SPE 57286
New Experimental Approaches in Minimum Miscibility Pressure (MMP) Determination
Nor Idah Kechut, SPE, Zahidah Md. Zain, SPE, Noraini Ahmad, PETRONAS Research & Scientific Services Sdn. Bhd.
and DM Anwar Raja DM Ibrahim, SPE, PETRONAS Carigali Sdn. Bhd.
Copyright 1999, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 1999 SPE Asia Pacific Improved Oil Recovery
Conference to be held in Kuala Lumpur, Malaysia, 25–26 October 1999.
This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
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Abstract
Miscible CO2 gas injection has nowadays become one
of the most important enhanced oil recovery (EOR)
processes. For optimal displacement efficiency, CO2
flooding should be conducted at pressures greater than a
minimum miscibility pressure (MMP), which is a function
of temperature and composition of injection gas. The MMP
has been defined as the minimum pressure at which the
injected gas and the oil become miscible with each other.
Approaching miscibility, the interfacial tension (IFT)
between phases decreases resulting in decreased residual oil
saturation, hence, higher oil recovery efficiency.
This paper presents two new experimental approaches
to determine the MMP for the miscible CO2 gas injection.
The first approach consists of measuring the interfacial
tension (IFT) between the injected gas and the oil at
reservoir temperature and varying pressures using a
prototype Vapour Liquid Equilibrium-Interfacial Tension
(VLE-IT) equipment. The miscibility of the injected gas
and the oil is evaluated on the basis of the vanishing IFT
between the two phases.
The second experimental approach involves the MMP
determination by displacement test using a prototype Gas
Extraction & Miscibility Analyser (GEMA)*. The invention
incorporates a capillary-sized unpacked column or a micro-
slim tube (MST) as opposed to the conventional packed
slim-tube widely reported in literature. The MMP analysis
time reduces up to one tenth of the conventional slim tube
or sand-pack flood. * patent pending1
It is demonstrated in this study that the approaches are
reliable and fast for determining CO2 MMPs. The IFT
method yields the quantitative information and the IFT
MMP obtained is verified by the micro-slim tube
displacement tests. The MMP obtained also falls within the
range of values predicted by published correlations.
Introduction
Capillary force as the consequence of the interfacial
tension (IFT) between the oil and water is probably the
most important force, which results in large quantities of
the oil originally in place in a reservoir rock being
unrecoverable by the conventional gas-drive or water flood
methods. As shown in Figure 12 it is apparent that if the
capillary number becomes infinite, residual oil saturation
can be reduced to its lowest possible value that gives
highest oil recovery. At infinite capillary number, the IFT
between the oil and the displacing fluid is zero and the two
phases become miscible with each other.
R e s id u a l o il s a tu ra tio n , % P V
C a p . n o = u µ /σ
w h e re u = v e lo c ity
µ = v is c o s ity
σ = in te rfa c ia l te n s io n
C a p illa ry n u m b e r
Figure 1: Dependence of residual oil saturation on
capillary number (from Stalkup)
The miscible CO2 flooding is one of the enhanced oil
recovery (EOR) techniques for achieving low IFT. The
technique has received considerable attention in the
industry for CO2 high displacement efficiency and
relatively low cost. At a pressure greater than the CO2
MMP, miscible recovery of reservoir oil can be achieved. It
is important to know the CO2 MMP for screening and
selecting reservoirs for CO2 injection projects since the
2 Nor Idah Kechut, Zahidah Md. Zain, Noraini Ahmad, DM Anwar Raja DM Ibrahim
candidate reservoir must be capable of withstanding an
average reservoir pressure greater than the CO2 MMP for
obtaining the highest recovery3. It also determines the
model to be used in predicting or simulating reservoir
performance as a result of CO2 injection.
A prior well-known method used to determine MMP
is the 'slim-tube' method2,3,4,5,10,11 which involves loading oil
sample into a column packed with porous media (having
internal diameter (ID) of 4 to 19 mm5) and then injecting
gas/gases to displace/extract the oil.
The problems with this conventional apparatus include
the difficulties associated with the relatively large column
diameter used and the difficulties in obtaining uniform
packing. The non-uniform porosity and flow rates that
occur as a result give rise to transverse concentration
fingers, making it more difficult to obtain accurate and
reproducible data repeatedly in a consistent manner
between laboratories. To minimise this effect, it is often
necessary to operate at extremely low flow rates so that
molecular diffusion can dampen the unwanted transverse
compositional variations. As a consequence, it can take
several days to run optimal tests with a slim-tube packed
column. Therefore, there is still a need for a measuring
apparatus that can determine MMP more accurately and
quickly with direct measurement of displacement recovery
and visual confirmation to avoid error and ambiguity as
disclosed in the prior method.
This paper demonstrates the use of the VLE-IT
equipment to measure IFT of stock tank oil (STO) with CO2
gas at reservoir temperature of 77 oC and various pressures.
By making a plot of IFT against pressure, the MMP value is
obtained by extrapolation to zero IFT. This paper also
describes a new approach in determining MMP whereby an
unpacked transparent capillary column with ID of 0.32 mm
is used rather than the conventional packed column. Due to
the standardised nature of the column, repeatability between
laboratories can be achieved. This new approach can thus
be adopted as a standard method to experimentally
determine the CO2 MMP for an oil.
Approach I: MMP from Interfacial Tension (IFT)
Measurement
Apparatus and procedure. The VLE-IT equipment and its
major components are illustrated in Figure 26. It consists of
a fixed volume cell made of 316 s/s with glass windows on
opposite sides and it can withstand pressures up to 10,000
psi and temperatures up to 150 oC. There is a light source to
illuminate the windows to permit the capture of drop profile
images by using a camera system on the opposite side. The
camera system is connected to a monitor and a PC equipped
with a frame grabber and image analysis software.
There are also two variable volume chambers
connected to the cell by computer-controlled switching
valves, which determine the mixture flow between the first
variable volume chamber and the capillary tip located in the
57286
upper portion of the cell. Pressure and temperature in the
cell and chambers are displayed continuously on the
monitor.
H igh
Temperature
Densitometer T V Monitor &
Video Recorder
VLE-IT Cell & Enclosure
Frame Grabber
Board
Computer Control
& Data Processing
Micro Video Camera
& Illumination Printer
Figure 2: VLE-IT Equipment Major Components
Test selections are made interactively, allowing the
user to set the test criteria. The chamber volumetric rates
can be varied from 1 to 50 cm3/min and a constant pressure
mode is used to adjust liquid and/or vapour volumes during
mixing, and to eventually set the position of the gas-liquid
interface in the VLE-IT cell.
The densities of liquid and gas phases are measured
using a PAAR DMA 512P density-measuring cell, which is
connected to mPDS 2000 evaluation unit. The external cell
is heated to the desired temperature by a computer-
controlled heating block.
Drop volume and pendant drop techniques are used in
the IFT measurement. The drop volume technique
requires running the variable volume chambers of the
equipment at slow rates. The volume of a drop (Vd) is given
by:
Vd = flow rate x [time/number of drops] ………...[A1]
The IFT (σ) is then calculated using equation:
σ = [Vd (ρ1 - ρ2)gc . F / r] ..………………. [A2]
where F is a function of r/Vd1/3 based on the work by
Harkins and Brown7, extrapolated from tables given by
Lando and Oakley8.
In the alternative pendant drop technique, the image
of the drop hanging from the tip is captured and analysed.
The image analysis applies a computational procedure
derived by Rotenberg etal9 for obtaining IFT and contact
angle from the shape of an axisymmetric fluid interface.
In the procedure, an interface profile from a
mathematically derived curve that satisfies the Laplace
capillary equation is constructed:
σ(1/ R1+ 1/ R2 ) = ∆P ………………………. [A3]
57286 New Experimental Approaches in Minimum Miscibility Pressure (MMP) Determination 3

where ∆P = pressure difference across the interface system since miscibility between two phases is achieved
surface of a pendant drop, R1, R2 = two principle radii of when there is no IFT between them. It can be seen in Figure
curvature 3 that the best-fitted line to the IFT data up to 1913 psig,
In this study, the IFT value obtained by the drop intersects the zero IFT axis at a pressure of about 2400 psig.
volume technique was used as the first estimate to match
the shape of the physically observed pendant drop to the Pressure IFT values (mN/m)
(psig)
mathematically derived one. Iterative calculations were then
Drop Volume Pendant drop
made using an in-house program called DROP until the best 1206 7.24 7.00
fit between the two shapes was obtained. The IFT values 1330 5.49 5.40
were then plotted against pressure. The curve was 1435 3.98 4.00
extrapolated to zero IFT in order to get the MMP value. 1515 3.53 3.50
1913 0.64 0.41
Validation with published values. To validate the
performance of the VLE-IT equipment, IFT was determined Table 3: IFT for STO-CO2 @ 77 oC
for a methane-pentane mixture. A good agreement of results
8
was obtained for both drop volume and pendant drop
Drop Volume
methods. The values are also within the range of published 7

Pendant drop
results as shown in Table 1. 6

Calculated
5

IFT (mN/M)
Pressure IFT by drop IFT by pendant IFT reported in literature
4
(bar) volume drop (mN/m)
(mN/m) (mN/m) 3

70 6.32 6.42 6.2 to 6.5 2 2400 psig

106 2.91 3.01 2.8 to 3.3
130 1.44 1.40 1.2 to 1.5 1

0
Table 1: IFT for methane-pentane @ 24 oC 0 500 1,000 1,500 2,000 2,500 3,000 3,500 4,000

PRESSURE (PSIG)

Results. The measurements of equilibrium IFT were Figure 3: Interfacial tension for STO with CO2
performed at reservoir temperature and selected pressures
on a STO the properties of which are given in Table 2.
Approach II: MMP from Micro-slim Tube
Compo. Weight % Compo. Weight % Displacement Tests
C7 0.46 C18 2.88
C8 3.41 C19 2.58 Apparatus and procedure. The Gas Extraction &
C9 7.72 C20 2.14 Miscibility Analyser (GEMA), which incorporates a micro-
C10 10.36 C21 1.81 slim tube (MST) apparatus, is shown schematically in
C11 12.03 C22 1.62
Figure 4.
C12 11.60 C23 1.51
C13 10.26 C24 1.34
C14 8.92 C25 1.43
C15 7.89 C26 1.22
C16 4.96 C27 1.03 TV Monitor &
Video Recorder
C17 4.02 C28 0.80 Micro-slim tube
in oven
Density = 0.8267 g/cc
MWt. = 170.4

Table 2: Stock tank oil composition used Computer Control

Micro-video camera & Data Processing

The test pressures were selected so as to allow two

phases to exist in the VLE-IT cell at test conditions. The
gas and STO were pre-equilibrated in the cell before drop
profile images were acquired. The determination of MMP Supercritical fluid
extractor Gas Chromatograph

for one oil – gas system took about 3 to 4 days, including

the time taken for heating and cleaning the unit.
The results of the VLE-IT experiments are tabulated in
Table 3 and presented in Figure 3. The results show that
increasing the pressure decreases the IFT until it reaches
zero at a certain pressure. This pressure is the MMP of the
Figure 4: Schematic diagram of GEMA
The MST is an unpacked, coiled fused silica capillary
column of 30 m long with 0.32 mm ID, can withstand
pressures up to 4000 psig and temperatures up to 300 oC.
4 Nor Idah Kechut, Zahidah Md. Zain, Noraini Ahmad, DM Anwar Raja DM Ibrahim 57286

The Pore Volume of the system is approximately 3.71 cm 3. Validation with published values. The micro-slim tube
A coiled stainless steel column having ID of 0.32 to 0.53 was calibrated against displacement tests on hexadecane-
mm can also be used especially when operating at much CO2 at 50 oC as conducted by Johnson & Pollin10. Table 4
higher pressures. and Figure 5 show the comparison of the two systems.
The supply of the solvent and the sample is by The recovery profile in both cases is the same i.e. the
mercury-free, rapid recharge high-pressure syringe pumps. recovery increases gradually until it levels off at certain
The pumps are computer programmable and pulseless with pressure. Considering the different nature of the 'slim-tube'
option of constant pressure, constant rate and used, the 12.5% difference in the obtained MMP values is
programmable pressure or rate. deemed acceptable.
There are 4-ports and 6-ports switching valves which
determine the flow path of the fluid. The MST is housed in Parameter This study Johnson & Pollin
a constant temperature oven. Elevated temperatures are Slim tube 30m x 0.32 mm ID 15 m x 6.35 mm ID
Packing un-packed 100-140 mesh glass beads
achieved by means of Watlow heating tapes inside the oven
Linear rate, cm/hr 18 650 500
and also around the pumps, controlled by electronic MMP obtained 2100 2400
temperature controller through a computer program.
The ultra-violet (UV) detector at the outlet end of the Table 4: Displacement tests on C16 - CO2 @ 50 oC
MST indicated the CO2 breakthrough. When using the
fused silica capillary column, the interface of the fluids
100
flowing in the tube throughout the test can also be observed MMP~2100 psig
using a scanning micro-video camera mounted near the
80
periphery of the column.
A series of displacement tests were conducted at
60
various pressure levels. For each displacement test, the MMP~2400 PSIG
% recovery

MST was filled with oil at 77oC and test pressure. The small
40
bore capillary column permits a high linear displacement this study
rate of 311 cm/min (0.25 cm3/min) resulting in time needed
20 Johnson & Pollin
per test of only 2 to 3 hours (including cleaning). The
relatively small height equivalent to a theoretical plate 0

(HETP) in a capillary column ensures thousands of multiple
contacts between the injected gas and oil, which cannot be
practically achieved in the conventional slim tube.
The volumes of displaced oil and CO2 injected at
breakthrough were either obtained directly from the pump
readings or by multiplying the displacement rate with the
displacement time. The displacement time is referred to as
the time taken for the oil to first hit the UV detector until
the onset of CO2 breakthrough. The test was terminated
when the response stabilised.
The recoveries at breakthrough as calculated using
equation [A4] were used in determining the MMP. It has
been reported2,3 that the ultimate recovery as well as
breakthrough recovery result in the same interpretation for
miscibility pressure.
% Recovery =
0 500 1,000 1,500 2,000 2,500 3,000
Pressure, psig
Figure 5: Comparison of MMP from micro-slim tube
and conventional slim tube for hexadecane with CO2
Results. The results of the displacement tests are
summarised in Table 5. Although the displacement tests
data obtained were not indicative of the ultimate recovery to
be achieved from a core flood or on a reservoir scale, they
were used to distinguish miscible displacements from
immiscible ones and to show the effect of pressure on
displacement efficiency. Thus, the CO2 MMP determined
was the minimum pressure at which CO2 could generate
miscibility with the test oil through multiple-contact
process. Nevertheless, the experiment gives potential
operating pressure/s, which is one of the most critical
elements in reservoir management.

(displaced oil volume at breakthrough) x 100 … [A4] Pressure % recovery

(psig)
Pore Volume
1000 79.23
1500 83.95
The recoveries were plotted against test pressures. The 2000 88.18
2500 88.78
experimental CO2 MMP was reported as the pressure at
3000 91.15
which the two best straight lines representing the miscible 3500 93.61
and immiscible breakthrough intersect. Generally, the test 4000 91.36
was considered as a miscible displacement when more than
80% of oil in place was recovered at CO2 breakthrough11. Table 5: Displacement tests on STO - CO2
57286 New Experimental Approaches in Minimum Miscibility Pressure (MMP) Determination 5

Apart from achieving 80% recovery, the UV response
and the observation of flowing fluids interface were also
used to determine whether each test was a miscible
displacement. For example, the displacement at 1500 psig
was considered immiscible although the percentage
recovery exceeded 80% since sharp fluid interface was
observed throughout the test and the UV response was
erratic at breakthrough indicating that two phases existed.
Figure 6 shows the difference in the UV response for
immiscible displacement at 1500 psig and miscible
displacement at 3500 psig.
P = 1500 psig (immiscible)
absorbance
Both techniques are faster than the conventional slim-
tube displacement test or the sand-pack experiment, which
usually take 3 to 4 weeks to complete.
Comparison with predicted MMP by EOS & published
correlations. A phase-behaviour computer software
(LABSIM) which consists of several programs utilising the
Peng-Robinson Equation-of-state (EOS) was used to
simulate the multiple contact processes. The EOS was
calibrated by matching the saturation pressure of the
reservoir from which the STO was taken.
As shown in Table 6, the MMP values obtained from
both techniques in the present study are in good agreement
CO2 breakthrough with each other and fall within the range of predicted MMP
by EOS and published correlations.

Technique/Correlation MMP (psig)

time, min This study IFT technique 2400
Micro-slim tube technique 2300
EOS Prediction LABSIM 2200
P = 3500 psig (miscible) CO2 breakthrough
Glaso 3018
Published Correlations Johnson & Pollin
absorbance

2182
Cronquist 2400

time, min Table 6: Comparison of MMP

Conclusions
Figure 6: Comparison of the UV detector response for
immiscible (at 1500 psig) and miscible (at 3500 psig) 1. A new approach using prototype VLE-IT
displacement for STO with CO2 equipment involving the measurement of oil/gas
interfacial tensions was successfully applied in
It is shown in Figure 7 that the two best straight lines determining the CO2 MMP with a STO.
representing the miscible and immiscible breakthrough
intersect at 2300 psig. Thus, the MMP is taken to be 2. A new approach in slim-tube test using unpacked
approximately 2300 psig. capillary column was proven to be capable of
determining the MMP. The tests yielded an MMP
100
value equivalent to the MMP determined from the IFT
90 technique.
80
% recovery

MMP ~ 2300 psig 3. Comparisons of IFT measurements and MMP

70
obtained in this study with previously published
60 studied systems show that the techniques using both
prototype equipment are reliable.
50
0 1,000 2,000 3,000 4,000 5,000
Pressure, psig

4. A comparison of the extrapolated pressure with

Figure 7: Stock tank oil recoveries obtained in micro- MMP estimated by micro-slim tube tests indicates that
slim tube displacements by CO2 at 77oC the concept of “lower limiting interfacial tension”
provides a very good experimental measure of MMP.
Comparison of Results
5. The short time needed to complete the MMP
IFT-MMP vs. MST-MMP. The results reveal that the IFT- determination tests using either VLE-IT or MST of
MMP (2400 psig) matches closely with MST-MMP (2300 GEMA demonstrates the practicality of utilising the
psig). The slightly higher IFT-MMP is however expected new approaches/techniques to determine the
since the discontinuity on a recovery versus pressure plot equilibrium interactions between crude oil and the
may not correspond to the true miscibility (zero IFT) but injected gas.
corresponds to a low enough IFT to efficiently displace oil
from the MST11.
6 Nor Idah Kechut, Zahidah Md. Zain, Noraini Ahmad, DM Anwar Raja DM Ibrahim 57286

Nomenclature 10.Johnson, J.P., Pollin, J.S., "Measurement & Correlation of CO2

Minimum Miscibility Pressure" SPE/DOE 9790 Second Joint
F= correction factor (Lando and Oakley) Symposium on EOR, Tulsa, Oklahoma.
fc = empirically derived correction factor for drop
11.Holm, L.W., Josendal, V.A., "Mechanism of Oil Displacement by
volume method (Harkin and Brown) Carbon Dioxide", Journal of Petroleum Technology p1427-1436.
gc= gravitational acceleration
∆P= pressure difference across the interface 12.Thomas, F.B., Zhou, X.L., Bennion, D.B., "A Comparative Study
R1= principle radius of curvature of RBA, P-x, Multicontact and Slim-tube Results" Journal of
R2 = principle radius of curvature Petroleum Technology, February 1994, Vol. 33, No. 2, p17-26.
r= radius
s = arc length
Vd= drop volume
σ= interfacial tension
ρ= density

Acknowledgement
The authors would like to thank the management of
PETRONAS and PETRONAS Research and Scientific
Services Sdn. Bhd. for permission to publish this work.
Sincere appreciation is also extended to the technicians and
support staff for their valuable contribution.

References

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Miscibility Analyser Method and Apparatus

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3. Yellig, W.F., Metcalfe, R.S., "Determination and prediction of

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Investigation of Miscible Displacement by CO2" SPE #3483.

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