REE168865 DOI: 10.
2118/168865-PA Date: 19-July-14 Stage: Page: 396
Phase Behavior and Minimum Miscibility
Pressure in Nanopores
Tadesse Weldu Teklu, SPE, Najeeb Alharthy, SPE, Hossein Kazemi, SPE, Xiaolong Yin, SPE, and
Ramona M. Graves, SPE, Colorado School of Mines; and Ali M. AlSumaiti, SPE, The Petroleum Institute, Abu Dhabi
Summary
Numerous studies indicate that the pressure/volume/temperature
(PVT) phase behavior of fluids in large pores (designated “un-
confined” space) deviates from phase behavior in nanopores (des-
ignated “confined” space). The deviation in confined space has
been attributed to the increase in capillary force, electrostatic
interactions, van der Waals forces, and fluid structural changes.
In this paper, conventional vapor/liquid equilibrium (VLE)
calculations are modified to account for the capillary pressure and
the critical-pressure and -temperature shifts in nanopores. The
modified VLE is used to study the phase behavior of reservoir
fluids in unconventional reservoirs. The multiple-mixing-cell
(MMC) algorithm and the modified VLE procedure were used to
determine the minimal miscibility pressure (MMP) of a synthetic
oil and Bakken oil with carbon dioxide (CO2) and mixtures of
CO2 and methane gas.
We show that the bubblepoint pressure, gas/oil interfacial ten-
sion (IFT), and MMP are decreased with confinement (nano-
pores), whereas the upper dewpoint pressure increases and the
lower dewpoint pressure decreases.
Introduction
Numerous authors have reported that the PVT phase behavior in
nanopores of an unconventional reservoir (hereafter referred to
as “confined” space) deviates from the bulk (designated as “un-
confined” space) PVT properties. The publications include Morish-
ige et al. (1997), Shapiro and Stenby (1997), Zarragoicoechea and
Kuz (2004), Singh et al. (2009), Travallonia et al. (2010), Sapmanee
(2011), Devegowda et al. (2012), Nojabaei et al. (2013), Teklu et al.
2013, and Alharthy et al. (2013). In this paper, conventional VLE
calculation for unconfined space is extended to confined space by
including capillary pressure and the shift in critical temperature and
critical pressure in confined pores. Specifically, we evaluate the con-
fined-space physical properties, such as (a) bubblepoint and dew-
point at a given pressure or temperature, (b) IFT of an oil/gas
mixture, and (c) MMP of a reservoir oil with injection gas. In the fol-
lowing sections, we present the computational details.
Thermodynamics in Nanopores
Many studies indicate that the PVT properties of fluids and their
phase behavior in nanopores (confined space) deviate from the
phase behavior in the PVT cell (unconfined space). The deviation
in confined space is a result of large capillary pressures, electro-
static and van der Waals forces, and the fluid structural changes.
When the pore size becomes very small, the capillary pressure
between the wetting phase and the nonwetting phase becomes sig-
nificantly larger than in conventional reservoirs and affects phase
equilibrium pressures. When the pore size is decreased further,
the elevated interaction between the fluid molecules and pore
walls starts to change the physical properties of the bulk fluid
such as critical pressure and critical temperature, density, viscos-
ity, and surface tension.
Copyright V
C 2014 Society of Petroleum Engineers
This paper (SPE 168865) was accepted for presentation at the Unconventional Resources
Technology Conference, Denver, 12–14 August 2013, and revised for publication. Original
manuscript received for review 25 June 2013. Revised manuscript received for review 4
January 2014. Paper peer approved 7 February 2014.
396
ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015
Total Pages: 8
In the last 20 years, the phase behavior of petroleum fluids in
unconventional reservoirs has received much attention (Brusilov-
sky 1992; Shapiro and Stenby 1997, 2001; Zarragoicoechea and
Kuz 2004; Singh et al. 2009; Travallonia et al. 2010; Sapmanee
2011; Devegowda et al. 2012; Firincioglu et al. 2012; Nojabaei
et al. 2013; Teklu et al. 2013; Alharthy et al. 2013). In what fol-
lows, we present three practical topics related to the phase behav-
ior of petroleum fluids in nanopores of unconventional
reservoirs—critical-temperature and -pressure and phase envelop-
ing shift, capillary pressure effect on phase behavior, and MMP in
nanopores.
Critical-Temperature and -Pressure Shift in Nanopores. Con-
fined space or pore proximity alters the fluid properties and phase
behavior; these effects are captured in the literature by shifting
the critical properties (Sapmanee 2011; Devegowda et al. 2012).
Morishige et al. (1997) showed experimentally that the critical
temperature of argon, nitrogen, oxygen, ethylene, and CO2 in
MCM-41 (MCM stands for mobil composition of matter that is a
class of mesoporous materials) of pore radius rp ¼ 1:2; 1:4;
1:8; 2:1 nm is reduced significantly. Zarragoicoechea and Kuz
(2004) modeled the reduction of critical temperature by applying
the van der Waals model and reported a good match of their
model and the experimental data by Morishige et al. (1997). The
Zarragoicoechea and Kuz (2004) model relates the relative criti-
cal-temperature shift quadratically to the ratio of the Lennard-
Jones collision diameter and the pore-throat radius, rLJ =rp (Eq.
1), in which rLJ can be calculated from the bulk critical properties
with Eq. 3 (Bird et al. 2007). On the basis of the van der Waals
theory, the critical-pressure shift has a dependence on rLJ =rp sim-
ilar to that of the critical-temperature shift (Eq. 2). However, this
is not yet experimentally proved, and the experiments will be dif-
ficult to perform (Zarragoicoechea and Kuz 2004). Similar results
of critical-temperature and critical-pressure shifts for alkanes in
slit pores are reported by Singh et al. (2009) by performing the
Grand Canonical Monte Carlo (GCMC) simulation approach:
 2
Tcb  Tcp rLJ rLJ
DTc ¼ ¼ 0:9409  0:2415 ; . . . . . ð1Þ
Tcb rp rp
 2

Pcb  Pcp rLJ rLJ
Dpc ¼ ¼ 0:9409  0:2415 ; . . . . . ð2Þ
Pcb rp rp
and
sffiffiffiffiffiffiffi
3 Tcb
rLJ ¼ 0:244 ; . . . . . . . . . . . . . . . . . . . . . . . . . . ð3Þ
pcb
where rp is pore-throat radius (nm), DTc is relative critical tem-
perature shift (dimensionless), Tcb is bulk critical temprature shift
(K), Tcp is pore critical temperature (K), rLJ is Lennard-Jones size
parameter (collision diameter) (nm), Dpc is relative critical pres-
sure shift (dimensionless), pcb is bulk critical pressure (atm), and
pcp is pore critical pressure (atm).
Figs. 1 and 2 show the critical temperature and pressure shift
for CO2, light hydrocarbon components, and lumped Bakken-oil
components (Table 1) calculated using Eq. 1. Fig. 3 shows the
critical-temperature and critical-pressure relative change vs.
rLJ =rp of CO2, light hydrocarbon components, and lumped
August 2014 SPE Reservoir Evaluation & Engineering
 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 397 Total Pages: 8

1,200 80
70
1,000
60
r=∞
800 r=∞
r = 30 nm 50 r = 30 nm

Pc [atm]
Tc [k]
r = 20 nm r = 20 nm
600 r = 10 nm 40 r = 10 nm
r = 5 nm r = 5 nm
30
400 r = 4 nm r = 4 nm
r = 3 nm 20 r = 3 nm
200 r = 2 nm r = 2 nm
10
0 0
CO2 C1 C2 C3 C4 C5–6 C7–12 C13–21 C22–80 CO2 C1 C2 C3 C4 C5–6 C7–12 C13–21 C22–80
Components Components

Fig. 1—Critical temperatures of CO2, light hydrocarbon gases, Fig. 2—Critical pressures of CO2, light hydrocarbon gases, and
and Bakken-oil lumped components in nanopores. Bakken-oil lumped components in nanopores.

TABLE 1—BAKKEN-OIL AND INJECTION-GAS COMPOSITIONS AND EOS PARAMETERS (Tres 5 241º F)

Composition Properties Binary-Interaction Parameters

Oil Gas 2a Gas 2b Gas 2c Tc ( F) Pc (psia) x CO2 C1 C2

CO2 – 1 0.9 0.8 87.6 1071 0.225 – – –

C1 0.36736 – 0.1 0.2 –124.66 655.02 0.0102 0.1 – –
C2 0.14885 – – – 89.97 721.99 0.1028 0.13 0.005 –
C3 0.09334 – – – 205.97 615.76 0.152 0.135 0.0035 0.0031
C4 0.05751 – – – 299.208 546.46 0.1894 0.13 0.0035 0.0031
C5–-6 0.06406 – – – 415.479 461.29 0.2684 0.125 0.0037 0.0031
C7–12 0.15854 – – – 593.25 363.34 0.4291 0.12 0.0033 0.0026
C13–21 0.0733 – – – 872.1 249.61 0.7203 0.12 0.0033 0.0026
C22–80 0.03704 – – – 1,384.5 190.12 1.0159 0.12 0.0033 0.0026

Bakken-oil components at different pore radii. Fig. 3 conveys the critical-pressure reduction for smaller pores is higher than for
same information as Figs. 1 and 2 combined, except both Figs. 1 larger pores. It is also observed that the reduction is more signifi-
and 2 are in absolute values, whereas Fig. 3 is in relative values. cant for heavier components for the same pore size, because the
As can be seen from these figures, the critical-temperature and pore can fit a fewer number of heavy-component molecules than
the lighter molecules. When only a few molecules can be fit into
the width of the pore, the validity of the bulk properties starts to
0.5 become challenged. For this reason, we limit the use of Eqs. 1 and
2 to the pore radius of  3 nm in this study. As shown in Fig. 3,
when rp ¼ 3 nm, even for the largest molecule, C2280 ,
0.4
rLJ =rp  0:35, which means one can fit approximately six mole-
C22–30 cules into the width of the pore. Fig. 3 also shows that Bakken oil
ΔTc* or ΔPc*

0.3 (most reservoir-fluid components including CO2) falls in the

C7–12 C13–21
2 nm range of experimental data used to develop Eq. 1 for  3 nm of
C4 C5–6 3 nm pore-radius confinement. At a 2-nm pore-radius confinement,
0.2 C2 C3
5 nm C1321 and C2280 of Bakken-oil lumped components fall outside
C1 10 nm
CO2
the range of experimental data used to develop Eq. 1 by Zarragoi-
0.1 20 nm
coechea and Kuz (2004), which is rLJ =rp  0:37. On the basis of
30 nm
1 μm
Eq. 1, Eq. 2, and Fig. 3, the changes in the critical properties can
0 be ignored for pore radius > 30 nm. If we ignore the quadratic
0 0.1 0.2 0.3 0.4 0.5 0.6 term, Eqs. 1 and 2 show that the relative reduction in critical tem-
σLJ/rp perature or critical pressure is inversely proportional to pore ra-
dius and directly proportional to the collision diameter.
Fig. 4 shows the confined (at rp ¼ 3 nm and rp ¼ 10 nm) and
Fig. 3—Critical-temperature and –pressure relative change vs. the unconfined (rp ¼ infinity) phase envelopes for Bakken oil (Ta-
rLJ =rp for CO2, light hydrocarbon gases, and lumped Bakken-oil
ble 1), in which the confined one is generated by applying the crit-
components at different pore radii. Data points of the same color
correspond to a certain pore size, with each point representing a ical-temperature and critical-pressure shift at a pore-throat radius
component from CO2 to C22–80 (the same order as in the list of of 3 nm and 10 nm with Eqs. 1 and 2, respectively. The phase-en-
Table 1 from top to bottom and as indicated in the figure for the velope calculation uses a Peng-Robinson equation-of-state (EOS)
3-nm pore-radius case). Note for 3-nm and higher pore radii, CO2 flash-calculation procedure (Danesh 1998).
and C1 relative-shift data are overlapping. This plot shows that:
(a) the critical-property shift of heavier components for the same
pore radius is higher; (b) the critical-property shift increases Capillary Pressure. The effect of capillary pressure in nano-
with confinement; and (c) as confinement decreases (e.g., 1 lm pores is significant, and one should also consider its effect on the
), critical-property shift approaches zero. phase behavior when dealing with nanopores of unconventional

August 2014 SPE Reservoir Evaluation & Engineering 397

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015

 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 398 Total Pages: 8

4,000 Saturation point @ r = INF

4,000
Saturation point @ r = INF
Saturation point @ r = 10 nm Tres = 241°F Saturation point @ r = 10 nm
Saturation point @ r = 3 nm Saturation point @ r = 3 nm
3,500 3,500
T = 950°F
3,000 3,000
Pressure, psi

Pressure, psi
2,500 2,500

2,000 2,000

1,500 1,500

1,000 1,000

500 500

0 0
0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200

Temperature, °F Temperature, °F

Fig. 4—Phase envelope of Bakken oil in unconfined
(rp 5 infinity) pores and confined (rp 5 3 nm and rp 5 10 nm)
pores. The solid lines with symbols were obtained from calcula-
tions. Near critical points, convergence is difficult. Thus, we
used dashed lines to qualitatively mark the near-critical region,
and we marked the critical points with diamond-shaped dots.
reservoirs. For pores of single sizes, the effect of capillarity can be
Fig. 5—Capillary pressure effect on phase-envelop shift and
the bubblepoint- and dewpoint-pressure changes for the
Bakken oil.
where v is the scaling exponent, mostle 3.6 or (in this study
v ¼ 3.6); q L=V si the molar density of bulk liquid/vapor phases
(mole/cc); and PL=V is the liquid/vapor givn by PL=V ¼
XNc XNc

incorporated into the conventional flash, conventional flash (VLE),
calculation algorithm (Brusilovsky 1992; Shapiro and Stenby 1997,
2001; Firincioglu et al. 2012; Nojabaei et al. 2013). In this study,
we model the phase behavior by considering the capillary pressure
in nanopores with Eqs. 4 through 6 and comparing the results with
a case in which there is no capillary pressure effect ðpcap ¼ 0Þ.
The equilibrium condition of the vapor (V) and liquid (L)
phases with capillary pressure is described by the following sys-
tem of equations (Brusilovsky 1992; Shapiro and Stenby 2001):
) 
lL;i ðpL ; xi Þ ¼ lV;i ðpV ; yi Þ;
2rVL cosh ; . . . . . . . . . . . . . . . . . . ð4Þ
pcap ¼ pV  pL ¼
r
where lL/V,i is the chemical potential of liquid/vapor phase of
each component, rVL is the IFT between vapor and liquid phase, h
is the contact angle (h ¼ 1808 assumed for this study), p is pres-
sure, and x and y are liquid and vapor mole fraction (respectively),
and r is radius.
The IFT between the liquid and gas phases can be estimated
with the the parachor model noted next (Zuo and Stenby 1998):
rVL ¼ ðPL q L  PV q V Þv ; . . . . . . . . . . . . . . . . . . . . . . ð5Þ
3,000
2,500
2,000
Pbubble, psi
xi Pi and PV ¼ yi Pi ; where Pi is the parachor of pure com-
i¼1 i¼1
ponents ¼ (8.21307þ1.97473 xi) Tci1:03406 p0:82636
ci , where xi, Tci,
and Pci are the acentric factor (), critical temperature (K), and
critical pressure (bar) of each component, respectively.
After the capillary pressure is determined with Eqs. 4 and 5,
the conventional VLE or flash calculation that assumes zero capil-
larity ( pL ¼ pV ) can be modified with Eq. 6 (Shapiro and Stenby
2001) in each iteration level until convergence within specified
tolerance is achieved:
  
pcap pL /L;i
Kcap;i ¼ 1  Ki ¼ Ki ; where Ki ¼ ; . . . . . ð6Þ
pV pV /V;i
where Kcap,i is the equilibrium ratio of each component corrected
for capilary pressure Ki is the equilibirium of each component,
and /L/V,i is the fugacity coefficient of liquid/vapor phases of each
component.
Applying the capillary pressure effect on equilibrium ratio, we
notice a significant shift of the phase envelope—especially for
pore radii of 10 nm and lower. The phase-envelope shift caused
by capillary pressure is shown in Fig. 5. The bubblepoint and
lower dewpoint clearly are suppressed with confinement, whereas
the upper dewpoint increases with confinement. Bubblepoint sup-
pression caused by capillarity at reservoir temperature for the case
of Bakken oil at different pore radii is given in Fig. 6. Capillarity
modifies not only the location of the phase boundary but also the
equilibrium compositions of the vapor and liquid phases and the
IFT. Fig. 7 shows the effect of capillarity on the IFT at a given
pressure and reservoir temperature of a 1:1 mixture (by mole) of
Bakken oil and CO2.

1,500
Combined Critical-Property Shift and Capillary Pressure
1,000
Effect. As we have seen, both capillary pressure and critical-
property shift play significant roles in altering the phase behavior
of fluids at nanopore scale. Before we look at how this combined
500 effect alters laboratory (unconfined) MMP of reservoir fluids with
injected gas, we first investigate how the combined effect alters
0 the phase envelope, bubblepoint, dewpoint, and the IFT of a mix-
1 10 100 1000 ture of a given oil and injection gas.
Pore radius, nm Fig. 8 is the phase-envelope shift caused by only critical-pres-
sure and -temperature shift and as a result of both capillary pres-
Fig. 6—Bubblepoint-pressure decrease of Bakken oil at reser- sure effect and critical-temperature and -pressure shift.
voir temperature (241º F). The effect of confinement on bubble- Fig. 9 shows the bubblepoint suppression caused by (a) only
point can be neglected above a 40-nm pore radius. critical-temperature and -pressure shift, (b) only capillary pressure

398 August 2014 SPE Reservoir Evaluation & Engineering

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015

 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 399 Total Pages: 8

20 Pressure 4,500 Saturation point @ r = INF

Saturation point @ r = 10 nm (only TcPc shift)
1,000 psi

Interfacial Tension, σ, [dyn/cm]

18 4,000 Saturation point @ r = 10 nm (both TcPc shift and Pcap)
Tres = 241 °F Saturation point @ r = 3 nm (only TcPc shift)
16 Saturation point @ r = 3 nm (both TcPc shift and Pcap)
3,500
14
1,500 psi 3,000

Pressure, psi
12
10 2,500

Tdew at Pdew = 1,000 psi

8 2,000 psi 2,000
6
1,500
4 2,500 psi
1,000
2
0 500
1 10 100 1000
Pore radius, nm 0
0 200 400 600 800 1,000 1,200

Fig. 7—IFT vs. pore radius of a 1:1 mixture (by mole) of Bakken Temperature, °F
oil and CO2 at reservoir temperature and different pressure (up
to 2,500 psi, in which the mixture is in a two-phase region). This Fig. 8—Phase-envelope shift of the Bakken oil in unconfined
plot shows: (a) the effect of capillarity on IFT is significant at (r 5 infinity) and confined (r 5 3 nm and r 5 10 nm) pores. The
lower pressure and becomes less at higher pressure; (b) the solid curves include critical-temperature and critical-pressure
cutoff radius, above which capillary pressure has marginal shifts only, whereas the dashed curves include both capillary
effect on IFT, reduces in the direction of the arrow with increas- pressure and critical-temperature and -pressure shifts.
ing pressure. For example, at 1,500 psi, the cutoff pore radius
is approximately 100 nm, whereas at 2,500 psi, the cutoff radius
reduces to approximately 20 nm. 1,200

1,000
3,000
800
2,500 Tdew, °F
600

2,000
Pbubble, psi

400

1,500 (a) Only Tc & Pc shift

200 (b) Only Pcap
1,000 (c) Both Pcap and Tc & Pc shift
0
(a) Only Tc & Pc shift 1 10 100 1000
500 (b) Only Pcap Pore radius, nm
(c) Both Pcap and Tc & Pc shift
0 Fig. 10—Bakken-oil dewpoint temperature at 1,000 psi at differ-
1 10 100 1000
ent pore radii: (a) critical-temperature and -pressure effect, (b)
Pore radius, nm capillary pressure effect, and (c) critical-temperature and pres-
sure shift and capillary pressure effect.
Fig. 9—Bakken-oil bubblepoint-pressure change at different
pore radii and at reservoir temperature: (a) critical-temperature
and -pressure effect, (b) capillary pressure effect, and (c) criti- effect, and (c) combined capillary pressure and critical-property
cal-temperature and -pressure shift and capillary pressure shift at a constant temperature of 241 F. Interestingly, when the
effect. confinements are 5 nm and lower, Case (c) has less suppression
than Case (b). One can also see this comparison in Figs. 5 and 8 at
the same temperature. This prediction is reasonable because the
temperature condition in Case (c) is close to the shifted critical
20 Pressure point, which reduces the IFT and the capillary pressure.
Fig. 10 shows dewpoint-temperature shift at the constant
Interfacial Tension, σ, [dyn/cm]

18 1,000 psi
1,000-psi dewpoint pressure of the Bakken oil at different con-
16 finement levels: (a) caused by only critical-pressure and -tempera-
14 ture shift, (b) caused by only the capillary pressure effect, and (c)
12 1,500 psi caused by combined capillary pressures and critical-property shift.
At this dewpoint pressure (1,000 psi), the effect of capillary pres-
10
sure is to increase the dewpoint temperature with increasing the
8 2,000 psi level of confinement. The effect of the critical-property change,
6 on the other hand, is to decrease the dewpoint temperature with
4 2,500 psi
increasing confinement. When the two mechanisms act together,
then net result is close to that of only critical-property change,
2
which suggests that, at this pressure, the critical-property change
0 with confinement is the dominant mechanism to alter the phase
1 10 100 1000
Pore radius, nm
behavior. At another pressure, the relative importance of the two
mechanisms could be slightly different, as one can observe from
Fig. 11—Semilog plot of IFT vs. pore radius of 1:1 mixture (by Figs. 5 and 8.
mole) of Bakken oil and CO2 at reservoir temperature and differ- Fig. 11 is a semilog plot of the IFT vs. pore radius for a 1:1 (by
ent pressure. Solid lines show the effect of capillary pressure, mole) mixture of Bakken oil and CO2 at reservoir temperature and
and dotted lines show the combined effect caused by capillarity at given pressure. The solid lines represent the effect solely as a
and critical-property shift. result of the capillary pressure, and the dashed lines present the

August 2014 SPE Reservoir Evaluation & Engineering 399

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015

 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 400 Total Pages: 8

TABLE 2—OIL COMPOSITION, INJECTION-GAS COMPOSITIONS, AND EOS PARAMETERS (Tres 5 160º F)

Composition Properties Binary-Interaction Parameters

o
Oil Gas 1a Gas 1b Gas 1c Tc ( F) Pc (psia) x CO2 C1 C4

CO2 – 1 0.9 0.8 87.9 1071 0.225 – – –

C1 0.2 – 0.1 0.2 –116.6 667.8 0.0104 0.1 – –
C4 0.15 – – – 305.65 550.7 0.201 0.1257 0.027 –
C10 0.65 – – – 652.1 305.7 0.49 0.0942 0.042 0.008

combined effect of capillary pressure and critical-property shift.
From this plot, one can deduce that (a) both capillary pressure and
critical-properties shift may be neglected when analyzing their
effect on IFT (or MMP) for pore radius greater than 100 nm and (b)
for a 50-nm pore radius and lower, their effect on IFT (or MMP) is
worth considering because the combined effect of both critical-
property shift and the capillarity results in significant deviations in
the IFTs from the unconfined IFTs. The unconfined IFTs are
approximately equal to the values at a 1000-nm pore radius.
MMP in Nanopores
MMP is the lowest pressure at which miscibility between the injected
gas and reservoir oil is achieved when the IFT between oil and gas
vanishes after multiple contacts. MMP is measured in the laboratory
in sand-packed slim tubes (Yellig and Metcalfe 1980), in the rising-
bubble apparatus (Christiansen and Haines 1987), or by the vanish-
ing-IFT technique (Rao 1997). In these experimental methods, the
gas and oil come into contact either in presence or absence of a porous
medium. Both experimental approaches are applicable in conven-
tional reservoirs since in large pores phase behavior is not affected by
confinement. Measuring MMP in unconventional reservoirs with real
confinement is a significant challenge that has not been undertaken.
One can calculate MMP to a good accuracy by computational
methods that use fluid-flow and thermodynamic phase-equilib-
rium principles. In the slimtube simulation, one can determine
MMP with a 1D compositional gas/oil fluid-flow simulator
(Stalkup 1987). In the nonflow approach, which involves a prede-
termined mixing approach, a single cell or multiple connecting
cells were used (Metcalfe et al. 1973; Zick 1986; Luks et al.
1987; Jaubert et al. 1998). The multiple-cell mixing involves sim-
ulation of gas/oil mixing in a series of 5 to 500 cells that are con-
nected and initially filled with oil. Typically, gas is mixed in the
first cell at a trial pressure and, assuming complete mixing within
the cell, the equilibrium phases are calculated. Then, the excess
volume of the cell (i.e., part of the equilibrium gas) is carried to
3
r = 4 nm
2.5 r = 20 nm
unconfined
2 3.5
the second cell and mixed with the fluid in that cell. This process
continues for all subsequent cells until 1.2 pore volumes of gas
are injected (Metcalfe et al. 1973; Jaubert et al. 1998).
Another approach of determining the MMP uses method of char-
acteristics (MOC) (Wang and Orr 1997). In the MOC approach,
MMP is reached when any one of the Nc 1 key tie-lines becomes
critical (is equal to zero). The MMC algorithm developed by
Ahmadi and Johns (2011) combines the MOC and traditional mix-
ing-cell algorithm to determine the MMP. Their algorithm succes-
sively increases the number of cells (contact numbers) until all the
Nc 1 key tie-lines are developed. The key tie-lines are injection
(gas) tie-line, oil tie-line, and other Nc 3 crossover tie-lines. And
MMP is reached at a pressure in which any of the Nc 1 tie-line
length (TL) is reduced to zero (Appendix A). A study by Teklu et al.
(2012) modified the MMC algorithm by tracking a minimization
function that involves equilibrium ratios instead of TLs.
In this study, we investigated the effect of the capillary pres-
sure and the critical-property change on phase behavior and IFT
in the Thermodynamics in Nanopores section; now, we proceed to
study how they affect the MMP of oil and injected gas in nano-
pores of given scales.
The MMPs of two reservoir-oil compositions with CO2 and
mixtures of CO2 and methane are studied, with and without con-
sidering the effects of confinement. The reservoir-oil composition,
gas composition, reservoir temperature, and other fluid properties
are listed in Tables 1 and 2. Table 1 is an unconventional-oil
composition from the Bakken (Oil Composition and Properties
from Nojabaei et al. 2013), and Table 2 is a three-component syn-
thetic-oil composition.
The MMP results of 100% CO2 gas injection for the synthetic
oil and Bakken oil are shown in Figs. 12 and 13, respectively.
Critical-temperature and critical-pressure shifts and capillary
pressure effects discussed in the Thermodynamics in Nanopores
section are applied for the confined cases of a pore radius of 4 nm
and higher. Only results of r ¼ 4 nm, r ¼ 20 nm, and r ¼ infinity
(unconfined) are shown in the plots, for neatness.
5
r = 4 nm
4.5
4 r = 20 nm
unconfined

3
f(Ki, pn)

f(Ki, pn)

1.5
2.5

2
1
1.5

0.5 1

0.5
0
0
500 700 900 1,100 1,300 1,500 1,700 1,900 500 1,000 1,500 2,000 2,500
Pressure, psi Pressure, psi

Fig. 12—The f ðKi ; p n Þ vs. pressure for synthetic oil and 100% Fig. 13—The f ðKi ; p n Þ vs. pressure for Bakken oil and 100% CO2
CO2 injection gas at different pore radii. At a 4-nm pore radius, injection gas at different pore radii. At a 4-nm pore radius,
approximately a 200-psi reduction in MMP is observed com- approximately a 130-psi reduction in MMP is observed com-
pared with the unconfined pore. pared with the unconfined pore.

400 August 2014 SPE Reservoir Evaluation & Engineering

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015

 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 401 Total Pages: 8

3.5 unconfined, 100%CO2 5

unconfined
r = 4 nm, 100%CO2
3 4.5
unconfined, 90%CO2 & 10%CH4
r = 4 mm, only Tc & Pc shift
r = 4 nm, 90%CO2 & 10%CH4
4
2.5 unconfined, 80%CO2 & 20%CH4 r = 4 mm, with Pcap and Tc & Pc shift
r = 4 nm, 80%CO2 & 20%CH4 3.5
f(Ki, pn) 2
3

f(Ki,pn)
1.5 2.5

1 2

1.5
0.5
1
0
500 1,000 1,500 2,000 2,500
0.5

Pressure, psi 0
500 700 900 1,100 1,300 1,500 1,700 1,900
Fig. 14—The f ðKi ; p n Þ vs. pressure for synthetic oil and 100%- Pressure, psi
CO2, 90%-CO2 /10% CH4, and 80% CO2/20% CH4, injection gas
for unconfined (solid lines and symbols) pore and a 4-nm pore-
Fig. 15—The f ðKi ; p n Þ vs. pressure for synthetic oil and 100%
radius confinement (dashed lines and smaller symbols).
CO2 injection gas at a 4-nm confinement with only critical-tem-
perature and -pressure shift effect (solid line with diamond-
Compared with the unconfined case, in 4-nm-radius pores, the shaped symbols), with both capillary pressure and critical-
reduction in the MMP was approximately 200 psi for the synthetic property shift effect (solid line with triangular-shaped symbols),
oil (Fig. 12) and approximately 130 psi for the Bakken oil (Fig. and unconfined cases (solid line with circle-shaped symbols).
13). For a pore radius of 20 nm and higher, the effect of confine-
ment on MMP is marginal. In Figs. 12 and 13, the MMP was esti-
mated by finding the minimum of the objective function • Most of the reduction in MMP caused by confinement is attrib-
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
XNc ffi uted to critical-temperature and critical-pressure shifts.
n 2
f ðKi ; p Þ ¼ min ð1  K i Þ , which is typically a small • For a pore radius of 20 nm and higher, the confinement effects
i¼1
on MMP and other phase behavior are marginal.
number but not exactly zero (Appendix A). Finally, we would like to comment that the work presented
Similar trends are observed for the cases of 90%-CO2/10%- here is theoretical and applies only for a single pore size. Further
CH4 and 80%-CO2/20%-CH4 gas injections. The MMP increases studies should be conducted to model the reality of a rock, which
with increasing the percentage of impurity in the injected CO2 contains complex surface-chemical heterogeneities and pore-size
gas, as can be seen in Fig. 14 for the synthetic-oil case. The reduc- distributions. With these heterogeneities, it will be challenging to
tion in MMP is observed to increase with increasing the percent- conduct and to interpret phase-behavior experiments with real
age of methane. For the case of 80%-CO2/20%-CH4 gas injection, rocks. Theoretical studies with proper considerations of these het-
approximately a 500-psi reduction in MMP is observed at a 4-nm erogeneities, therefore, need to be developed.
pore radius compared with unconfined pore.
The MMP reduction only caused by capillary pressure and Nomenclature
only caused by critical-temperature and critical-pressure shifts K ¼ equilibrium constant
was also assessed. As can be seen in Fig. 15, considering only Kcap ¼ equilibrium constant corrected for “capillary”
critical-property shift reduces the MMP by up to 130 psi. The cap- Nc ¼ number of components, –
illary pressure effect reduces MMP further, and thus a total MMP p ¼ pressure, psi
reduction of approximately 200 psi is predicted considering both pc ¼ critical pressure, psi
effects at a 4-nm pore radius compared with unconfined pore. pcap ¼ capillary pressure, psi
pcb ¼ bulk critical pressure, psi
Conclusions and Recommendations pcp ¼ pore critical pressure, psi
The conventional VLE-calculation algorithm was extended to PL ¼ liquid parachor
confined pore of nanopore scale by accounting for (1) the critical- PV ¼ vapor parachor
pressure and critical-temperature shifts and (2) the capillary pres- rp ¼ pore-throat radius, nm
sure effect on the thermodynamic phase equilibrium in confined Tc ¼ critical temperature,  F
pores. The effect of confinement on bubblepoint, dewpoint, and Tcb ¼ bulk critical temperature,  F
IFT of a given mixture of oil and injection gas was studied. The Tcp ¼ pore critical temperature,  F
MMC algorithm for MMP determination was extended to uncon- Tres ¼ reservoir temperature,  F
ventional reservoir systems with nanopores with the extended z ¼ molar fraction, –
VLE-calculation algorithm. The MMPs of a synthetic oil and Dpc ¼ relative critical-pressure shift, –
Bakken oil during injection of CO2 and mixtures of CO2 and CH4 DTc ¼ relative critical-temperature shift, –
were studied, including the confinement effect. The predictions of rLJ ¼ Lennard-Jones size parameters, nm
our models can be summarized as follows: rVL ¼ IFT between vapor and liquid phases, dynes/cm
• Bubblepoint decreases significantly with combined capillary q ¼ molar density
pressure and critical-property shift effects. / ¼ fugacity coefficient, –
• Typically, the upper dewpoint increases and the lower dewpoint l ¼ chemical potential, J 
decreases with increasing confinement. h ¼ contact angle, h ¼ 180 for this study
• IFT of a mixture of oil and injection gas at a given pressure and v ¼ scaling exponent, in this work, v ¼ 3:6
temperature decreases significantly with confinement. x ¼ acentric factor, –
• For a pure CO2-gas injection, up to a 200-psi reduction in MMP
can be determined for a pore radius of 4 nm compared with
unconfined pores. For a mixture of CO2 and CH4 injection gas, Acknowledgments
even though the actual MMP value increases compared with The authors would like to thank Abu Dhabi National Oil Com-
pure CO2 gas, the reduction of MMP caused by confinement pany, The Petroleum Institute, Abu Dhabi; Marathon Center of
can reach up to 500 psi. Excellence for Reservoir Studies; Unconventional Natural Gas

August 2014 SPE Reservoir Evaluation & Engineering 401

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015

 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14
and Oil Institute; and Center for Earth Materials, Mechanics, and
Characterization at Colorado School of Mines for their support of
this study. Special thanks to Jeffrey S. Brown for his valuable dis-
cussion and comments.
References
Ahmadi, K. and Johns, R.T. 2011. Multiple-Mixing-Cell Method for
MMP Calculations. SPE J. 16 (4): 733–742. SPE-116823-PA. http://
dx.doi.org/10.2118/116823-MS.
Alharthy N., Nguyen T.N., Teklu T.W. et al. 2013. Multiphase Composi-
tional Modeling in Small-Scale Pores of Unconventional Shale Reser-
voirs. Presented at SPE Annual Technical Conference and Exhibition,
New Orleans, Louisiana, 30 September–2 October. SPE-166306-MS.
http://dx.doi.org/10.2118/166306-MS.
Bird, R.B., Stewart, W.E., and Lightfoot, E.N. 2007. Transport Phenom-
ena. Revised second edition, John Wiley & Sons.
Brusilovsky, A.I. 1992. Mathematical Simulation of Phase Behavior of
Natural Multicomponent Systems at High Pressures With an Equation
of State. SPE Res Eval & Eng 7 (1): 117–122. SPE-20180-PA. http://
dx.doi.org/10.2118/20180-PA.
Christiansen, R.L. and Haines, H.K. 1987. Rapid Measurement of Minimum
Miscibility Pressure With the Rising-Bubble Apparatus. SPE Res Eval &
Eng 2 (4): 523527. SPE 13114. http://dx.doi.org/10.2118/13114-PA.
Danesh, A. 1998. PVT and Phase Behaviour of Petroleum Reservoir Flu-
ids. Vol. 47. Elsevier.
Devegowda, D., Sapmanee, K., Civan, F. et al. 2012. Phase Behavior of
Gas Condensates in Shales Due to Pore Proximity Effects: Implica-
tions for Transport, Reserves and Well Productivity. Presented at An-
nual Technical Conference and Exhibition, San Antonio, Texas, 8–10
October. SPE-160099-MS. http://dx.doi.org/10.2118/160099-MS.
Firincioglu, T., Ozkan, E., and Ozgen, C. 2012. Thermodynamics of Multi-
phase Flow in Unconventional Liquids-Rich Reservoirs. Presented at
SPE Annual Technical Conference and Exhibition, San Antonio, Texas,
8–10 October. SPE-159867-MS. http://dx.doi.org/10.2118/159867-MS.
Jaubert, J.N., Wolff, L., Neau, E. et al. 1998. A Very Simple Multiple
Mixing Cell Calculation to Compute the Minimum Miscibility Pres-
sure Whatever the Displacement Mechanism. Ind. Eng. Chem. Res. 37
(12): 4854–4859. http://dx.doi.org/10.1021/ie980348r.
Luks, K.D., Turek, E.A., and Baker, L.E. 1987. Calculation of Minimum
Miscibility Pressure. SPE Res Eng 2 (4): 501–506. SPE-14929-
PA.http://dx.doi.org/10.2118/14929-PA.
Metcalfe, R.S., Fussell, D.D., and Shelton, J.L. 1973. A Multicell Equilib-
rium Separation Model for the Study of Multiple Contact Miscibility
in Rich-Gas Drives. SPE J. 13 (3): 147–155. SPE-3995-PA. http://
dx.doi.org/10.2118/3995-PA.
Morishige, K., Fujii, H., Uga, M. et al. 1997. Capillary Critical Point of
Argon, Nitrogen, Oxygen, Ethylene, and Carbon Dioxide in MCM-41.
Langmuir 13 (13): 3494–3498. http://dx.doi.org/10.1021/la970079u.
Neoschil, J. and Chambrette, P. 1978. Converge Pressure Concept a Key
for High Pressure Equilibria, SPE 7820 (submitted to SPE, not pub-
lished but available in the eLibrary).
Nojabaei, B., Johns, R.T., and Chu, L. 2013. Effect of Capillary Pressure
on Phase Behavior in Tight Rocks and Shales. SPE Res Eval & Eng 16
(3): 281–289. SPE-159258-PA. http://dx.doi.org/10.2118/159258-PA.
Peng, D. and Robinson, D.B. 1976. A New Two-Constant Equation of
State. Ind. Eng. Chem. Fundamentals 15 (1): 59–64. http://dx.doi.org/
10.1021/i160057a011.
Rachford, H.H. and Rice J.D. 1952. Procedure for Use of Electronic Digi-
tal Computers in Calculating Flash Vaporization Hydrocarbon Equilib-
rium. J. Pet Technol 4 (10): 19. SPE-952327-G-PA. http://dx.doi.org/
10.2118/952327-G-PA.
Rao, D.N. 1997. A New Technique of Vanishing Interfacial Tension for
Miscibility Determination. Fluid Phase Equilibria 139 (1): 311–324.
http://dx.doi.org/10.1016/S0378-3812(97)00180-5.
Sapmanee, K. 2011. Effects of Pore Proximity on Behavior and Produc-
tion Prediction of Gas/Condensate. MS thesis, Mewbourne School of
Petroleum and Geological Engineering, University of Oklahoma,
September.
Shapiro, A.A. and Stenby, E.H. 1997. Kelvin Equation for a Non-ideal
Multicomponent Mixture. Fluid Phase Equilibria 134 (1): 87–101.
http://dx.doi.org/10.1016/S0378-3812(97)00045-9.
402
ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015
Stage: Page: 402 Total Pages: 8
Shapiro, A.A. and Stenby, E.H. 2001. Thermodynamics of the Multicom-
ponent Vapor-Liquid Equilibrium Under Capillary Pressure Differ-
ence. Fluid Phase Equilibria 178 (1): 17–32. http://dx.doi.org/
10.1016/S0378-3812(00)00403-9.
Singh, S.K., Sinha, A., Deo, G. et al. 2009. Vapor-Liquid Phase Coexistence,
Critical Properties, and Surface Tension of Confined Alkanes. J. Phys.
Chem. 113 (17): 7170–7180. http://dx.doi.org/10.1021/jp8073915.
Stalkup, F.I. 1987. Displacement Behavior of the Condensing/Vaporizing
Gas Drive Process. Presented at the SPE Annual Technical Conference
and Exhibition, Dallas, Texas, 27–30 September. SPE-16715-MS.
http://dx.doi.org/10.2118/16715-MS.
Teklu, T., Alharthy, N., Kazemi, H. et al. 2013. Minimum Miscibility
Pressure in Conventional and Unconventional Reservoirs. Presented at
Unconventional Resources Technology Conference, Denver, Colo-
rado, 12–14 August. URTeC 1589572/SPE 168865.
Teklu, T., Ghedan, S.G., Graves, R.M. et al. 2012. Minimum Miscibility
Pressure Determination: Modified Multiple Mixing Cell Method. Pre-
sented at SPE EOR Conference Oil and Gas West Asia, Muscat, Oman,
16–18 April. SPE-155454-MS. http://dx.doi.org/10.2118/155454-MS.
Travallonia, L., Castierb, M., Tavaresa, F.W. et al. 2010. Critical Behavior
of Pure Confined Fluids From an Extension of the Van Der Waals
Equation of State. J. Supercrit. Fluids 55 (2): 455–461. http://
dx.doi.org/10.1016/j.supflu.2010.09.008.
Wang, Y. and Orr, F.M. 1997. Analytical Calculation of Minimum Misci-
bility Pressure. Fluid Phase Equilibria 139 (1): 101–124. http://
dx.doi.org/10.1016/S0378-3812(97)00179-9.
Whitson, C.H. and Michelsen, M.L. 1989. The Negative Flash. Fluid Phase
Equilibria 53: 51–71. http://dx.doi.org/10.16/0378-3812(89)80072-X.
Yellig, W.F. and Metcalfe, R.S. 1980. Determination and Prediction of
CO2 Minimum Miscibility Pressures. J. Pet Technol 32 (1): 160–168.
SPE-7477-PA. http://dx.doi.org/10.2118/7477-PA.
Zarragoicoechea, G.J. and Kuz, V.A. 2004. Critical Shift of a Confined
Fluid in a Nanopore. Fluid Phase Equilibria 220 (1): 7–9. http://
dx.doi.org/10.1016/j.fluid.2004.02.014.
Zick, A.A. 1986. A Combined Condensing/Vaporizing Mechanism in the
Displacement of Oil and Enriched Gases. Presented at SPE Annual
Technical Conference and Exhibition, Louisiana, 5–8 October. SPE-
15493-MS. http://dx.doi.org/10.2118/15493-MS.
Zuo, Y. and Stenby, E.H. 1998. Prediction of Interfacial Tensions of Res-
ervoir Crude Oil and Gas Condensate Systems. SPE J. 3 (2): 134–145.
SPE-38434-PA. http://dx.doi.org/10.2118/38434-PA.
Appendix A—MMC Algorithm for MMP
Determination
Here, we summarize the MMC algorithm developed by Ahmadi
and Johns (2011). The minimization function involving the equi-
librium constant proposed by Teklu et al. (2012) can be used at
Step 5.
• Step 1. At the reservoir temperature, assume a pressure substan-
tially less than the MMP (for example, 500 psi) as the starting
point of an MMP calculation.
• Step 2. For first contact, start with two cells filled with injection
gas (zgas ) and oil composition (zoil ). Mix the injection gas and
reservoir oil to obtain mixture composition (zmix ) such that
zmix ¼ ð1  bÞzoil þ bzgas . We used b ¼ 0:5, which is equiva-
lent to a 1:1 molar mixing.
Then, the mixture composition resulting from b ¼ 0:5 is flashed
with a cubic EOS such as the Peng-Robinson EOS (Peng and
Robinson 1976) to obtain the first-contact equilibrium liquid (x)
and vapor (y) compositions. Negative flash (Neoschil and
Chambrette 1978; Whitson and Michelsen 1989) is used in
solving the Rachford-Rice equation (Rachford and Rice 1952).
• Step 3. For second contact, mix zgas with x, and y with zoil , to
obtain two new overall mixture compositions; x and y are from
the first contact. Then, flash these two overall compositions to
obtain two equilibrium liquid and vapor compositions with
b ¼ 0:5.
• Step 4. Increase the contact number, as shown in Fig. A-1, until
all the Nc 1 key tie-lines are developed and converged to
within specified tolerance. Thus, after N contacts, we have 2
N þ 2 cells. Key tie-line is developed when the TL between
August 2014 SPE Reservoir Evaluation & Engineering
 REE168865 DOI: 10.2118/168865-PA Date: 19-July-14 Stage: Page: 403 Total Pages: 8

G O 1st Contact and an MSc degree in petroleum engineering from Universiti

Teknologi Petronas, Malaysia.
G X Y O 2nd Contact Najeeb Alharthy is a PhD candidate in petroleum engineering
at Colorado School of Mines. He earned a BS degree in electri-
cal engineering from the University of Texas at Austin and a
G X Y X Y O 3rd Contact
Masters degree in petroleum engineering from Colorado
School of Mines. Alharthy’s main area of research is the mod-
G X Y X Y X Y O 4th Contact eling of unconventional liquid-rich shale reservoirs. He is a
member of SPE and the Society of Exploration Geophysicists.
Hossein Kazemi is the Chesebro’ Distinguished Professor of Pe-
G X Y X Y X Y X Y O Nth Contact troleum Engineering at Colorado School of Mines and Codir-
ector of Marathon Center of Excellence for Reservoir Studies.
Condensing Condensing/ Vaporizing He earned BS and PhD degrees in petroleum engineering
Miscibility Vaporizing Miscibility from the University of Texas at Austin. Kazemi is a member of
Miscibility the National Academy of Engineering and a Distinguished
Member and an Honorary Member of SPE. He retired from
Fig. A-1—Balanced binary-tree data structure of MMC method of Marathon Oil Company in 2001 after serving as the Director of
increasing the number of contacts until Nc 21 key tie-lines are Production Research, Manager of Reservoir Technology, and
developed in a single pressure trial (Ahmadi and Johns 2011). Executive Technical Fellow. At Colorado School of Mines,
Kazemi teaches graduate courses and supervises research in
reservoir modeling, well testing, and improved oil- and gas-re-
three neighboring cells is constant or the slope of the three covery processes.
neighboring cells is zero within a specified tolerance. Xiaolong Yin is an assistant professor in the Petroleum Engi-
• Step 5. Either of A or B that follows can be used as a minimiza- neering Department at the Colorado School of Mines. Before
tion function at this stage; in this study, we used (B): joining the school, he was a post-doctoral researcher in chem-
qX ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ical engineering at Princeton University. Yin’s research focuses
Nc
A. Calculate TL, TL ¼ i¼1
ðxi  yi Þ2 , for each key on computational fluid dynamics, suspension, porous media,
and phase behavior. He holds a BSc degree in theoretical
tie-line found in Step 4 and determine the minimal TL; MMP is and applied mechanics from Peking University, an MS degree
the pressure at which the minimal TL approaches zero within a in mechanical engineering from Lehigh University, and a PhD
specified tolerance (Ahmadi and Johns 2011). degree in chemical engineering from Cornell University.
B. Calculate the function that involves
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  equilibrium con- Ramona M. Graves is the Dean of the College of Earth
XNc 2 Resource Sciences and Engineering and a professor of petro-
n
stant (K), f ðKi ; p Þ ¼ ð1  Ki Þ as proposed by
i¼1 leum engineering at the Colorado School of Mines. She holds a
Teklu et al. 2012, for each key tie-line in Step 4 and determine Doctorate degree in petroleum engineering and a BS degree
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
XNc ffi in both mathematics and physics. Graves has an extensive
2
the smallest—that is, f ðKi ; pn Þ ¼ min i¼1
ð1  K i Þ . background in multidisciplinary reservoir characterization, rock
mechanics, environmental issues in petroleum development
This approach is proposed because f ðKi ; pn Þ is a decreasing and production, and high-powered laser/rock/fluid interaction.
function of pressure and approaches zero at MMP. She has taught industry short courses on these topics through-
• Step 6. Increase pressure ð pnþ1 Þ and repeat Steps 2 through 5, out the US, South America, Australia, Russia, the Far East, and
until MMP is determined. For better accuracy, the last few pres- Europe. Graves is a Distinguished Member of SPE and holds an
sure trials can be refined. The minimization function should Honorary Doctorate from the Mining University of Leoben, Aus-
approach zero as the pressure gets close to the MMP. However, tria, awarded in recognition of her scientific achievements and
contributions to the field of petroleum engineering.
convergence is difficult near the point of miscibility, and we
had to resort to the use of the pressure at which the minimiza- Ali AlSumaiti is an assistant professor in the Petroleum Engineer-
tion functions no longer decrease as the MMP. The values of ing Department at the Petroleum Institute, Abu Dhabi. His
MMP obtained are still in good agreement with those found in research is focused on the area of enhanced oil recovery, nu-
the literature. merical reservoir simulation, and unconventional reservoirs.
Currently, AlSumaiti is the Upstream Research Coordinator for
the Petroleum Institute Research Center. He is also responsible
for designing the new enhanced-oil-recovery laboratories in
Tadesse Weldu Teklu is a PhD candidate in petroleum engi- the center. AlSumaiti worked as a reservoir engineer with
neering at Colorado School of Mines. His research includes ex- Zakum Development Company. He has been an active SPE
perimental and numerical aspects of the enhanced oil member, and serves as a board member in the Abu Dhabi SPE
recovery, and phase behavior of conventional and uncon- Chapter. AlSumaiti holds a BS degree from Louisiana State Uni-
ventional reservoirs. Teklu holds a BSc degree in electrical and versity, Baton Rouge, and MS and PhD degrees from Colorado
computer engineering from Addis Ababa University, Ethiopia, School of Mines, all in petroleum engineering.

August 2014 SPE Reservoir Evaluation & Engineering 403

ID: jaganm Time: 16:02 I Path: S:/3B2/REE#/Vol00000/140015/APPFile/SA-REE#140015