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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)
process
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
immiscibility).
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
processes
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
system
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
1250
300
P-x diagram The composition is expressed as a mole
fraction of the more volatile
component
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
axis
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
mol%
The composition of only 1
phase exists decreases with
increasing T
The cricondenbar is also the
critical pressure where two
87
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.
1090
At 160°F, The system
would be single phase at
all compositions above
about 1090 psi
0.72
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=
100%
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
component.
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
160°F
At these conditions, all
C1/n-C4 mixtures & n-
C4/C10 mixtures are
miscible.
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
miscible.
2500
C1/C10 mixtures are not
miscible at all
conditions.
This is consistent with
160 pseudoternary diagram.
Pseudoternary diagram
Representation of
more than 3
components is an
approximation.
C2-C6 is a pseudo
component in this
diagram.
Ternary diagram Changing either
temperature or pressure
modifies the shape of the
curve
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
concentrations
Higher pressure is
favorable for the
development of miscibility
between different
component
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
phases
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
conditions
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
miscible
The displacement of oil by
propane at that condition
will be miscible process.
Both methane and propane
exist as gas at atmospheric
conditions
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
point)
Hence displacement of
propane by methane at these
conditions would be
miscible
Fig 6.4 verifies this behavior.
2000
150
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
6.10)
Reservoir conditions: 160°F and 2500 psi.
Solution
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
miscibility?
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
CO2
Condensing gas
Condensing/ Vaporizing
Vaporizing-gas
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
conditions:-
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
temperature
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
CO2
For pure CO2, the MMP is
0.136
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.
Solution:
Holm & Josendal’s Yellig & Metcalf’s
1630
1880
130
130 0.136
X vol
Aston’s correlation: pCO 2 8.78 10 4 T
1.06
M wC 5
1.78
X int
pCO 2 8.78 10 4 130 185.81.78 0.667 0.136 1581
1.06
Comparison of % error
The measured value of MMP for this oil using the slim
tube apparatus is 1,500 psia.
Comparison of error:
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
ZRT
v
p
0.4 10.73psi.ft 3 / R.lbm.mol 730R
v 2.09ft 3 / lbm mol
1500 psia
1
0.48 lbm mol/ft 3
2.09
0.48 lbm mol/ft 3 44 lbm/lbm mol 21.1 lbm/ft 3
270
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
chart.
0.3
66
Fluid Viscosity
Mobility ratio of displacement process is a direct
function of viscosities of displaced and displacing
fluids.
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
HCs.
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
SPECIAL TOPIC
Chapter outline
Introduction
Phase Behaviour related to Miscibility
FCM and MCM Processes
MMP and MME Processes
CO2 Injection
CO2 Injection Problems and Enhancements
83
CCS & CO2-EOR
Power CO2
sector Oil
recovery
+ CCS production
well
CO2 /water
injection well
Additional
CO2 / water oil recovery
(WAG)
CO2
geologic
storage Oil
84
CO2-EOR
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
CO2.
Under ideal conditions, miscibility conditions can be
reached very quickly.
85
CO2 Displacement Process
86
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.
89
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
project.
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
CO2.
Anthropogenic sources: Stack gas from coal-fired power plant,
ammonia plant, etc. But source is impure.
90
Mechanism of CO2 Flooding
Viscosity Reduction
Oil Swelling
IFT Reduction
Oil Vaporization
Miscibility Effect
Blow-down Recovery (gas drive when CO2 is
immiscible)
Increase in Injectivity
91
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.
92
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
process.
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
acidic.
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
reservoirs).
93
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.
94
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
system.
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.
95
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
mobility.
Other methods of
mobility control: Use
of foams and polymer
in conjunction with
CO2 injection.
97
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
fluids.
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
water.
The gas loss due to
solubility in water is
significant.
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.
Problems
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
reservoirs.
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
100%.
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
process.
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
oil
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
sweep.
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
experiments.
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
effects.
The viscous/gravity ratio, Rv/g defined in field units as:
2050uo L
Rv / g
kp 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.