Enhanced Oil Recovery –

Miscible Displacement Processes

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Introduction
▪ Miscible displacement processes
► Processes where the effectiveness of displacement results primarily from
miscibility between the oil in place and the injected fluid
► Hydrocarbon solvents, CO2, flue gas and nitrogen

▪ Classification
► First contact miscible (FCM) – involves injection of a displacement fluid that is
miscible with crude oil
► Multiple contact miscible (MCM) – miscible conditions are developed in situ
through composition alteration of the injected fluid or crude oil

▪ In immiscible displacement processes, such as waterflooding,

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► Part of the crude oil is trapped as isolated drops, reducing the relative
permeability to oil essentially to zero and continued injection of the displacing fluid
becomes ineffective as the fluid simply flows around the trapped oil
► This may be overcome by application of miscible displacement processes where
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interfacial tension (IFT) is eliminated

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▪ Schematic of an idealized FCM displacement process
▪ Solvent – mixture of low MW hydrocarbons (LPG)
▪ If the process is operated as secondary recovery
► The oil is displaced efficiently ahead of LPG slug, leaving little or no residual oil

▪ If the process is operated as tertiary process

► The injected solvent must displace enough of the water phase to contact the
residual oil and then displace the oil as single-phase mixture with the solvent

▪ Primary solvent (expensive) followed by larger volume of less© 2015 UPES

expensive fluid
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▪ Under proper conditions, injected methane, which is not miscible in all
proportions with oil, might extract certain hydrocarbon components
from the oil as flow occurs through reservoir.
▪ The enriched methane slug could thus become miscible with the oil.
▪ Hence, such processes are sometimes called dynamic miscible
processes.
▪ In either FCM or MCM processes, low MW hydrocarbons, mixtures of
hydrocarbons (LPG), CO2, N2 or mixtures of these can be used as
miscible displacing agents.
▪ Miscibility development depends on phase behavior of the system
► Pressure/temperature diagrams
► Pressure/composition diagrams
► Ternary diagrams
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Pressure/Temperature diagrams
▪ System, existing at ‘M’,
undergoes an isothermal
pressure reduction follows
the path M-L-K-J-I, for a
fixed composition system

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Pressure/Composition diagrams
▪ If the pressure is increased
from the state ‘A’,
► At Dew point, liquid
composition will be x1.
► In between B and C, liquid
composition will be x2 and
vapour composition will be y2.
► At Bubble point, vapour
composition will be y1.

▪ The binary pair would be

miscible over all possible
concentrations at pressures
greater than p4 and
pressures less than p0.

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Ternary diagrams

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▪ Fig 6.12 illustrates the increase
in pressure from 2500 to 3250
psia at a constant temperature of
1600F.
▪ At higher pressure, the system is
single phase over a broader
range of possible concentrations;
i.e. a higher pressure is
favourable for the development of
miscibility between different
components.

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FCM Process
▪ An FCM process normally consists of injecting a relatively small
primary slug that is miscible with the crude oil, followed by
injection of a larger, inexpensive secondary slug.
▪ Ideally, the secondary slug should be miscible with the primary
slug; thus, phase behaviour must be considered at both the
leading and trailing edges of the primary slug.
▪ Clark illustrated the general conditions of first-contact miscibility
and immiscibility as shown in figs 6.13 A through 6.13 C

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Determination of reservoir pressures required for FCM
displacements
▪ Example 6.1 – 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 of methane. Assume that the crude oil is represented
by n-decane and reservoir conditions are 1600F and 2500 psi.
Using the data presented in figs 6.4 and 6.10, determine
whether miscible conditions would exist at the front and back of
the solvent slug.
▪ Example 6.2 – Suppose the oil of example 6.1 is to be
displaced by methane at a reservoir temperature of 1600F,
what pressure would be required to achieve first contact
miscibility?
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Fig 6.14 – phase behaviour considerations for FCM

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MCM process
▪ An 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 and mass
transfer between reservoir oil and injected fluid.
▪ Classified as
► Vaporizing-gas (lean-gas) displacement process
► Condensing and Condensing/Vaporizing-gas (enriched gas)
displacement process
► CO2 miscible displacement processes

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Vaporizing-gas displacement process
▪ Injected fluid, generally, is lean gas (mostly methane and other
low MW Hydrocarbon
▪ Composition of the injected gas is modified as it moves through
the reservoir so that it becomes miscible with reservoir oil
▪ Injected fluid is enriched in composition through multiple
contacts with the oil, during which the intermediate components
in the oil are vaporized into injected gas
▪ Under proper conditions, this enrichment can be such that the
injected fluid of modified composition will become miscible with
the oil at some point in the reservoir
▪ From that point on, under idealized conditions, a miscible
displacement occur
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▪ Assume reservoir crude oil is at C
▪ Injected fluid is shown at A
▪ Miscibility may be created in a
dynamic fashion in the reservoir
▪ Gas A mixes with oil C, the resulting
composition of the mixture lie along
the line AC, say at point ‘a’
▪ Mixture ‘a’ is in two phase region
and separates into vapour at V1 and
liquid at L1
▪ Vapor V1 moves ahead of liquid L1
and contacts fresh oil of
composition C; the resulting mixture © 2015 UPES
is along line V1C, say at point ‘b’
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▪ Mixture b separates into vapour V2 and liquid L2
▪ The process continues with the vapour-phase composition changing
along the saturated vapour curve, V3, V4, etc.
▪ Finally at point e, the vapour becomes miscible with oil C because the
mixing line entirely lies in the single-phase region
▪ From this point, as the displacement continues the process will be
miscible for an ideal process.
▪ However, miscibility will not be generated for all combinations of
injected gases and crude oils.
▪ An example, as shown in fig 6.18, where miscibility does not result.

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▪ Assume reservoir oil is at ‘B’
▪ Assume gas ‘A’ mixes with oil B
along line AB, yielding mixture
which gives vapour V1 and liquid L1
▪ Vapor V1 moves ahead and mixes
with oil B, which gives V2 and L2.
▪ As the process continues, the
vapour will change by successive
mixing only to point V3 and further
enrichment will not occur
▪ The composition change ceases
because line V3L3, when extended
passes through ‘B’
▪ This process will continue as
immiscible process © 2015 UPES

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▪ Distinction between the processes that will and will not be miscible is
determined by the limiting tie-line, illustrated by ‘line mn’ in fig 6.18
▪ This line is a tangent to the binodal curve at critical point ‘O’
▪ Fig 6.12 shows the general effect of pressure on the process

▪ As pressure is increased, two

phase envelope becomes
progressively smaller and the
critical point shifts towards lower
concentration of intermediates.
▪ Limiting tie-line thus shifts toward
lower concentration of
intermediates in the oil and more
oils develop miscibility with a dry
gas of composition such as gas A
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▪ The minimum pressure at which the limiting tie-line just passes through
the reservoir oil composition is called MMP.
▪ MMP is the minimum pressure at which in-situ miscibility can be
achieved in the MCM process for a specified fluid system.
▪ In the vaporizing MCM process, the injected gas composition must lie to
the left and the reservoir oil composition must lie on or to the right of
limiting tie-line, as shown in fig 6.17

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Condensing and condensing/vaporizing-gas displacement

▪ In the condensing process or enriched-gas processs, injected fluid

generally contains larger amounts of intermediate molecular weight
hydrocarbons and thus is more expensive.
▪ Reservoir oil near the injection well is enriched in composition by
contact with injected fluid put into the reservoir
▪ Hydrocarbon components are condensed from the injected fluid into
the oil and thus the process is called condensing process
▪ Under proper conditions, the oil will be sufficiently modified in
composition to become miscible with additional injected fluid and a
miscible displacement will ensue.
▪ However, it has been recognized that the process is often one of a
combination of condensing and vaporizing mechanisms.

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▪ Condensing/vaporizing
► Light intermediates in injected gas (C2 to C4) condense into reservoir oil
► Middle intermediates (C4+) are vaporized from the oil, preventing the
development of miscibility
► As the injection continues, the condensation of the light intermediates
contained in the injected gas into the first oil contacted diminishes
because this oil becomes saturated.
► But, the vaporization of the middle intermediates continues, with the result
that the injected gas is slightly enriched.
► As this condensation/vaporization process moves downstream, the gas
becomes enriched to a greater extent because it contacts more oil.
► The enrichment occurs to the point that the gas nearly becomes miscible
with the original oil and results in an efficient displacement even though
miscibility is never completely developed.

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Condensing
▪ Injected fluid (A) & Oil (C)
▪ Injected fluid A mixes with oil C. the
resulting composition is along line
AC, say at a point ‘a’.
▪ Mixture ‘a’ is in two-phase region and
separates into vapor V1 and liquid
L1.
▪ Vapor V1 moves ahead of liquid L1.
Liquid L1 mixes with additional
injected gas A and the resulting fluid
is along AL1, say ‘b’
▪ Mixture ‘b’ separates into V2, L2
▪ It continues with oil phase
composition changing from L2, L3,
L4 etc. © 2015 UPES

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▪ 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.
▪ From this time, the process will become miscible and will continue as
miscible process because the mixture resulting from mixing along line
ALn will be miscible with fluids ahead of this point.
▪ Here, fluids A and C are on the either sides of the tie-line mn.
▪ If the injection fluid were at point ‘B’, to the left of this line, miscibility
would not be achieved.
▪ Since, at some point during the process, extension of one of the lines
LnVn would pass through the point B and further modification of the
oil-phase composition would not occur.
▪ The process would then continue as immiscible displacement
process.
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▪ For a given injection-fluid/crude oil pair, MMP in condensing gas
process is the minimum pressure at which the limiting tie line mn
passes through the injection fluid composition.
▪ Thus, in condensing MCM process, 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.
▪ At a fixed pressure, the minimum enrichment at which the limiting tie
line passes through the injection gas composition is called the
minimum miscibility enrichment (MME).
▪ Mechanism proposed by Zick – Condensing/Vaporizing

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CO2 miscible displacement process
▪ CO2 is not FCM with most crude
oils at normal reservoir conditions.
▪ However, in-situ development of
miscibility will occur under proper
conditions of pressure,
temperature and composition.
▪ In general, the process behavior is
analogous to vaporizing process
but under some conditions, the
phase behavior is more complex
and two liquid phases or two liquid
phases and a vapor phase form.
▪ On a pseudoternary plot, as
shown in fig 6.22, the process can © 2015 UPES
be shown.
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▪ At temperatures above about 1200F, the phase behavior diagram for
CO2/(C2 – C6)/C7+ is similar in appearance to the C1/(C2 – C6)/C7+
▪ Differences being,
► at the same temperature and pressure, the two phase envelope is much
smaller for the CO2 system than for the CH4 system.
► The limiting tie-line for the CO2 system tends to have a slope that is
more parallel to the CO2/C7+ side of the ternary diagram than the C1
system.

▪ Thus miscibility can be generated between CO2 and reservoir oils at

lower pressures than between CH4 and reservoir oil.
▪ This characteristic of CO2, the ability to generate miscibility at much
lower pressures provides its primary advantage over methane.
▪ If methane was added to the CO2/hydrocarbon system, the phase
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behavior would be changed.

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▪ Adding methane increases the miscibility pressure
► For a given oil, a higher pressure is required for miscibility if C1 is present in the
displacing fluid.
► This is also true for non-condensable gases such as N2 or O2

▪ Presence of H2S is also helpful for development of miscibility

▪ At lower temperatures (about 1200F and less), CO2 phase behavior is
often such that two liquid phases or two liquid phases and a vapor
phase are formed, description of which on a pseudo ternary diagram
is much complex.

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Experimental verification of the role of phase behavior
in miscible displacement
▪ Demonstrated by Metcalfe and
Yarborough
▪ 40 mol% butane and 60 mol%
decane with CO2 as displacing
fluid
▪ At 1900 psia and 1600F, fig 6.26
▪ The three components are
miscible over all compositions,
making it FCM displacement.
▪ Oil recovery was 99% of OOIP

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▪ At 1700 psia, with all other
variables held constant
▪ A small two phase envelope
exists but the oil composition lies
to the right of limiting tie line.
▪ Produced fluid composition
changed in a linear manner from
initial oil composition to vicinity of
critical point
▪ Compositions then moved
around two phase envelope and
finally to pure CO2.
▪ Consistent with MCM process, oil
recovery was 90% OOIP © 2015 UPES

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▪ At 1500 psia, both oil and
injected fluid are to the left of the
limiting tie line and thus,
achievement of miscibility would
not be expected.
▪ The produced fluid concentration
changed almost linearly from
initial composition to a point on
two phase envelope.
▪ Then, it became two phase,
indicating immiscible
displacement.
▪ Oil recovery was 81% OOIP.
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▪ The Metcalfe and Yarborough data show the manner in which the
development of miscibility affects the oil recovery for a relatively
simple system.
▪ FCM process, in which displacing fluid is miscible in all proportions
with displaced phase, has essentially 100% efficiency at the
microscopic level.
▪ Recovery efficiency is also high in MCM process, however, the factors
contributed to reduced efficiency are
► Miscibility must be developed in-situ
► Complete miscibility may not exist across the entire miscible zone
► Dispersion may lead to a temporary or at some locations, permanent loss of
miscibility

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References

▪ Willhite, G. P. and Green, D. W., Introduction to

EOR processes, SPE Textbook series, Texas,
1998.

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