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Prepared by:
Nor Roslina Rosli, PhD
Chapter outline
 Introduction
 Phase Behaviour related to Miscibility
 FCM and MCM Processes
 MMP and MME Processes
 CO2 Injection
 CO2 Injection Problems and Enhancements
Miscible Displacement Process
 Is a process where the effectiveness of the displacement
results primarily from miscibility between the oil and the
injected fluid.
 Examples: hydrocarbon fluid, CO2, flue gas, N2
 Miscibility can be either First Contact Miscibility (FCM) or
Multiple Contact Miscibility (MCM)
 The trapped oil that being in contact with the displacing
fluid is in isolated drop form depending on the wettability
(Kro= 0)
 To displace this trapped oil effectively, a miscible
displacement should be applied
 IFT will be eliminated if the fluid become miscible.
Water-alternating gas (WAG)
 The figure shows and idealized FCM displacement.
 If the process is used as secondary recovery, the oil will
be displaced efficiently leaving little or no residual oil.
 If the process is used as tertiary recovery (post
waterflood), the fluid must be injected enough to
displace the water to contact with the residual oil and
to displace it as a single phase mixture.
 Mixing oil and solvent resulting in higher viscosity
mixture than the pure solvent.
Miscible Displacement Process
 Miscible solvent is usually expensive hence the injected solvent
slug must be relatively small for economic reason.
 For this, the injected solvent must be followed by less expensive
fluid such as water or lean gas.
 The secondary slug should be miscible with the primary slug.
 When water is used as the secondary slug instead of lean gas, a
residual solvent saturation will be retained in the rock (due to
 In MCM, the oil and injected solvent are not miscible upon the
first contact at reservoir conditions.
 The process depends on modification of the oil or injected
solvent compositions to such a degree that the fluids become
miscible as the solvent moves through the reservoir.
Miscible gases
 Various gases and liquids are suitable for use as
miscible displacement agents in either FCM or MCM
 These processes depend on:-
 Reservoir pressure
 Reservoir temperature
 Compositions of the crude oil and the injected solvent
 To develop miscibility, it depends on the phase
behavior of the system
Phase Behavior Related to Miscibility
 Problems in dealing with crude oils:-
 Complex fluids made of numerous chemical components
 Exact chemical composition usually is not known
 Hence the common practice is to use approximate methods
 Various method exist to represent the vapor/liquid phase
behavior of multicomponent systems:-
 Pressure/Volume
 Pressure/Temperature
 Pressure/Composition
 Ternary diagram
 Provide a convenient way to present the boundaries of the
single & multiphase regions
P-T Diagram (Multiple component)
 This diagram is for a fixed overall composition
 Pbub & Pdew meet at Pc
 Pc is where the properties of liquid and gas
become identical.
 All points within ABC curve consist of two phases.
 Two phases can exist at a pressure & temperature
greater than Pc.
 The system originally exists as a single fluid phase
at M
 At point L, the system changes to a saturated
liquid phase with a single bubble of vapor present
at a negligible volume.
 More vapor is formed as the pressure is reduced
further where at K the system is 50/50 volume %
mixture of liquid and vapor.
 All liquid vaporizes at J except for a single drop of
negligible liquid.
 Further pressure reduction causes the system to
exist as a vapor without any liquid present.
P-T Diagram (Different Composition)
 This diagram is for
several different
composition of an
ethane/n-heptane binary
 The dashed line is the
locus of the critical point
conditions for those
different compositions
P-T Diagram (Different Composition)
 At 300°F, a pressure
greater than about 1250
psia is required before all
possible mixtures of
ethane and n-heptane
are miscible


P-x diagram  The composition is expressed as a mole
fraction of the more volatile
 If the P is increased on a system
represented by A, no phase change
occurs until the dew point B is reached
at p1
 At B, an insignificant amount of liquid
form with a composition given by x1
 As the P is increased, more liquid
forms and the compositions of the
coexisting liquid and vapor phases are
given by projecting the ends of the
straight, horizontal line through the
two-phase region of the composition
 Upon further compression, the system
becomes totally liquid
 The binary pair would be miscible over
all possible concentrations at p0>P>p4
P-x Diagram
 The diagram shows data for
a system (methane/butane)
at several T.
 For example, at 100°F, two
phases will not be formed
above a methane conc of 87
 The composition of only 1
phase exists decreases with
increasing T
 The cricondenbar is also the
critical pressure where two
phases can exist.
 Complete miscibility will
exist above this P for all
methane/n-butane mixtures
P-x Diagram
 This diagram shows 3
different T.
 At 160°F, The system
would be single phase at
all compositions above
about 1090 psi

P-x Diagram
 The diagram shows mol% of C1 added to
a reservoir fluid mixture originally
containing 30.8% C1, 55.4% n-C4, and
13.8% C10
 Again, Pc is where Pb and Pd meet.
Properties of liquid and gas are identical.
 Single phase exist above the phase
boundary lines where two phase exist
below it
 For example if C1 is to be added at a
constant pressure of 2000 psia (at 160°F),
the mixture will be a single phase as long
as that C1 concentration was less than 25
mol% and more than 97 mol%.
 If the system pressure is increased to the
cricondenbar pressure or higher, any
25 97 addition of all concentration of C1 into
the reservoir mixture will be single phase
P-x Diagram
 The diagram shows
additional two different
gases containing different
concentration of C4
 If a heavier component
such as C4 is added gas
phase, it will shift both Pb
& Pd into lower pressures.
 Miscibility between the
added gas and the reservoir
fluid could be achieved at a
lower pressure compared
with the added gas C1=
Ternary diagram
 Compositional phase diagram for three component mixtures
must be plotted in such way that the compositions of all of them
can be displayed.
 Each apex of the triangle corresponds to 100% of a single
 The usual convention is to plot the lightest component at the top
and the heaviest at the lower left.
 Each side of the triangle represents two component mixtures
 The left side of the triangle represents all possible mixtures of
the light and heavy components.
 Composition usually plotted in mole fraction or mole percent
 Both P & T are constant for a single diagram.
Ternary diagram  Point 1 represents 100%
component B
 Point 2 represents 30%
component A, and 70%
component C
 Point 3 represents a mixture
which consists of 50%
component A, 30% component
B, and 20% component C
 Line 4 – 3 length represents the
composition of component A
 Line 5 – 3 length represents the
composition of component B
 Line 6 – 3 represents the
composition of component C
 Point 7 represents 50%
component B, 15% component
A, and 35% component C.
Ternary diagram

 Point P is
 40% A
 40% B
 20% C
 Point M is
 67.5% A
 32.5% C
Ternary diagram  The diagram shows the
phase behavior for the
ternary system of C1, n-C4,
and C10 at 2500 psia and
 At these conditions, all
C1/n-C4 mixtures & n-
C4/C10 mixtures are
 C1/C10 mixtures are not
miscible at all conditions.
 This is consistent with
previous P-x diagram for
miscibility between C1 and
n-C4 (Fig 6.4)  next slide.
 Any composition that lays in
that envelope is an
immiscible mixture
P-T Diagram Confirmation
 At 160°F, a pressure
about 250o psia,
 All C1/n-C4 mixtures &
n-C4/C10 mixtures are
 C1/C10 mixtures are not
miscible at all
 This is consistent with
160 pseudoternary diagram.
Pseudoternary diagram
 Representation of
more than 3
components is an
 C2-C6 is a pseudo
component in this
Ternary diagram  Changing either
temperature or pressure
modifies the shape of the
 The diagram shows an
increase in pressure from
2500 to 3500 psia at a
constant T of 160°F
 At higher pressure, the
system is single phase over
a broader range of possible
 Higher pressure is
favorable for the
development of miscibility
between different
First Contact Miscibility (FCM)
 FCM normally consists of injecting a relatively small
primary slug that is miscible with the crude oil followed by
injecting a larger & less expensive secondary slug
 Economic considerations are important in determining the
slug sizes
 Secondary slug must be miscible with the primary slug
hence the phase behavior must be considered at both
leading and trailing edges of the primary slug
 Residual saturation of the primary slug material will be
trapped and bypassed if the slugs chosen are not miscible
with each other
Example conditions of FCM
 Methane and crude oil
are partially soluble in
one another.
 However, at reservoir
conditions they do not
mix at all and form two
 Hence, the
displacement of crude
oil by methane will be
immiscible flood.
 Higher molecular weight
hydrocarbons e.g. propane or
LPG are completely soluble
with oil at most reservoir
 Oil exists as liquid and
propane exists as gas at
atmospheric conditions
 If the condition is increased
to reservoir condition, both
propane and crude oil exist
as liquid
 These two liquid will
completely mixed hence
 The displacement of oil by
propane at that condition
will be miscible process.
 Both methane and propane
exist as gas at atmospheric
 At reservoir condition
methane still appears to be a
gas while propane is a liquid
 These fluids will mix in all
proportions and appear to be
a single phase gas (fluid
since it is above critical
 Hence displacement of
propane by methane at these
conditions would be
 Fig 6.4 verifies this behavior.

Example 1
 Example 1: Determination of Pressure Required for
FCM with a Butane Primary Slug
 An FCM miscible displacement is to be designed in which a
slug of butane is the primary displacing solvent. The
butane slug is to be displaced by dry gas consisting
essentially of methane. Assume that the crude oil is
represented, in a phase-behavior sense, by n-decane and
reservoir conditions are 160°F and 2500 psi. Determine
whether miscible conditions would exist at the front and
back of the solvent (butane) slug. (Use data in Fig 6.4 and
Reservoir conditions: 160°F and 2500 psi.
 Fig 6.4: The locus point for C4/C10
is not given. But at 160°F and 2500
psi, C4 is in liq state. So C4 and C10
will be miscible.
 The locus point for C1/C4 mixture
is well above the locus critical
point, therefore miscible.
 Ternary diagram Fig 6.10 confirms
miscibility of C4/C10 and C1/C4.
 Note: If P is reduced to 1500 psi, C1
would bypass C4, and trapped in
the reservoir.
Example 2
 Suppose the oil of 5200

previous example is to be
displaced by methane at a
reservoir temperature of
160°F. What pressure
would be required to
achieve first-contact
The should be higher than 5200 psi for the
system to be a single phase over the total
concentration range, thus to be miscible.
Note: Rock would fracture at this P. 160
Pseudoternary diagram for FCM
Example 1:
 Assuming primary slug is
intermediate components
(C2– C6), secondary slug is
light components (C1 or
N2), and the crude oil is
mixture C7+
 The diagram shows that
miscibility exists between
the primary and secondary
slug materials but not
always between primary
slug and crude oil
Pseudoternary diagram for FCM
Example 2:
 The diagram shows that miscibility
exists between both crude oil –
primary slug and primary slug –
secondary slug
 This condition is required for an
ideal FCM process
 It also shows that the primary slug
can be diluted with light component
and still be miscible with crude oil.
 It gives the maximum composition of
light component when it is mixed
with the primary slug to be miscible
with crude oil.
Pseudoternary diagram for FCM
Example 3:
 The diagram shows the
phase boundaries for a
system in which
miscibility exists
between primary slug
and crude oil but not
between the primary
slug and secondary slug.
Multiple Contact Miscibility (MCM)
 MCM displacement process is one in which the condition
of miscibility is generated in the reservoir through in-situ
composition changes resulting from:-
 Multiple-contacts
 Mass transfer between reservoir oil and injected fluid
 MCM are classified as:-
 Vaporizing-gas (lean gas) displacements
 Condensing-gas displacements
 Condensing/vaporizing-gas (enriched-gas) displacements
 CO2displacements
Multiple Contact Miscibility

Condensing gas

Condensing/ Vaporizing

• Injected fluid is • Injected fluid • CO2 is not FCM • A combination of

generally a generally contains with most crude oil condensing and
relatively lean gas larger amounts of at normal reservoir vaporizing
that contains intermediate- temperature and mechanisms
mostly methane molecular-weight pressure • The light
and other low hydrocarbons more • The process intermediate
molecular-weight expensive behavior is components in the
hydrocarbons • Hydrocarbon analogous to the injected gas (C2–
• Intermediate components are vaporizing process C4) will condense
components in the condensed from • Under some into the reservoir
oil are vaporized injected fluid into conditions, the oil and the middle
into the injected the oil phase behavior is intermediate
gas • The oil will be more complex and components (C4+)
• Miscibility sufficiently will form either are vaporized from
displacement will modified in twoliquid phases or the oil into the gas
occur composition to two liquid phases phase
become miscible and a vapor phase • Miscibility will be
with additional achieved
injected fluid continuing the gas
Vaporizing-gas (Lean Gas)
Displacement Process
LO = saturated VO = saturated
vapor curve  Reservoir crude oil is
liquid curve
represented by point C &
the injected fluid is point A
 The injected fluid is
classified as dry gas
 From the locus of critical
points, it shows that a very
O = Critical / high pressure is required to
plait point generate a FCM (Fig 6.4).
 Miscibility may be created
in a dynamic fashion.
Vaporizing-gas (Lean Gas)
Displacement Process
 At the leading edge of the displacement
front, gas A mixes with oil C resulting a
composition of mixture along line AC at
point a
 Mixture a is in 2-phase region and
separates into vapor V1 & liquid L1
 Since V1 is more mobile than L1, V1 moves
ahead of L1 and contacts fresh oil at
composition C while L1 remains behind to
mix with more pure solvent resulting a
mixture along line V1C at point b
 Mixture b separates into V2 & L2
 The process continues with the vapor-
phase composition changing along the
saturated vapor curve, V3, V4… etc
 Finally, at point e the vapor becomes
miscible with oil C because the mixing
line lies entirely in the single-phase region
Vaporizing-gas (Lean Gas)
Displacement Process
 Miscibility will not be generated for all
combinations of injected fluid and reservoir
 Diagram shows that miscibility does not
 Assume gas A mixes with oil B along line AB,
yielding mixture a which gives vapor V1 and
liquid L1
 Vapor V1 moves ahead and mixes with new
oil B, which gives V2 and L2
 As the process continues, the vapor will
change by successive mixing only to point V3
 Further enrichment will not occur since the
composition change ceases because when
line V3L3 is extended, it passes through point
 Mixtures of V3 and B will be along the tie-line
and further enrichment of the vapor the
intermediate and heavy components will not
 The determination of any process miscibility is
determined by the limiting tie-line, mn
 mn is tangent to the bimodal curve at critical point
 The injected dry gas is enriched by vaporizing
intermediate and heavy components from the oil
 Critical point can be shifted towards lower
concentration of intermediates in the oil by
increasing the system pressure, hence more oil can
develop miscibility with A
 The minimum pressure at which the limiting tie-
line just passes through the reservoir oil
composition is called the MMP
 MMP is the minimum pressure at which in-situ
miscibility can be achieved in MCM process for a
specified fluid system
 In vaporizing MCM process, the injected gas
composition must lie to the LEFT and the reservoir
oil composition lie on or to the RIGHT of the
limiting tie-line
 Typical applications of this process are at pressures
well above 3000 psi
Condensing-Gas Displacement
 Reservoir crude oil is
represented by point C and the
injected fluid is represented by
point A
 The injected fluid contains
significant amount of
intermediate components (C2–
 The process depends on the
condensation of these
components into the reservoir
oil hence modifying the oil
 Then, the modified oil then
becomes miscible with the
injected fluid.
1. The injected fluid A mixes with oil
C and resulting a composition
along line AC at point a
2. Mixture a is in the two-phase
region and separates into vapor V1
and liquid L1
3. Vapor V1 moves ahead of liquid L1
and causing L1 immobile. L 1
mixes with additional gas A and
the resulting fluid is along mixing
line AL1 at point b
4. Mixture b separates into vapor V2
and L2
5. The process continues with the
oil-phase composition changing
from L2 , L3 , L4 … Ln
6. For the tie-line through mixture e,
the immobile oil Ln becomes
miscible with the injected fluid
because mixing line ALn will lie
entirely in the single-phase region
 If the pressure were changed, the 2-
phase region would be modified and
limiting tie-line will shift
 The MMP in a condensing-gas
process is the minimum pressure at
which the limiting tie-line just passes
through the injection fluid
 The injected fluid composition must
lie on or to the right and the oil
composition must lie to the left of the
limiting tie-line
 The minimum enrichment at which
the limiting tieline passes through the
injection gas composition at a fixed
pressure is called minimum
miscibility enrichment (MME)
CO2 Displacement Process
 The description for CO2
miscible displacement process is
same as for the high pressure
vaporizing process
 Its ability to generate miscibility
with reservoir oils at lower
pressures than methane
provides the primary advantage
over methane
 Can refer to Figure 6.4
 The miscibility pressure would
be increased if methane is
added. Also true for the
presence of other
noncondensable gas (N2, O2).
So impurities in CO2 in
detrimental to miscibility
Experimental Verification
 The relationship between phase behavior and oil recovery
in an experimental linear displacement test was
demonstrated by Metcalfe and Yarborough
 Crude oil to be recovered was a binary mixture:-
 40 mol% butane
 60 mol% decane
 Displacing fluid was pure CO2
 The porous medium consisted of an 8 ft long and 2 in
diameter Berea sandstone core
 No water present in the displacement
 Local thermodynamic equilibrium was assumed to exist
Experimental Verification
 At 1900 psia and 160°F, the
3 components are miscible
over all compositions
 The displacement was an
FCM displacement
 The reduced liquid
concentration essentially
followed the ideal mixing
line from the oil
composition to the pure
CO2 apex
 Oil recovery was 99% of
Experimental Verification
 At 1700 psia and same
temperature, a small two-phase
envelope exists
 The oil composition lies to the
right of the limiting tie-line
 The produced fluid composition
changed in essentially a linear
manner (after CO2 was first
detected in the effluent) from
the initial oil composition
 Compositions then moved
around the twophase envelope
and finally to pure CO2
 Consistent with MCM process
 Oil recovery was 90% of OOIP
 At 1500 psia, both oil and
injected fluid are to the left of
the limiting tie-line hence
miscibility would not be
 Produced fluid concentration
changed almost linearly from
the initial composition to a
point on the two-phase
 Effluent then became two-
phase indicating an
immiscible displacement
 Recovery was 81% of OOIP
Conclusion from Experiment
 Development of miscibility affects oil recovery for a
simple system.
 An FCM process, the displacing fluid is miscible in all
proportions with the displaced fluid, had ~100%
 Recovery in an MCM is much less than FCM.
 Immiscible displacement results in lower recovery
than MCM.
Experimental Measurement of
 Determination of miscibility condition as the condition
that miscibility is achieved during FCM or MCM process is
very important for designing a miscible displacement
process. Temperature, pressure and solvent injection
composition are three major parameters that determine the
miscibility condition.
 Methods have been designed to measure MMP and MME.
 Minimum Miscibility Pressure (MMP)
 Minimum pressure required for achieving miscibility
 Minimum Miscibility Enrichment (MME)
 Mole fraction of enriching agent to reach miscibility at a given
Experimental Measurement of
 Slim-tube test & rising-bubble
apparatus (RBA).
 Typically consists of a SS steel tube
5/6 “ ID and about 40 ft long
 The tube is packed with fine grade
sand or glass beads (size of 100
 Tube is coiled so that the flow is
horizontal & neglect the gravity
 Pump forcing the fluids and the
pressure is controlled by a BPR
 The coiled tube are placed inside a
constant temperature bath
 A visual cell also is at the outlet to
observe the fluid product.
Experimental Results
 Recoveries are plotted as a
function of displacement
 MMP is assumed to be the
P at the break in the curve
(the pressure above which
very little additional
recovery occurs
 The recovery was
calculated as the % of oil
produced at CO2
 A displacement is
considered miscible when
more than 80% of OOIP is
Experimental Measurement of
MMP/MME  An alternative approach has been
used especially for condensing-gas
drive process is to measure the
MME at a fixed pressure
 Repeated displacements are run
with increasingly higher
concentrations of intermediate
compound such as C2+ in the
displacing solvent
 The diagram shows a typical result
from slim-tube displacements for
two different pressures
 Visual observation &
chromatographic analyses of the
effluents can provide additional
information about the
displacement and phases.
Prediction of MMP
 MMP is commonly predicted from
 Empirical correlations based on experimental results
 Phase behavior calculations based on an EOS and computer modeling

• Relatively simple to apply

• Predicted value can be significantly error
Empirical • Typically used as a screening tool

• More reliable results

• Requires availability of composition data for the reservoir
Application of
• Such data often not available
EOS • Calculations are complex and need to be calibrated
Empirical Correlations
Condensing- Vaporizing- CO2 Miscible
Gas Drive Gas Drive Displacement
• Benham’s • Stalkup’s • Holm &
Correlation Correlation Josendal’s
• Mungan’s
• Yellig &
• Aston’s
Condensing-Gas Drive:
Benham’s Correlation
 Is based on a study of the calculated mixed behavior of various
mixtures of five different reservoir fluids with intermediates (C2
through C4 mixtures) and methane (C1)
 Phase behavior was represented on pseudoternary diagrams
(right triangles were used instead of equilateral)
 Benham et al calculated the critical pressures and temperatures
for a number of mixtures of reservoir fluids, methane, and
 The correlations considered:-
 Pressure: 1500 – 3000 psia
 Temperature: 70 – 260°F
 Average molecular weight of C5+ in the reservoir: 180 – 240
 Average molecular weight of C2 to C4 in the displacing fluid: 34 –
Example calculation using
Benham’s Correlation: Calculation
of MMP for a Condensing-Gas
Displacement Process
 Assume that a reservoir that is to be flooded with a
condensing-gas process is at 150°F. The average
molecular weight of the C5+ fraction of the reservoir
oil is 200. A displacement gas is available with the
composition 60 mol% CH4, 30 mol% C3H8, and 10
mol% C4H10. The maximum pressure at which the
displacement can be conducted is 2000 psia.
Determine whether multiple-contact miscibility can
be achieved at these conditions.
1. Determine the mol% of the
intermediates component
2. Calculate the average molecular
weight of the intermediates.
 75% C3, 25% C4
 MW = 0.75(44)+ 0.25(58) 2070
= 47.5  Use lines 49
3. Intersect the mol% of the
intermediates component with
the reservoir oil average
molecular weight line.
4. Determine the miscibility
pressure of the mixture.
 MMP = 2070 40%

Conclusion: The MMP is above the operating P. Therefore miscibility cannot be achieved.
Suggestion: The composition of the intermediates must be increased to achieve miscibility.
Vaporizing-gas Drive:
Stalkup’s Correlation
 Limited info is available for MMP prediction in
vaporizing-gas drive.
 Stalkup’s correlation: For estimating miscibility
pressure with a lean hydrocarbon gas
 Was developed from data on nine oils on these
 Temperature: 140 – 265°F
 Saturation pressures of reservoir oil: 596 – 4035 psia
 Average MW of C7+ in the reservoir oil: 149 – 216
 MMP: 3250 – 4750 psia
Stalkup’s Correlation
Correlations related to pure CO2
Miscible Displacement
 Holm & Josendal’s and
Mungan’s Correlations
were developed as an
extension of Benham’s
 Gives MMP as a
function of T and MW
 The correlation is
applicable for a
displacing fluid that is
pure CO2
CO2 Displacement:
Yellig & Metcalf’s Correlation
 An even simpler correlation.
 MMP was correlated as a
single curve as a function of
 If Pb> MMP, hence Pb= MP
 Accounts for the possible
formation of two phases
when the pressure is below
the bubble point pressure of
the reservoir oil
 Applicable for pure CO2
displacing phase
Aston’s Correlation
 Aston et al developed correlation for pure & impure
 For pure CO2, the MMP is
 X vol 
pCO 2  8.78  10 4
T  M wC 5 
1.06 1.78
 
 X int 
 When CO2 is impure, the MMP is affected.
Aston’s Correlation
When CO2 is impure,
the MMP is affected.
A correction factor was
proposed for impurities
in CO2.
Example: Calculation of MMP with
different correlations
 It is desired to estimate the MMP for a specified crude
oil. 100% CO2 is to be considered as the displacing
fluid. The reservoir temperature is 130°F, the C5+
molecular weight for oil components is 185.8, the
volatiles make up 5 mol% of the oil and the
intermediates 7.5%. The ratio of ole fractions of
volatiles to intermediates in the oil is 0.667.
Holm & Josendal’s Yellig & Metcalf’s



130 0.136
 X vol 
Aston’s correlation: pCO 2  8.78 10  4 T 
M wC 5  
 
 X int 
pCO 2  8.78 10  4 130 185.81.78 0.667 0.136  1581
Comparison of % error
 The measured value of MMP for this oil using the slim
tube apparatus is 1,500 psia.
 Comparison of error:

Correlation MMP, psia Error, %

Holm & Josendal 1880 [(1880-1500)/1500] 100= 25%

Yellig & Metcalf 1630 [(1630-1500)/1500] 100= 8.7%

Aston 1,581 [(1581-1500)/1500] 100= 5.4%

EOS Phase Behavior Calculations
 EOS are used to predict behavior by predicting
fugacity coefficients, which then predicts phase
equilibrium, K values.
 A typical approach is to apply the generalized Redlich-
Kwong EOS with appropriate mixing rules.
 CO2/hydrocarbon system can be complex where 3 or
more phases can exist.
 Sophisticated EOS modeling with computer
technology is required
Fluid Properties in Miscible
 The performance of a miscible displacement process
depends on the fluid physical properties that affect the
flow behavior in the reservoir.
 Fluid density
 Fluid Viscosity
 Additional properties:
 Surface tension
 Diffusion coefficient
 CO2 solubility
 Other transport & thermodynamic properties
Fluid density
 Density difference between displacing and displaced flud
can cause gravity override, underride, or fingering.
 Densities at reservoir T & P differ from those at surface
 The change in density as a function of T & P can be
 The densities of fluids used in miscible displacement
generally are smaller than crude oil (except in the case of
 Gas density can be calculated with EOS, pv = ZRT, where Z
is the compressibility factor.
Compressibility factor, Z
Fluid density: Calculation of C3
 Consider propane at a temperature of 270°F and a
pressure 1,500 psia. Calculate the density.

At this condition, C3
is above Tc and Pc.

T 730
TR    1 .1
Tc 666
Find value for Z from
p 1500 Figure 6.41
pR    2.43
pc 617.4
Gas density
0.4 10.73psi.ft 3 / R.lbm.mol  730R
v  2.09ft 3 / lbm mol
1500 psia
  0.48 lbm mol/ft 3
  0.48 lbm mol/ft 3  44 lbm/lbm mol  21.1 lbm/ft 3

Crude oils tend to have densities between 50 to 60 lbm/ft3.

The density of propane is about 40 to 50% of a density of crude oil.
Compare results with this
At 270°F & 1,500 psia
ρ = 0.34 g/cm3
= 21.2 lbm/ft3

Calculations of CO2 density
 Calculate the CO2 density at 150°F & 1500 psia (These
conditions are above the critical P&T).
 Pc =1073 psia; Tc = 547.7°R
 Z ~ 0.54
Check results with this

CO2 density at 150°F &

1500 psia.

ρCO2 = 0.3 g/cm3 = 18.7



Fluid Viscosity
 Mobility ratio of displacement process is a direct
function of viscosities of displaced and displacing
 
 For miscible displacement, M d
 oil
D inj
 Where µd = viscosity of displaced fluid
 µD = viscosity of displacing fluid
Viscosity of hydrocarbon gases
 Katz et al. (1959) in
Handbook of Natural
Gases, presents
viscosity data for
natura gases and
intermediate MW
 Example here show
viscosity data for C3.
Typical value of
viscosity at conditions
270°F and 1500 psia, is
µ = 0.036 cp.
CO2 Viscosity
 Viscosity of CO2 as a
function of T & P is
given here.
 At 1500 psi & 150°F
(above critical point
of CO2), the viscosity
is 0.025 cp. 0.025
Chapter outline
 Introduction
 Phase Behaviour related to Miscibility
 FCM and MCM Processes
 MMP and MME Processes
 CO2 Injection
 CO2 Injection Problems and Enhancements

Power CO2
sector Oil
+ CCS production

CO2 /water
injection well

CO2 / water oil recovery
storage Oil

Depleted oil field

 A volume of CO2 is injected to mobilize and displace
residual oil.
 Intermediate and higher MW HC are extracted into the
CO2-rich phase through multiple contacts between oil and
 Under ideal conditions, miscibility conditions can be
reached very quickly.

CO2 Displacement Process

CO2 Phase Diagram
 Tc = 87.8°F = 31°C,
 Pc = 1071 psi = 7.39 MPa
 Thus in most cases, the
injected fluid is above Tc.

Above: A chamber containing two phases of carbon dioxide--liquid and gas. As

temperature and pressure increase (from left to right), the two phases merge to
become a supercritical fluid. (Source: NASA & University of Leeds) 87
Criteria for Applications of CO2
 Oil gravity of less than 25° API (heavy oil) is
considered unfavorable for CO2 EOR.
 A highly fractured reservoir is unfavorable because it
provides a conduit from injection to producing well.
 Adequate and reliable source of CO2 at reasonable cost
is a primary prerequisite.
 Depth is important because the minimum miscibility
pressure is usually above 1200 psi requiring a depth of
greater than 2500 ft.
 The viscosities of reservoir oil in most CO2 projects is
about 1 cp.
Why CO2?
 CO2 is a good flooding agent
 CO2 is currently discharged into the atmosphere and could be a major
contributor to greenhouse effect
 The use of CO2 in improving the oil recoveries have been used since
 CO2 in liquid state (Tc= 87.8°F & Pc= 1073 psi) is a rather unique for oil
recovery agent
 CO2 flooding can be applied in both miscible & immiscible
displacement processes.
 The recovery of oil from CO2 flooding is highly dependable on phase
behavior between CO2, water, and reservoir oil
 CO2 -oil phase behavior strongly affects fluid flow by altering:-
 Mobility Ratios, IFT, Kr , Rates of mass transfer

Sources of CO2
 Source of CO2 is a crucial factor.
 Gas must be available for a long time (up to 20 years).
 Gas must be relatively pure. Impurities can cause problems:
 Methane will increase MMP
 H2S hazardous & cause environmental problems
 The supply must be continuous, not interrupted.
 Miscible bank may deteriorate and threaten the success of the
 Unforeseen conditions e.g. fires, strikes, changing market may
cause temporary shut down of a plant that supplies CO2.
 Natural sources is the best. Can come from wells that produce
CO2. Oil companies will lease basins that are good prospects for
 Anthropogenic sources: Stack gas from coal-fired power plant,
ammonia plant, etc. But source is impure.
Mechanism of CO2 Flooding
 Viscosity Reduction
 Oil Swelling
 IFT Reduction
 Oil Vaporization
 Miscibility Effect
 Blow-down Recovery (gas drive when CO2 is
 Increase in Injectivity

Recycling CO2
 CO2 often channels in a reservoir and breaks through
at production wells relatively early in the process.
 Since the fuel value of CO2 = zero, it is separated from
other produced gases, recompressed, and re-injected.
 Recycling CO2 adds to the project cost, but is less
expensive than purchasing new CO2.

Advantages of CO2 Flooding
 Swells oil and reduces viscosity
 Forms miscibility with oil
 Acts as solution-gas drive, even if complete miscibility is not achieved.
 The miscible front, if lost, will regenerate itself as it does with the lean gas
 Unlike LPG, CO2 will become miscible with oils that have been depleted of
C2-C4 fractions.
 CO2, highly soluble in water, causes water to swell and becomes slightly
 Miscibility can be attained above 1500 psi in many reservoirs.
 CO2 is non-hazardous, non-explosive gas that causes no environmental
concern is large quantities are lost to the atmosphere.
 May be available from anthropogenic (flue gas) or natural sources (CO2
Disadvantage of CO2 EOR
 Solubility of CO2 in water may increase volume needed for
oil miscibility, this can be overcome by the increased volume
of CO2-saturated water.
 The low viscosity of any free CO2 gas at low reservoir P will
promote early breakthrough to the producing well, reducing
sweep efficiency. Production of large volumes of diluted gas
requires expensive cleanup and recycling facilities.
 After miscibility is attained, the oil is less viscous than
reservoir oil, causing fingering and premature breakthrough.
 Injection of water is often necessary to reduce fingering.

Disadvantage of CO2 EOR
 CO2 forms H2CO3 with water which is highly corrosive.
Special metal alloys and coatings for facilities are needed.
Corrosion mitigation adds cost of the process.
 Alternate injection of water and CO2 requires a dual
injection system, adding to the cost and complexity of the
 Large volumes of CO2 are needed. It may take 5-10 MMcf of
gas to produce 1 barrel of stock tank oil.
 CO2 is normally not available locally, requiring long distance
pipelines. CO2 pipelines are more subject to breakdown than
natural gas pipelines, thus causing expensive delays and
interferes with the project.
Mobility ratio of CO2-EOR
 The viscosity of injected CO2 is small (0.06 – 0.10 cp)
depending on reservoir T & P.
 Oil & water are displaced by CO2 under unfavorable
mobility ratio, M.
 This leads to fingering of the CO2 through the oil
phase, and poor macroscopic displacement efficiency.

d oil
M 
 D inj
Water-Alternating-Gas (WAG)
 To overcome the
fingering problem,
inject slugs of CO2
and water alternately.
 The purpose of
injecting water in to
reduce the relative
permeability and
thereby reduce its
 Other methods of
mobility control: Use
of foams and polymer
in conjunction with
CO2 injection.

Density difference between CO2 &
water & oil
 At injection conditions, CO2 has a specific gravity of
about 0.4 (depending on the reservoir)
 Depending on the oil density, CO2 can tend to move to
the top of the formation and to override the displaced
 In some cases, this gravity effect is exploited by
flooding from the top of the reservoir and displacing
fluids downdip, but this can only be done where the
reservoir structure is suitable.
CO2 Solubility
 In CO2-EOR, it is useful
to calculate the amount
of CO2 that is dissolve in
 The gas loss due to
solubility in water is
 Loss of CO2 is larger at
lower T and lower P.
Effect of Salinity on Solubility in Water
 If water has a salinity of
3% to 10% total dissolved
solids, the loss of CO2
will be less.
 Miscible fluids generally have small viscosities and
therefore fingering and poor volumetric sweeps result.
 Reservoir heterogeneities magnify this problem.
 Density difference contributes to poor volumetric
contact because of gravity overrride unless these
density difference can be use to advantage in dipping
 The fluids applicable at moderate reservoir P are
expensive and limited supply.
MCM Process: Other gases
 Other gases are suitable as MCM displacement fluid:
 Relatively dry HC gases with high CH4 content
 N2
 Flue gases
 These gases require much higher pressures to achieve
miscibility than CO2.
 These other gases are more suitable for deep reservoirs
where high pressures can be achieved without fracturing
the rock.
 Rule of thumb: Fracturing P = 0.6psi/ft of depth.
 Is fracturing P is exceeded, the reservoir rock will fail and
injected fluid will channel through the fractures, bypassing
the oil.
Factors Affecting Displacement
Efficiency of Miscible Processes
 Displacement efficiencies at microscopic and
macroscopic level in a miscible process are less than
 Efficiency depends on a number of factors, including
whether the displacement is conducted as a secondary
or tertiary process.
 In secondary process, it is assumed that there is no
mobile water, unless it is injected as part of the
 In tertiary process, both oil and water are mobile and
will be displaced.
Microscopic Displacement
Efficiency: No Mobile Water
 When conducted as a secondary process, the IFT between
the displacing and displaced phases is zero (miscible; oil &
water mixed in 1 phase).
 Based on Nc correlations, if σow = zero, Nc = max (∞),
microscopic displacement = max.
 Residual saturation in portions of the rock contacted by
displacing fluid = zero.
 Dispersion and mixing at microscopic level, combined with
the associated phase behavior, are the major reasons that
microscopic displacement efficiencies in MCM processes
conducted in the absence of mobile water are not 100%.
(Typically 90-97%)
Macroscopic Displacement
Efficiency: No Mobile Water
Four major factors affect the recovery efficiency:
 Mobility ratio
 Viscous fingering
 Gravity segregation
 Reservoir homogeneity
Effect of Mobility Ratio
 M is a dimensionless number. M
 If M < 1, it is favorable. inj
 If M > 1, flow is unstable (viscous fingering).
 The viscosities of miscible solvents are small (< 0.1 cp)
thus M is unfavorable.
 M range from 4 to 86 in MCM process, 4 to 40 in FCM.
 This results in poor areal sweep.
Effect of Mobility Ratio
 EA is a strong function of M.
 At M = 0.2  90% efficiency
 At M = 10  50% efficiency.
Effect of Viscous Fingering
 The result of high M is viscous fingering.
 An adverse viscosity ratio in a miscible process results
in viscous fingering, which leads to reduced volumetric
 The effect of viscous fingering on displacement
efficiency in an MCM processis more complicated.
Effect of Viscous Fingering
 Fig.6.55 shows results from two sets of
 In the first set, CO2 was used to
displace an oil (Soltrol™) at conditions
at which the process was FCM.The M=
16,which is unfavorable.
 In the second set, CO2 displaced a
crude'oil (Wasson crude) in an MCM
process conducted at a pressure above
the MMP. The viscosity ratio was 21.
 There was no mobile water present in
the experiments.
 In both sets of experiments, the oil
recovery was delayed becauseof the
adverse mobility ratio; i.e., there was
early breakthrough of CO2
 The implication is that an interaction
or synergism occurs between viscous
fingering and phase behavior to cause
liquid-phase dropout and trapping.
Effect of Gravity
 A dimensionless group is used to characterize gravity
 The viscous/gravity ratio, Rv/g defined in field units as:
2050uo L
Rv / g  
kp h
Example: Vertical Sweep Efficiency
at Breakthrough – CO2 EOR
 Consider the displacement of an oil by CO2 in a linear
system. The effective length of a horizontal reservoir is
500 ft and the thickness is 40 ft. Calculate the sweep
efficiency at breakthrough at the downstream end of
the reservoir.