 25 40.82 1.571 3.46 L-Y 82.05 0.9968
70.26 24.66 40.31 1.590
17
3.4. Materials
Three crude oil samples were used in this study: Arab AH-50, Gullfaks C and west Texas
intermediate. Carbon dioxide (99.5% purity) and nitrogen (99.995% purity) were purchased from
Praxair and were used without further purification. Carbon dioxides critical temperature and
pressure are 30.95oC and 7.38MPa. Nitrogens critical temperature and pressure are -240oC and
1.30MPa.
3.5. Requirement of the drop shape analysis
The drop shape analysis software used (DSA 1.90.0.14) requires the capillary needle diameter,
the local gravitational acceleration, and the density difference between the liquid (crude oil) and
gas phase (CO2/N2).
3.5.1. Crude oil density measurement
In this work, the use of correlations was not feasible due to the large amount of data needed by
the correlation. Hence the measurement of crude oil density was carried out in the laboratory
using a Pycnometer (purchased from VWR International) according to ASTM standard D1217
12.
18
Table 3.2 shows the calculated density data.
Table 3.2. : Crude oil density data
Crude Oil Temperature Density (g/cm3)
Gullfaks C 22oC 0.873
Arab AH-50 22oC 0.911
West texas intermediate 22oC 0.903
Gullfaks C 60oC 0.837
3.5.2. Carbon dioxide Density
There are numerous correlations that have been generated to estimate carbon dioxide density.
However the most popular data for carbon dioxide density are does published by Span and
Wagner in 2004. Hence carbon dioxide density data at the pressure and temperature conditions
of interest i.e., 100-600 psia and 220C and 600C were calculated by using peace software. These
data were validated and compared with data presented by Span & Wagner, (1994) obtained from
the National Institute of Standards and Technology (NIST) website. The average density of
carbon dioxide decreases with increasing temperature and increases with pressure.
19
Table 3.3: Carbon dioxide density data
Density (g/cm3)
Temperature (0C)
220C 60 0C
Pressure (psia)
100 0.0129 0.0113
200 0.0271 0.0232
300 0.0421 0.0355
400 0.0593 0.0488
500 0.0791 0.0630
600 0.1016 0.0780
Figure 3.4 shows that the change in density of the Gullfaks C crude with temperature is more
obvious as pressure increases.

20
0.09
22 Degrees 60 degrees
0.08
0.07
Density (g/cm3) 0.06
0.05
0.04
0.03
0.02
0.01
0
0 100 200 300 400 500 600
Pressure (psia)
Figure 3.4: Variation of carbon dioxide density with temperature
3.5.3 Nitrogen Density
Nitrogen density at the pressure and temperature conditions of interest i.e., 100-600 psia and
220C were calculated by using peace software. This data was compared and validated with data
presented by Span et al., (2000) obtained from the National Institute of Standards and
Technology (NIST) website. The average density of nitrogen increases with increasing pressure.
The nitrogen densities were calculated using the ideal gas law as the as the error due to
compressibility at the highest pressure of 600 psia is 2.5 percent.

21
Table 3.4: Variation of nitrogen density with pressure
Density
(g/cm3)
Temperature (0C)
220C
Pressure (psia)
100 0.0079
200 0.0158
300 0.0237
400 0.0317
500 0.0396
600 0.0475
0.05
0.045
0.04
0.035
Density (g/cm3)
0.03
0.025
0.02
0.015
0.01
0.005
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 3.5: Variation of nitrogen density with pressure at 22 0C

22
3.6 DSA Measurement
Figure 3.6: Flow sheet of the PD-E1700 (EUROTECHNICA, 2008)
The schematic of the pendant drop apparatus is shown in Figure 3.6. The equipment was first
calibrated using deionized water and atmospheric air until a satisfactory value of 70.26 mN/m
was obtained. The view cell was then filled with gas (CO2 or N2) until the predetermined
pressure was reached using the screw pump on the gas cylinder. About ten minutes was allowed
for the pressure in the chamber to stabilize. Finally, crude oil was then added to the liquid supply
tank (TL1) with valve A shut. Valve B was then shut and valve A opened. The screw piston
pump (PG1) was then operated anti-clockwise to suck the crude oil into the cylinder. Once the
cylinder was full, PG1 was operated clockwise with valve A open to allow some crude into TL1
and allow trapped air bubbles to be released. Valves A and B were then closed and valve C
opened. PG1 was operated clockwise again till a small amount of crude oil was released into a
glass beaker. Valve C was then closed and valve B slowly opened while PG1 was operated
clockwise till crude oil emerged at the capillary. After the crude oil pendant drop was formed in
the gas phase, a digital image of each drop was taken and stored on the computer hard drive. The
23
DSA software determined the IFT and other output parameters which were also stored on the
computer hard drive.
The IFT of each crude oil drop was measured and the drops were replaced five times as old drops
were withdrawn from the capillary and new drops were created to ensure repeatability and
accuracy of the data. The measurements were done within five to ten seconds of contact with the
gas phase. At the end and the beginning of each test, the entire system was cleaned by flushing it
with methanol three times and drying with compressed air. IFT measurements were taken for the
three crude samples at 22oC degrees and six pressures ranging from 100-600 psi. The first
contact miscibility pressure of the Gullfak C sample was measured by measuring IFT at an
assumed average temperature of 600C and three pressures ranging from 100-300 psi. The
summary of data collected is shown in Tables 4.1 to 4.7.

CHAPTER 4 RESULTS AND DISCUSSION
Interfacial tension was measured for the Gulffaks C, Arab AH-50 and West Texas intermediate
dead crude oil samples using carbon dioxide and nitrogen gas over a pressure of 100 to 600 psia
and 220C and IFT was also taken for the Gullfaks C dead crude at an assumed reservoir
temperature of 600C and over a pressure of 100 to 300 psia.
The DSA results are presented in Tables 4.1 to 4.7 below. These tables contain analyzed
parameters which include interfacial tension [MN/m], pendant drop volume [l] and pendant
drop surface area [mm*2]. Other parameters also present in the tables that were not considered
includes the pendant drop left, right and middle contact angles (Theta (L,R,M ) [deg]), the drop
base diameter [mm], the fit error [m], the method L-Y and the magnification factor [pix/mm].
Interfacial tension, pendant drop volume and drop surface area measurements were plotted
against pressure ranging from 100 to 600 Psi and at 22oC. The Gullfaks C crude samples
interfacial tension, pendant drop volume and pendant drop surface area measurements using
carbon dioxide gas was also plotted against pressures of 100, 200 and 300 Psi at 60oC. The DSA
measurement for this is shown in Table 4.7. Tables 4.1 to 4.3 shows the measurement data for
the three crude oil samples using carbon dioxide at 220C while Table 4.4 to 4.6 shows the
measurement data using nitrogen also at 220C.
Figures 4.1 to 4.3 shows the variation of the three crude samples pendant drop volume with
pressure using carbon dioxide, Figures 4.4 to 4.6 shows the variation in the pendant drop surface
area with pressure using carbon dioxide and Figures 4.7, 4.8 and 4.9 shows the variation of
interfacial tension with pressure using carbon dioxide. All of these tests were carried out at an
experimental temperature of 220C.
24
25
Figures 4.10 to 4.12 shows the variation of the three crude samples pendant drop volume with
pressure using nitrogen, Figures 4.13 to 4.15 shows the variation in the pendant drop surface area
with pressure using nitrogen and Figures 4.16, 4.17 and 4.18 shows the variation of interfacial
tension with pressure using nitrogen. All of these tests were carried out at an experimental
temperature of 220C.
DSA measurement was also carried out at an assumed reservoir temperature of 600C for the
Gullfaks C crude sample using carbon dioxide over a pressure ranging from 100 to 300 psia. Table
4.7 shows these DSA measurements and Figure 4.19 shows the variation of interfacial tension with
pressure while Figure 4.20 shows the variation of interfacial tension with temperature.
26
4.1. Crude oil and carbon dioxide systems at 220C
Table 4.1: DSA measurement for Arab AH-50 using carbon dioxide
100 Psi , 220C
Fit-
Drop IFT Vol Area BD MAG
Theta(L)[deg] Theta(R)[deg] Theta(M)[deg] Er Method
No. [mN/m] [l] [mm*2] [mm] [pix/mm]
[m]
1 22.37 88.6 88.6 88.7 9.2 20.81 1.56 1.55 L-Y 112.25
2 22.47 88.4 88.4 884 9.27 20.92 1.561 1.5 L-Y 112.01
3 22.31 89.4 89.4 89.4 9.16 20.68 1.57 1.52 L-Y 112.3
4 22.44 96 96 96 8.98 19.97 1.617 1.28 L-Y 111.6
5 22.48 90.3 90.3 90.3 9.23 20.74 1.566 1.52 L-Y 111.61
Average 22.41 9.17 20.62 1.574
200 Psi , 220C
Fit-
[m]
1 21.1 90.8 90.8 90.8 8.93 20.14 1.591 1.36 L-Y 110.29
2 21.23 82.1 82.1 82.1 9.22 21.13 1.579 1.69 L-Y 110.15
3 21.31 93 93 93 8.95 20.03 1.611 1.17 L-Y 109.67
4 21.06 95.4 95.4 95.4 8.95 20.03 1.611 0.99 L-Y 110.21
5 21.27 88.6 88.6 88.6 9.1 20.56 1.587 1.57 L-Y 109.85
Average 21.19 9.03 20.39 1.596
300 Psi , 220C
Fit-
[m]
1 19.2 91 91 91 8.17 18.89 1.586 0.8 L-Y 110.93
2 19.26 94.3 94.3 94.3 8.04 18.45 1.589 0.87 L-Y 110.72
3 19.4 94.9 94.9 94.9 8.09 18.51 1.614 0.81 L-Y 110.23
4 19.18 89.9 89.9 89.9 8.18 18.99 1.573 0.84 L-Y 111
5 19.35 91.3 91.3 91.3 8.22 18.95 1.587 0.89 L-Y 110.53
Average 19.28 8.14 18.76 1.59
400 Psi , 220C
Fit-
[m]
1 17.15 88.9 88.9 88.9 7.5 17.85 1.583 0.751 L-Y 110.733
2 17.28 96.1 96.1 96.1 7.22 16.94 1.631 0.871 L-Y 110.086
3 16.98 89 89 89 7.39 17.66 1.579 0.844 L-Y 111.234
4 17.12 90.1 90.1 90.1 7.46 17.7 1.59 0.772 L-Y 110.664
5 17 86.4 86.4 86.4 7.47 17.95 1.569 0.895 L-Y 111.102
Average 17.11 7.41 17.62 1.59
500 Psi , 220C
Fit-
[m]
1 14.39 91.81 91.81 91.81 6.22 15.42 1.581 1.063 L-Y 113.82
2 14.45 87.08 87.08 87.08 6.43 16.05 1.551 0.819 L-Y 113.57
3 14.53 96.24 96.24 96.24 6.02 14.81 1.603 0.935 L-Y 113.1
4 14.5 94.8 94.8 94.8 6.09 15.01 1.593 0.96 L-Y 113.17
5 14.46 84.68 84.68 84.68 6.5 16.3 1.546 0.704 L-Y 113.49
Average 14.47 6.25 15.52 1.575
600 Psi , 220C
Fit-
[m]
1 12.38 85.1 85.1 85.1 5.68 14.74 1.549 0.62 L-Y 112.955
2 12.37 88.82 88.82 88.82 5.56 14.33 1.555 0.74 L-Y 112.982
3 12.34 93.26 93.26 93.26 5.32 13.65 1.574 0.62 L-Y 112.824
4 12.31 89.77 89.77 89.77 5.48 14.14 1.553 0.67 L-Y 112.947
5 12.29 87.11 87.11 87.11 5.57 14.43 1.543 0.63 L-Y 112.973
Average 12.34 5.52 14.26 1.555
27
Table 4.2: DSA measurement of Gullfaks C using carbon dioxide

100 Psi , 220C
Fit-
[m]
1 24.29 99.4 99.4 99.4 10.1 21.47 1.665 1.067 L-Y 111.345
2 24.25 102.3 102.3 102.3 9.82 20.78 1.719 1.011 L-Y 111.447
3 24.26 97.55 97.55 97.55 10.21 21.78 1.635 0.98 L-Y 111.335
4 24.25 100.66 100.66 100.66 9.98 21.17 1.691 1.052 L-Y 111.401
5
Average 24.26 10.03 21.3 1.678
200 Psi , 220C
Fit-
[m]
1 22.52 96.11 96.11 96.11 9.66 21.03 1.614 0.895 L-Y 111.022
2 22.61 100.77 100.77 100.77 9.37 20.22 1.686 0.945 L-Y 111.065
3 22.54 95.34 95.34 95.34 9.73 21.18 1.616 1.012 L-Y 111.146
4 22.6 99.91 99.91 99.91 9.45 20.4 1.671 1.027 L-Y 111.079
5 22.56 97.32 97.32 97.32 9.62 20.87 1.634 0.987 L-Y 111.123
Average 22.57 9.57 20.74 1.644
300 Psi , 220C
Fit-
[m]
1 20.51 94.2 94.2 94.2 9 20.09 1.603 1.303 L-Y 110.837
2 20.54 98.2 98.2 98.2 8.79 19.46 1.645 1.331 L-Y 110.84
3 20.57 99.14 99.14 99.14 8.72 19.29 1.661 1.524 L-Y 110.825
4 20.49 96.25 96.25 96.25 8.88 19.76 1.622 1.249 L-Y 110.893
5 20.53 98.05 98.05 98.05 8.77 19.46 1.641 1.364 L-Y 110.892
Average 20.51 8.83 19.61 1.634
400 Psi , 220C
Fit-
[m]
1 18.25 91.53 91.53 91.53 8.32 19.09 1.597 1.225 L-Y 110.751
2 18.23 94.13 94.13 94.13 8.19 18.7 1.619 1.519 L-Y 110.647
3 18.03 90.06 90.06 90.06 8.24 19.05 1.586 1.909 L-Y 111.009
4 18.03 89.32 89.32 89.32 8.27 19.14 1.584 1.994 L-Y 110.791
5 18.02 93.4 93.4 93.4 8.1 18.61 1.607 1.545 L-Y 110.807
Average 18.11 8.22 18.92 1.599
500 Psi , 220C
Fit-
[m]
1 15.7 90.78 90.78 90.78 7.31 17.39 1.595 1.028 L-Y 110.833
2 15.69 91.35 91.35 91.35 7.29 17.31 1.596 1.123 L-Y 110.813
3 15.68 94.01 94.01 94.01 7.14 16.9 1.611 1.202 L-Y 110.772
4 15.7 92.34 92.34 92.34 7.24 17.18 1.601 1.182 L-Y 110.758
5 15.72 97.07 97.07 97.07 6.92 16.36 1.634 1.088 L-Y 110.747
Average 17.7 7.18 17.03 1.607
600 Psi , 220C
Fit-
[m]
1 13.35 88.82 88.82 88.82 6.45 15.92 1.587 1.226 L-Y 110.144
2 13.34 85.74 85.74 85.74 6.56 16.28 1.58 1.367 L-Y 110.072
3 13.36 84.29 84.29 84.29 6.61 16.45 1.579 1.46 L-Y 109.963
4 13.37 89.28 89.28 89.28 6.46 15.91 1.591 1.205 L-Y 109.74
5 13.39 86.03 86.03 86.03 6.61 16.33 1.588 1.241 L-Y 109.603
Average 13.36 6.54 16.18 1.585
28
Table 4.3: DSA measurement of West Texas Intermediate using carbon dioxide
100 Psi , 220C
Fit-
[m]
1 24.89 100.43 100.43 100.43 9.92 21.1 1.665 2.448 L-Y 110.352
2 24.95 99.52 99.52 99.52 10.03 21.46 1.623 2.226 L-Y 110.30676
3 24.88 98.62 98.62 98.62 10.08 21.69 1.605 2.018 L-Y 110.33715
4 24.92 96.46 96.46 96.46 10.25 22.15 1.582 1.928 L-Y 110.33981
5 24.93 94.67 94.67 94.67 10.32 22.25 1.582 2.011 L-Y 110.67834
Average 24.91 10.12 21.73 1.6114
200 Psi , 220C
Fit-
[m]
1 22.91 100.85 100.85 100.85 9.04 19.73 1.657 0.99 L-Y 111.264
2 22.9 101.67 101.67 101.67 8.95 19.52 1.672 1 L-Y 111.337
3 22.73 99.76 99.76 99.76 9.04 19.82 1.643 0.946 L-Y 111.726
4 22.94 102.19 102.19 102.19 8.92 19.43 1.689 0.941 L-Y 111.195
5 22.85 98.66 98.66 98.66 9.17 20.12 1.622 0.911 L-Y 111.447
Average 22.87 9.02 19.72 2
300 Psi , 220C
Fit-
[m]
1 20.82 95.2 95.2 95.2 8.57 19.41 1.572 0.751 L-Y 110.197
2 20.91 97.98 97.98 97.98 8.52 19.11 1.618 0.804 L-Y 109.873
3 21.01 99.19 99.19 99.19 8.5 18.96 1.64 0.774 L-Y 109.587
4 20.95 99.24 99.24 99.24 8.47 18.92 1.651 0.763 L-Y 109.756
5 20.84 97.37 97.37 97.37 8.5 19.13 1.5959 0.683 110.179
Average 20.91 8.51 19.11 1.615
400 Psi , 220C
Fit-
[m]
1 18.62 89.08 89.08 89.08 8.04 18.87 1.545 0.654 L-Y 110.067
2 18.58 90.86 90.86 90.86 7.98 18.65 1.568 0.595 L-Y 110.148
3 18.66 95.19 95.19 95.19 7.88 18.19 1.597 0.619 L-Y 109.765
4 18.67 96.78 96.78 96.78 7.81 17.95 1.617 0.759 L-Y 109.653
5 18.59 90.01 90.01 90.01 8.03 18.78 1.549 0.581 L-Y 110.059
Average 18.62 7.95 18.49 1.575
500 Psi , 220C
Fit-
[m]
1 16.31 96.71 96.71 96.71 6.91 16.39 1.614 1.182 L-Y 109.284
2 16.38 93.61 93.61 93.61 7.13 16.97 1.591 1.215 L-Y 109.309
3 16.28 94.12 94.12 94.12 7.05 16.79 1.588 1.103 L-Y 109.463
4 16.3 93.41 93.41 93.41 7.05 16.86 1.58 0.889 L-Y 109.967
5 16.28 91.79 91.79 91.79 7.1 17.06 1.566 0.846 L-Y 110.111
Average 16.31 7.05 16.81 1.589
600 Psi , 220C
Fit-
[m]
1 14.5 96.18 96.18 96.18 5.96 14.79 1.581 0.776 L-Y 109.715
2 14.62 98.46 98.46 98.46 5.88 14.47 1.632 0.992 L-Y 109.06
3 14.66 99.92 99.92 99.92 5.77 14.11 1.665 1.25 L-Y 108.785
4 14.62 97.61 97.61 97.61 5.97 14.66 1.611 1.01 L-Y 108.955
5 14.59 96.34 96.34 96.34 6.03 14.88 1.6 0.925 L-Y 109.285
Average 14.6 5.92 14.58 1.618
29
12
Arab AH-50
10 Linear (Arab AH-50)
Vol [l] 8
6
y = -0.0078x + 10.319
4 R = 0.9706
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.1: Variation Arab AH-50 drop volume with pressure using carbon dioxide at 22 0C
12
Gullfaks C
10 Linear (Gullfaks C)
8
Vol [l]
6 y = -0.0072x + 10.918
R = 0.9894
4
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.2: Variation of Gullfaks C drop volume with pressure using carbon dioxide at 22 0C
30
12
West texas intermediate
10 Linear (West texas intermediate)
Vol [l] 6 y = -0.0078x + 10.842

R = 0.9825
4
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.3: Variation of West Texas intermediate drop volume with pressure using carbon dioxide at 22 0C
The DSA measurements for the three crude oil samples using carbon dioxide gas are shown in
Tables 4.1 to 4.3. All the pendant drops formed for this study formed from the outer surface of the
capillary needle. Figures 4.1 to 4.3 above show that the pendant drop volume reduces in a linear
fashion as pressure increases. The volume of the first crude oil sample, the Arab AH-50 reduced
from 9.17l to 5.52l, that of the Gullfaks C sample reduced from 10.03l to 6.54l and the West
Texas intermediate samples pendant drop volume reduced from 10.12l to 5.92l .This occurred
due to increase in the force exerted by the carbon dioxide gas on the pendant drop. This same
phenomena explains the decrease in the pendant drop surface area as volume is directly
proportional to surface area. It can be seen that the change in volume of the three different crude
samples is approximately the same.

31
25
Arab AH-50
Linear (Arab AH-50)
20
Area [mm*2]
15
y = -0.0136x + 22.617
R = 0.9693
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.4: Variation Arab AH-50 drop surface area with pressure using carbon dioxide at 22 0C
25
Gullfaks C
Area [mm*2]
15 y = -0.0107x + 22.705
R = 0.9748
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.5: Variation of Gullfaks C drop surface area with pressure using carbon dioxide at 22 0C
32
25 West texas
intermediate
20 Linear (West texas
intermediate)
Area [mm*2]
15
y = -0.0129x + 22.917
R = 0.9538
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.6: Variation of West Texas intermediate drop surface area with pressure using carbon
dioxide at 22 0C
The DSA measurements for the three crude oil samples using carbon dioxide gas are shown in
Tables 4.1 to 4.3. Figures 4.4 to 4.6 above show that the pendant drop surface area reduces in a
linear fashion as pressure increases. The pendant drop surface area of the first crude oil sample, the
Arab AH-50 reduced from 20.62 mm2 to 14.26 mm2, that of the Gullfaks C sample reduced from
21.3 mm2 to 16.18 mm2 and the West Texas intermediate samples pendant drop surface area
reduced from 21.73 mm2 to 14.58 mm2. This change in the pendant drop surface area can be
explained as due to the increased force exerted by the carbon dioxide gas on the pendant drop. It
can be seen that the change in the pendant drop surface area for the three different crude samples is
approximately the same.

33
25
Arab AH-50
Linear (Arab AH-50)
20
IFT [mN/m]
15
y = -0.0208x + 25.073
R = 0.9885
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.7: Variation of Arab AH-50 interfacial tension with pressure using carbon dioxide at 22 0C
30
Gullfaks C
Linear (Gullfaks C)
25
20
IFT [mN/m]
15
y = -0.0222x + 26.849
R = 0.9962
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.8: Variation of Gullfaks C interfacial tension with pressure using carbon dioxide at 22 0C
34
30
West Texas Itermediate
25 Linear (West Texas Itermediate)
20
IFT [mN/m]
15
y = -0.021x + 27.056
R = 0.9984
10
0
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.9: Variation of West Texas intermediate interfacial tension with pressure using carbon
dioxide at 22 0C
The DSA measurements for the three crude oil samples using carbon dioxide gas at 220C are
shown in Tables 4.1 to 4.3. Figures 4.7 to 4.9 above show that the pendant drop IFT reduces as
pressure increases in a linear fashion. The IFT of the first crude oil sample, the Arab AH-50
reduced from 22.41 mN/m to 12.34 mN/m, that of the Gullfaks C sample reduced from 24.26
mN/m to 13.36 mN/m and the West Texas intermediate samples IFT reduced from 24.91 mN/m to
14.6 mN/m. It can be seen that the change in IFT for the three different crude samples over the
same pressure range is approximately the same.
Solving the trendline equations of the three crude oil samples for zero IFT yields a first contact
miscibility pressure of 1205 psia for the Arab AH-50, 1214 psia for the Gullfaks C sample and
1288 psia for the West Texas intermediate sample.

35
4.2. Crude oil and nitrogen systems at 220C
Table 4.4: DSA measurement of Arab AH-50 using nitrogen
100 Psi, 220C

Fit-
[m]
1 24.21 91.17 91.17 91.17 10.62 22.62 1.608 0.665 L-Y 110.69
2 24.23 100.73 100.73 100.73 10.4 22.1 1.622 0.38 L-Y 111.75
3 23.98 99.4 99.4 99.4 10.99 23.51 1.603 0.367 L-Y 112.33
4 23.94 88.4 88.4 88.4 10.84 23.14 1.598 0.449 L-Y 112.4
5 24.28 90.29 90.29 90.29 10.97 22.52 1.592 0.34 L-Y 112.36
Average 24.13 10.76 22.99 1.605
200 Psi, 220C
Fit-
[m]
1 23.82 92.1 92.1 92.1 9.72 21.45 1.572 1.51 L-Y 113.197
2 23.91 93.37 93.37 93.37 9.74 21.39 1.577 1.511 L-Y 112.996
3 23.95 89.31 89.31 89.31 9.8 21.76 1.537 1.629 L-Y 112.845
4 23.88 89.53 89.53 89.53 9.77 21.72 1.55 1.506 L-Y 112.99
5 23.96 91.86 91.86 91.86 9.77 21.56 1.55 1.49 112.7173
Average 23.9 9.76 21.58 2
300 Psi, 220C
Fit-
[m]
1 23.1 90.76 90.76 90.76 9.58 21.29 1.558 3.008 L-Y 111.731
2 23.15 89.23 89.23 89.23 9.62 21.46 1.549 2.57 L-Y 111.699
3 23.19 91.37 91.37 91.37 9.61 21.29 1.581 2.793 L-Y 111.627
4 23.06 88.06 88.06 88.06 9.59 21.49 1.544 2.4 L-Y 112.102
5 23.13 89.456 89.456 89.456 9.62 21.43 1.553 2.386 L-Y 111.9082
Average 23.13 9.6 21.39 1.557
400 Psi, 220C
Fit-
[m]
1 22.6 90.43 90.43 90.43 9.5 21.17 1.562 3.43 L-Y 111.767
2 22.5 88.91 88.91 88.91 9.51 21.27 1.557 3.086 L-Y 112.101
3 22.57 86.58 86.58 86.58 9.56 21.51 1.55 2.678 L-Y 112.115
4 22.63 85.56 85.56 85.56 9.6 21.63 1.546 2.562 L-Y 112.02
5 22.61 84.64 84.64 84.64 9.58 21.66 1.54 2.511 L-Y 112.127
Average 22.58 9.55 21.45 1.55
500 Psi, 220C
Fit-
[m]
1 22.16 87.41 87.41 87.41 9.49 21.33 1.551 2.873 L-Y 111.71
2 22.07 88.47 88.47 88.47 9.41 21.14 1.552 2.955 L-Y 112.026
3 22.21 85.61 85.61 85.61 9.51 21.49 1.547 2.511 L-Y 111.754
4 22.05 87.7 87.7 87.7 9.4 21.18 1.551 2.73 L-Y 112.215
5 22.1 84.95 84.95 84.95 9.45 21.43 1.542 2.397 L-Y 112.214
Average 22.12 9.45 21.31 1.55
600 Psi, 220C
Fit-
[m]
1 21.56 90.58 90.58 90.58 9.17 20.65 1.557 3.14 L-Y 112.182
2 21.52 86.3 86.3 86.3 9.19 20.96 1.54 2.637 L-Y 112.47
3 21.5 86.67 86.67 86.67 9.19 20.92 1.541 2.656 L-Y 112.607
4 21.48 90.4 90.4 90.4 9.13 20.6 1.554 3.074 L-Y 112.555
5 21.63 85.61 85.61 85.61 9.25 21.1 1.532 2.512 L-Y 112.323
Average 21.54 9.19 20.85 1.545
36
Table 4.5: DSA measurement of Gullfaks C using nitrogen
100 Psi ,220C

IFT Vol Area BD Fit-Er MAG
Drop No. Theta(L)[deg] Theta(R)[deg] Theta(M)[deg] Method
[mN/m] [l] [mm*2] [mm] [m] [pix/mm]
1 24.09 96.15 96.15 96.15 10.12 21.77 1.619 2.898 L-Y 112.211
2 24.04 94.97 94.97 94.97 10.11 21.85 1.588 2.588 L-Y 112.489
3 24.2 92.25 92.25 92.25 10.3 22.33 1.577 1.97 L-Y 112.168
4 24.23 93.03 93.03 93.03 10.28 22.24 1.573 2.055 112.088
5 24.1 90.76 90.76 90.76 10.34 22.47 1.564 1.786 L-Y 112.328
Average 24.13 10.23 22.13 1.582
200 Psi , 220C
1 23.97 89.73 89.73 89.73 10.46 22.71 1.572 1.499 L-Y 111.486
1.4383 111.48333
2 23.96 89.625 89.625 89.625 10.44 22.68 1.571 L-Y
333 33
3 23.96 90.54 90.54 90.54 10.4 22.57 1.572 1.479 L-Y 111.536
4 24 90.54 90.54 90.54 10.42 22.6 1.57 1.459 L-Y 111.498
5 23.93 89.17 89.17 89.17 10.43 22.71 1.565 1.452 L-Y 111.643
Average 23.96 10.43 22.65 2
300 Psi , 220C
1 23.73 95.12 95.12 95.12 10.15 21.91 1.595 1.735 L-Y 111.646
2 23.74 94.34 94.34 94.34 10.2 22.04 1.588 1.62 L-Y 111.607
3 23.61 88.98 88.98 88.98 10.33 22.58 1.557 1.701 L-Y 111.863
4 23.63 91.84 91.84 91.84 10.27 22.3 1.574 1.387 L-Y 111.821
5 23.65 90.1 90.1 90.1 10.34 22.52 1.562 1.686 L-Y 111.697
Average 23.67 10.26 22.27 1.575
400 Psi , 220C
1 23.22 89.83 89.83 89.83 10.32 22.48 1.576 2.367 L-Y 111.251
2 23.22 92.16 92.16 92.16 10.29 22.26 1.599 3.222 L-Y 110.915
3 22.89 83.27 83.27 83.27 10.37 22.95 1.572 1.732 L-Y 111.972
4 23.03 83.87 83.87 83.87 10.43 23 1.572 1.869 L-Y 111.644
5 23.15 84.58 84.58 84.58 10.47 23.02 1.569 1.959 L-Y 111.424
Average 23.1 10.38 22.74 1.578
500 Psi , 220C
1 22.78 90.69 90.69 90.69 10.21 22.24 1.578 2.525 L-Y 111.064
2 22.79 91.41 91.41 91.41 10.09 22.05 1.826 1.808 L-Y 111.044
3 22.7 92.87 92.87 92.87 10.01 21.83 1.583 2.099 L-Y 111.186
4 22.44 87.83 87.83 87.83 10 22.14 1.55 1.8 L-Y 111.858
5 22.45 86.82 86.82 86.82 10.04 22.26 1.551 1.9 L-Y 111.819
Average 22.63 10.07 22.1 1.618
600 Psi, 220C
1 22.29 91.74 91.74 91.74 10.02 21.89 1.586 2.672 L-Y 111.095
2 22.17 95.27 95.27 95.27 9.67 21.16 1.581 2.287 L-Y 111.353
3 22.25 89.99 89.99 89.99 10.02 22.02 1.567 2.376 L-Y 111.28
4 22.17 89.57 89.57 89.57 10.02 22.04 1.568 2.25 L-Y 111.453
5 22.26 89.92 89.92 89.92 10.05 22.05 1.568 2.376 L-Y 111.272
Average 22.23 9.96 21.83 1.574
37
Table 4.6: DSA measurement of West Texas intermediate using nitrogen

100 Psi ,220C
Drop IFT Vol Area BD Fit-Er MAG
Theta(L)[deg] Theta(R)[deg] Theta(M)[deg] Method
No. [mN/m] [l] [mm*2] [mm] [m] [pix/mm]
1 25.38 93.8 93.8 93.8 10.5 22.48 1.601 1.07 L-Y 110.66
2 25.59 91.2 91.2 91.2 10.74 23.01 1.606 1.1 L-Y 110.65
3 25.43 88.5 88.5 88.5 10.6 23.01 1.604 1.13 L-Y 112.71
4 25.59 92.3 92.3 92.3 10.56 22.71 1.585 1.06 L-Y 112.24
5 25.51 92.1 92.1 92.1 10.52 22.66 1.581 1.09 L-Y 112.42
Average 25.5 10.58 22.77 1.595
200 Psi , 220C
1 24.91 86.78 86.78 86.78 10.73 23.25 1.596 2.951 L-Y 111.88
2 24.83 89.24 89.24 89.24 10.53 22.83 1.584 2.914 L-Y 111.88
3 24.85 85.49 85.49 85.49 10.64 23.23 1.583 2.655 L-Y 111.88
4 24.87 87.08 87.08 87.08 10.58 23.04 1.578 2.788 L-Y 111.88
5 24.84 86.52 86.52 86.52 10.62 23.13 1.586 2.773 L-Y 111.88
Average 24.86 10.62 23.1 2
300 Psi , 220C
1 24.63 92.2 92.2 92.2 10.4 22.45 1.589 3.01 L-Y 111.88
2 24.64 92 92 92 10.41 22.48 1.587 3.01 L-Y 111.88
3 24.63 91.9 91.9 91.9 10.41 22.49 1.584 3.1 L-Y 111.88
4 24.64 90 90 90 10.5 22.76 1.579 3.2 L-Y 111.88
5 24.62 92.6 92.6 92.6 10.31 22.29 1.58 2.87 L-Y 111.88
Average 24.63 10.41 22.49 1.584
400 Psi , 220C
1 24.32 89.4 89.4 89.4 10.47 22.73 1.572 0.339 L-Y 113.068
2 24.36 88.7 88.7 88.7 10.5 22.83 1.569 0.382 L-Y 113.039
3 24.33 90.2 90.2 90.2 10.44 22.64 1.573 0.415 L-Y 113.106
4 24.28 89.7 89.7 89.7 10.42 22.66 1.571 0.327 L-Y 113.2456
5 24.35 90.2 90.2 90.2 10.42 22.62 1.572 0.322 L-Y 113.099
Average 24.33 10.45 22.7 1.571
500 Psi , 220C
1 23.97 92.3 92.3 92.3 10.26 22.24 1.579 0.2988889 L-Y 112.85
2 23.9 93.3 93.3 93.3 10.18 22.07 1.584 0.406 L-Y 113.052
3 24.03 93.9 93.9 93.9 10.22 22.07 1.589 0.313 L-Y 112.739
4 23.99 91.2 91.2 91.2 10.31 22.39 1.573 0.2911111 L-Y 112.8533333
5 23.98 92.1 92.1 92.1 10.27 22.27 1.576 0.316 L-Y 112.852
Average 23.97 10.25 22.21 1.58
600 Psi, 220C
1 23.74 95.7 95.7 95.7 10.11 21.78 1.609 0.375 L-Y 112.324
2 23.63 93.14 93.14 93.14 10.2 22.09 1.588 0.356 L-Y 112.591
3 23.59 91.39 91.39 91.39 10.26 22.28 1.579 0.571 L-Y 112.656
4 23.6 93.91 93.91 93.91 10.14 21.94 1.592 0.428 L-Y 112.621
5 23.66 96.32 96.32 96.32 10.03 21.62 1.609 0.374 L-Y 112.448
Average 23.64 10.15 21.94 1.595
38
9.8
Arab AH-50
9.7 Linear (Arab AH-50)
9.6
9.5
Vol [l]
9.4
9.3
y = -0.0013x + 10.016
9.2 R = 0.9444
9.1
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.10: Variation of Arab AH-50 drop volume with pressure using nitrogen at 22 0C
10.5
Gulfaks C
10.4 Linear (Gulfaks C)
10.3
Vol[l]
10.2
10.1
10
y = -0.0016x + 10.58
R = 0.9892
9.9
0 100 200 300 400 500
Pressure (psia)
Figure 4.11: Variation of Gullfaks C drop volume with pressure using nitrogen at 220C
39
10.7
West texas intermediate
10.6 Linear (West texas intermediate)
10.5
Vol [l] 10.4
10.3
10.2
y = -0.0011x + 10.798
R = 0.9582
10.1
0 100 200 300 400 500 600 700
Pressure(psia)
Figure 4.12: Variation of West Texas intermediate drop volume with pressure using nitrogen at 220C
The DSA measurements for the three crude oil samples using nitrogen gas are shown in Tables 4.4
to 4.6 . All the pendant drops formed for this study using nitrogen formed from the outer surface of
the capillary needle. Figures 4.10 to 4.12 above show that the pendant drop volume reduces in a
linear fashion as pressure increases. The volume of the first crude oil sample, the Arab AH-50
reduced from 10.8l to 9.19l, that of the Gullfaks C sample reduced from 10.23l to 9.96l and
the West Texas intermediate samples pendant drop volume reduced from 10.58l to 10.15l. The
increase in the force exerted by the nitrogen gas on the pendant drop can be used to explain this
reduction in volume. This same phenomena explains the decrease in the pendant drop surface area
as volume is directly proportional to surface area. It can be seen that the change in pendant volume
for the three different crude samples is approximately the same. However, the change in pendant
drop volume is very small compared to the change experienced using carbon dioxide.
40
21.7
21.6 Arab AH-50
21.5
21.4
Area [mm*2]
21.3
21.2
21.1
21
R = 0.8238
20.9
20.8
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.13: Variation of Arab AH-50 drop surface area with pressure using nitrogen at 22 0C
22.7
Gulfaks C
22.6
22.5 Linear (Gulfaks C)
22.4
Area [mm*2]
22.3
22.2
22.1
22
21.9
y = -0.0026x + 22.87
21.8 R = 0.9779
21.7
0 100 200 300 400 500
Pressure (psia)
Figure 4.14: Variation of Gullfaks C drop surface area with pressure using nitrogen at 22 0C
41
23.2
West texas
23 intermediate
Linear (West texas
22.8
intermediate)
Area [mm*2]
22.6
22.4
22.2
22 y = -0.0026x + 23.475
R = 0.9124
21.8
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.15: Variation of West Texas intermediate drop surface area with pressure using nitrogen at
22 0C
The DSA measurements for the three crude oil samples using nitrogen gas are shown in Tables 4.4
to 4.6 . Figures 4.13 to 4.15 above show that the pendant drop surface area reduces in a linear
fashion as pressure increases. The pendant drop surface area of the first crude oil sample, the Arab
AH-50 reduced from 22.99 mm2 to 20.85 mm2, that of the Gullfaks C sample reduced from 22.13
mm2 to 21.83 mm2 and the West Texas intermediate samples pendant drop surface area reduced
from 22.77 mm2 to 21.94 mm2. This change in pendant drop surface area can attributed to the
increased force exerted by the nitrogen gas on the pendant drop. It can be seen that the change in
the pendant drop surface area for the three different crude samples is approximately the same.
However, the change in pendant drop surface area is very small compared to that experienced
using carbon dioxide.

42
25
Arab AH-50
24.5
Linear (Arab AH-50)
24
23.5
IFT [mN/m]
23
22.5
22
y = -0.0054x + 24.785
21.5 R = 0.9826
21
0 100 200 300 400 500 600 700
Pressure (psia)
Figure 4.16: Variation of drop interfacial tension with pressure using nitrogen at 22 0C
24.5
Gullfaks C
23.5
IFT [mN/m]
y = -0.004x + 24.697
23 R = 0.9587
22.5
22
21.5
0 100 200 300 400 500 600 700
Pressure (Psi)
Figure 4.17: Variation of Gullfaks C drop interfacial tension with pressure using nitrogen at 22 0C
43
26
West Texas Intermediate
25.5 Linear (West Texas Intermediate)
25
IFT [mN/m] 24.5
24 y = -0.0035x + 25.714
R = 0.9737
23.5
23
0 100 200 300 400 500 600 700
Pressure (Psi)
Figure 4.18: Variation of West Texas intermediate drop interfacial tension with pressure using
nitrogen at 22 0C
The DSA measurements for the three crude oil samples using carbon dioxide gas at 22 0C are
shown in Tables 4.4 to 4.6 . Figures 4.16 to 4.18 above shows that the pendant drop IFT reduces as
pressure increases in a linear fashion from 200 psia. The IFT of the first crude oil sample, the Arab
AH-50 reduced from 24.13 mN/m to 21.54 mN/m, that of the Gullfaks C sample reduced from
24.13 mN/m to 22.23 mN/m and the West Texas intermediate samples IFT reduced from 25.5
mN/m to 23.64 mN/m. It can be seen that the change in IFT for the three different crude samples
over the same pressure range is approximately the same. However the change in IFT is very small
compared to that gotten using carbon dioxide.
Solving the trendline equations of the three crude oil samples for zero IFT yields a first contact
miscibility pressure of 4377 psia for the Arab AH-50, 5437 psia for the Gullfaks C sample and
8232.25 psia for the West Texas intermediate sample.

44
4.3 Gullfaks C using carbon dioxide at 600C
The pressures required to achieve first contact miscibility using nitrogen compared to carbon
dioxide is relatively large, on this basis, carbon dioxide was found to be a more suitable gas for
miscible flooding thereby confirming numerous literature work. Hence IFT measurement was
carried out for the Gullfaks C crude oil sample at an assumed reservoir temperature of 60 0C over a
pressure of 100 to 300 Psi and the DSA measurement is given in Table 4.7 below.
Table 4.7: DSA measurement of Gullfaks C using carbon dioxide at reservoir temperature
100 Psi, 600C

Fit-
[m]
1 21.64 91.19 91.19 91.19 9.95 21.71 1.618 4.25 L-Y 113.723
2 21.7 94.14 94.14 94.14 9.72 21.21 1.612 6.43 L-Y 114.496
3 21.7 91.74 91.74 91.74 9.89 21.6 1.607 5.978 L-Y 114.312
4 21.7 92.57 92.57 92.57 9.89 21.5 1.617 4.48 L-Y 113.746
5 21.77 92.64 92.64 92.64 9.9 21.56 1.62 5.645 L-Y 113.844
Average 21.7 9.55 21.45 1.55
0
200 Psi, 60 C
Fit-
[m]
1 20.6 90.56 90.56 90.56 9.42 21 1.576 3.24 L-Y 113.133
2 20.6 90.16 90.16 90.16 9.43 21.04 1.577 3.14 L-Y 113.159
3 20.61 90.72 90.72 90.72 9.42 20.97 1.577 3.255 L-Y 113.037
4 20.61 90.54 90.54 90.54 9.42 21 1.577 3.219 L-Y 113.07
5 20.62 90.89 90.89 90.89 9.41 20.96 1.577 3.217 L-Y 113.09
Average 20.61 9.42 20.99 2
0
300 Psi, 60 C
Fit-
[m]
1 18.91 90 90 90 8.91 20.21 1.573 1.75 L-Y 105.887
2 18.91 89.9 89.9 89.9 8.92 20.21 1.573 1.716 L-Y 105.887
3 18.92 90 90 90 8.92 20.22 1.573 1.685 L-Y 105.867
4 18.92 90 90 90 8.92 20.21 1.573 1.695 L-Y 105.878
5 18.93 90 90 90 8.92 20.22 1.572 1.664 L-Y 105.858
Average 18.92 8.92 20.21 1.573
45
22.5
Gullfaks C
21.5
21
IFT [mN/m
20.5
20
19.5
y = -0.0139x + 23.193
19
R = 0.9845
18.5
0 50 100 150 200 250 300 350
Pressure (psia)
Figure 4.19: Variation of Gullfaks Cs Interfacial tension with pressure using carbon dioxide at 600C
Figure 19 shows the variation in IFT with pressure at 600C over a pressure range of 100 to 300
psia. Solving the trendline equations for zero IFT yields a first contact miscibility pressure of
1668Psi for the Gullfaks C sample.This is higher than the estimated pressure at 220C .
25
Gulfaks C (60 Degrees)
24 Gullfaks C (22 degrees)
23
IFT [mN/m
22
21
20
19
18
0 50 100 150 200 250 300 350
Pressure (psia)
Figure 4.20: Variation of Gullfaks Cs Interfacial tension with temperature

46
Figure 4.20 shows that first contact minimum miscibility pressure increases with temperature
increase which goes against the general convention that minimum miscibility pressure reduces
with temperature increase. The number of data points used in plotting the IFT versus pressure
graph at 600C could be the cause of the difference in the result; however, more data points could
not be gotten at 600C due to equipment malfunction.

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS
1.1 Conclusions
Minimum miscibility pressure is an essential parameter in planning minimum miscibility
flooding .This parameter depends on the type of gas used as well as reservoir temperature.
This study has determined minimum miscibility pressure of carbon dioxide and nitrogen
separate system. The following are the conclusions that can be drawn from this experimental
work.
1) First contact minimum miscibility pressure can be obtained by measuring the variation in
pendant drop IFT data with temperature and pressure.
2) At a constant temperature, Crude oil pendant drop volume and surface area decreases
with increases in pressure.
3) Besides pressure increase, other parameters such as the density of the gas used affect the
pendant drop volume surface area and IFT.
4) Crude oil pendant drop forms the outer surface of the needle regardless of the gas used.
5) On the basis of IFT reduction with pressure increase, carbon dioxide is more suitable for
miscible flooding than nitrogen by more than 100 %.
6) More than three pressure data points are required to accurately estimate miscibility
pressure at a particular temperature.
7) Data generated from this study could be used as a basis to generate correlations that
predicts first contact miscibility pressure for the Arab AH-50, the Gullfaks C and the
West Texas intermediate crude samples using Carbon dioxide and Nitrogen.
49
48
5.2 Recommendations
1) A gas piston pump should be added to the pendant drop apparatus so as to increase the
range of pressure that can be used on the apparatus. The current set up restricts the
pressure range to that of the gas cylinder used.
2) More data points should be gotten at increased temperature and pressure to increase the
accuracy of IFT estimation.
3) The impact of gas density on the crude oil pendant drop volume, surface area and IFT
could be further investigated.

49
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MEASUREMENT OF CRUDE OIL INTERFACIAL TENSION TO

DETERMINE MINIMUM MISCIBILITY IN CARBON DIOXIDE

Submitted in partial fulfilment of the requirements

Copyright by Ibrahim O. Awari-Yusuf, 2013

Graduate Studies for acceptance a thesis entitled MEASUREMENT OF CRUDE OIL

INTERFACIAL TENSION TO DETERMINE MINIMUM MISCIBILITY IN CARBON

DIOXIDE AND NITROGEN by Ibrahim O. Awari-Yusuf in partial fulfilment of the

requirements for the degree of Master of Engineering.

Dated: August 19, 2013

DATE: August 19, 2013

AUTHOR: Ibrahim O. Awari-Yusuf

TITLE: MEASUREMENT OF CRUDE OIL INTERFACIAL TENSION TO

DEPARTMENT OR SCHOOL: Petroleum Engineering

DEGREE: MEng. CONVOCATION: October YEAR: 2013

Permission is herewith granted to Dalhousie University to circulate and to have copied

have supported me through the course of my studies.

LIST OF TABLES ................................................................................................................... vii

Table 3.1: Calibration data .................................................................................................16

Figure 2.1: Pure carbon dioxide phase diagram ................................................................ 5

= Oil density at reservoir conditions(lb/ft3)

= Fake density used in oil density calculation (lb/ft3)

= Pseudo liquid density (lb/ft3)

= Oil density at reservoir bubblepoint (lb/ft3)

= The difference in density of the two phases (Kg/m3)

= Adjustment of oil density due to pressure (lb/ft3)

= Adjustment of oil density due to temperature (lb/ft3)

= Weighted average surface gas specific gravity

= Stock tank oil specific gravity

= Separator gas specific gravity

= Interfacial tension (mN/m)

= Weighted average oil compressibility from bubble point pressure to a higher

= Bubblepoint pressure (psia)

= Pressure difference at a reference plane (psia)

= Principal radii of curvature

process (Danesh, 1998).

process would become semi miscible or immiscible (Fanchi, 2006).

Manrique, 2010; Farouq & Thomas, 1996).

This work is being carried out for the following reasons:

1) To understand the principles behind miscible gas injection as an EOR method .

gas for miscible flooding compared to nitrogen.

crude oil samples in carbon dioxide and nitrogen systems.

5) To determine if IFT varies linearly with pressure at non reservoir conditions.

while existing in a single indistinguishable phase.

2.2. Miscible flooding

LPG (Schlumberger, 2013).

2.3. Carbon dioxide flooding

(Stright Jr., Aziz, & Settari, 1977), etc.

2.3.1. Properties of carbon dioxide

depending on its temperature and pressure.

2.4. Nitrogen flooding

without fracturing the formation (Lindley, 2011).

2.4.1. Nitrogen properties

Nitrogen is a nontoxic, non-flammable gas at atmospheric conditions. It has a critical

atmospheric air by volume (Air Liquide, 2013).

2.5. Miscible flooding mechanism

oil, natural gas and the injected gas (Lindley, 2011).

2.6. Interfacial tension

and pressure (Schlumberger, 2013).

2.7. Minimum miscibility pressure

the porous media (Alomair et al, 2011)

2.8. Experimental methods for determining minimum miscibility

extrapolated from IFT data at reservoir conditions.

2.9. Crude oil density