Reservoir Engineering I

Barham S. Mahmood
E-mail: barham.sabir@koyauniversity.org
Petroleum Engineering Department
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Phase Behavior of Hydrocarbon

Systems
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• Definitions
• Phase behavior of pure substances
Pressure - temperature diagram (PT)
Pressure – volume diagram (PV)

• Two component systems

Pressure - temperature diagram (PT)
Pressure – volume diagram (PV)

• Multi-component hydrocarbon

 Low-shrinkage oil (heavy oil - black oil)

 High-shrinkage oil (volatile oil)
 Retrograde condensate gas
 Wet gas
 Dry Gas
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Having worked through this chapter the Student

will be able to:

General
• Define; system, components, phases, equilibrium, intensive and
extensive properties.

Pure Components
• Sketch a pressure-temperature (PT) diagram for a pure
component and illustrate on it; the vapor-pressure line,
critical point, triple point, sublimation-pressure line, the
melting point line, the liquid, gas and solid phase zones.
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 Define the critical pressure and critical temperature for a pure component.

 Sketch the pressure- volume (PV) diagram for a pure component

illustrating the behavior above the bubble point, between the bubble and
dew point and below the dew point.

 Sketch a series of PV lines for a pure component with a temperature

below, at and above the critical temperature.
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Two Components
 Plot a PV diagram for a 2 component system and identify
key parameters.
 Plot a PV diagram for a 2 component system and identify
key parameters and the relationship to the vapor pressure
lines for the two pure components.
 Draw a PT diagram for a two component system, to
illustrate the cricondentherm, cricondenbar and the region
of retrograde condensation.

 Define the terms cricondentherm and cricondenbar.

 Explain briefly what retrograde condensation is.
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Multicomponent Systems
 Sketch a PT and PV diagrams to illustrate the behavior at constant
temperature for a fluid in a PVT cell. Identify key features.

 Draw a PT diagram for a heavy oil, volatile oil, retrograde condensate

gas, wet gas and dry gas. Illustrate and explain the behaviour of
depletion from the undersaturated condition to the condition within the
phase diagram.

 Describe briefly with the aid of a sketch, the reasons for and the process
of gas cycling, for retrograde gas condensate reservoirs.
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Definitions
Before we consider the effect of temperature and pressure on hydrocarbon
systems we will define some terms:

System:

Amount of substances within given boundaries under specific conditions

composed of a number of components. Everything within these boundaries
are part of the system and that existing outside of the boundaries are not
part of the system. If anything moves across these boundaries then the
system will have changed.
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Components

Those pure substances which produce the system under all conditions. For

example, in the context of reservoir engineering, methane, ethane, carbon

dioxide and water are examples of pure components.

Phases

This term describes separate, physically homogenous parts which are

separated by definite boundaries.1 Examples in the context of water are the

three phases, ice, liquid water and water vapor.

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Equilibrium

When a system is in equilibrium then no changes take place with respect

to time in the measurable physical properties of the separate phases.

Intensive and extensive properties

physical properties are termed either intensive or extensive. Intensive

properties are independent of the quantity of material present. For
example density, specific volume and compressibility factor are intensive
properties whereas properties such as volume and mass are termed
extensive properties; their values being determined by the total quantity
of matter present.
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Phase behavior of pure substances

The Phase Diagram

• It is beneficial to study the behavior of a pure hydrocarbon under varying
pressure and temperature to gain an insight into the behavior of more
complex hydrocarbon systems.

• Phase diagrams are useful ways of presenting the behavior of systems.

They are generally plots of pressure versus temperature and show the
phases that exist under these varying conditions.
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Figure 1 gives a pressure - temperature phase diagram for a single-

component system on a pressure temperature diagram and the following
points are to be noted.
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Vapor Pressure Line

• The vapor pressure line divides regions where the substance is a
liquid, 2, from regions where it is a gas, 3.

• Above the line indicates conditions for which a substance is a liquid,

whereas below the line represent conditions under which it is a gas.

• Conditions on the line indicate where both liquid and gas phases
coexist.
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Critical Point

• The critical point C. is the limit of the vapor pressure line and defines the
critical temperature, Tc and critical pressure, Pc of the pure
substance.

• For a pure substance the critical temperature and critical pressure

represents the limiting state for liquid and gas to coexist.

• A more general definition of the critical point which is both applicable to

multi component as well as single component systems is; the critical
point is the point at which all the intensive properties of the gas and liquid
are equal.
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Triple Point
The triple point represents the pressure and temperature at which solid,
liquid and vapor co-exist under equilibrium conditions. Petroleum
engineers seldom deal with hydrocarbons in the solid state, however,
more recently solid state issues are a concern with respect to wax,
asphaltenes and hydrates.

Sublimitation-Pressure Line
The extension of the vapor-pressure line below the triple point represents
the conditions which divides the area where solid exists from the area
where vapor exists and is also called the sublimation - pressure line.
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Melting Point Line

The melting line divides solid from liquid. For pure hydrocarbons the
melting point generally increases with pressure so the slope of the line is
positive. (Water is exceptional in that its melting point decreases with
pressure).
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Pressure -Temperature Diagrams (PT)

Consider the behavior of a cell charged with a pure substance and the
volume varied by the frictionless displacement of a piston as shown in
figure 2, below.

Figure 2 Phase Changes

With Pressure at Constant
Temperature
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For example, following the path1 -2 in figure 3 on the pressure-temperature

diagram, i.e. holding temperature constant and varying pressure by expansion

of the cylinder.
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• As the pressure is reduced, the pressure falls rapidly until a pressure is

reached lying on the vapour pressure line

• A gas phase will begin to form and molecules leave the liquid. At further
attempts to reduce the pressure the volume of gas phase increases,
while liquid phase volume decreases but the pressure remains constant

• Once the liquid phase disappears further attempts to reduce pressure

will be successful as the gas expands.

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Above the critical temperature,

following the path 3 - 4, a decrease

in pressure will cause a steady

change in the physical properties, for

example a decrease in density but

there will not be an abrupt density

change as the vapour pressure line

is not crossed. No phase change

takes place.
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Consider the behavior of the system around the critical

point
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• If we go from point A to point B, by increasing the temperature, we go

though a distinctive phase change on the vapor pressure line where
two phases, liquid and gas co-exist

• If we now go a different route to B, starting with the liquid state at ‘A’ increase
the pressure isothermally (constant temperature ) to a value greater than Pc at
E. Then keeping the pressure constant increase the temperature to a value
greater than Tc at point F.

• Now decrease the pressure to its original value at G. Finally, decrease the
temperature keeping the pressure constant until B is reached. The system is
now in the vapor state and this state has been achieved without an abrupt
phase change.
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• The vapor states are only meaningful in the two phase regions. In areas
far removed from the two phase region particularly where pressure and
temperature are above the critical values, definition of the liquid or
gaseous state is impossible and the system is best described as in the
fluid state.
The pressure-temperature diagram for ethane is given in Figure 4.
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Pressure Volume Diagram (PV)

• The process just described in previous slides can also be
represented on a pressure-volume diagram at constant
temperature (Figure 5).
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• For a pure substance vapor pressures at bubble point

and dew point are equal to the vapor pressure of the
substance at that temperature

• Above the critical point, i.e. 3 - 4 , the PV behavior line

shows no abrupt change and simply shows an
expansion of the substance and no phase change. This
fluid is called a super critical fluid.

• A series of expansions can be performed at various

constant temperatures and a pressure volume diagram
built up and the locus of the bubble point and dew point
values gives the bubble point and dew point lines which
meet at the critical point
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• Conditions under the bubble point and dew point lines

represent the conditions where two phases coexist whereas
those above these curves represent the conditions where
only one phase exists. At the critical temperature the P,T
curve goes through the critical point
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Figure 7 Pressure-Volume Diagram of Ethane

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Two component systems

Reservoir fluids contain many components but we will first
consider a system containing two components, such a system
is called a binary

Pressure Volume Diagram

The behavior of a mixture of two components is not as
simple as for a pure substance. Figure 9 shows the P-V
diagram of a two-component mixture for a constant
temperature system.
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The isotherm is very similar to the pure component but the pressure
increases as the system passes from the dew point to the bubble point.
This is because the composition of the liquid and vapor changes as it
passes through the two-phase region

Figure 9 Pressure-Volume Line for a Two-Component System at Constant Temperature

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At the bubble point the composition of the liquid is essentially equal to

the composition of the mixture but the infinitesimal amount of gas is
richer in the more volatile component

Figure 9 Pressure-Volume Line for a Two-Component System at Constant Temperature

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At the dew point the composition of vapor is essentially the mixture

composition whereas the infinitesimal amount of liquid is richer in the less
volatile component.

Figure 9 Pressure-Volume Line for a Two-Component System at Constant Temperature

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The pressure-
volume diagram
for a specific n-
pentane and n-
heptane mixture
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Two component systems

Pressure Temperature Diagram
• Compared to the single line representing the vapour pressure curve for pure
substances there is a broad region in which the two phases co-exist.

• The two-phase region of the diagram

is bounded by the bubble point line
and the dew point line, and the two lines
meet at the critical point. Points within a
loop represent two-phase systems .

Figure 11 Pressure-Temperature Diagram for a

Two Component System
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Consider the constant temperature expansion of a particular

mixture composition
At 1 the substance is liquid
and as pressure is reduced
liquid expands until the
bubble point is reached.

The pressure at which the

first bubbles of gas appear
is termed the bubble point
pressure.

As pressure is decreased
liquid and gas co-exist
until a minute amount of
liquid remains at the dew
point pressure.

Further reduction of pressure

causes expansion of the gas
(point 2)
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• By carrying out a series of constant temperature expansions the phase

envelope is defined and within the envelope contours of liquid to gas ratios
obtained.

• These are called quality lines and describe the pressure and temperature
conditions for equal volumes of liquid. The quality lines converge at the
critical point.
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Critical Point

• In the same way as pure components, when more than one component is
present liquid and gases cannot coexist, at pressures and temperatures
higher than the critical point

• The critical point for a more than one component mixture is defined as a point
at which the bubble point line and dew point line join, ie. it is also the point at
which all the intensive properties of the liquid are identical

• A specific mixture composition will give a specific phase envelope lying

between the vapour pressure lines. A mixture with different proportions of
the same components will give a different phase diagram
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the critical temperature of the mixture TcAB lies between TcA and TcB
whereas the critical pressure PcAB lies above PcA and PcB. It is
important to note that the PcAB and TcAB of the mixture does not
necessarily lie between the Pc & Tc of the two pure components.
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The locus of the critical point of

different mixture compositions for
the ethane and n-heptane system
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Critical Point Loci for a Series

of Binary Hydrocarbon Mixtures
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End of Lec #9
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Retrograde Condensation
• Within the two phase region our two component system there can be
temperatures and pressures higher than the critical temperature where
two phases exist and similarly pressures

• These limiting temperatures and pressures are the cricondentherm

and cricondenbar

• The cricondentherm can be defined as the temperature above which

liquid cannot be formed regardless of pressure, or expressed
differently, as the maximum temperature at which two phases can exist
in equilibrium

• The cricondenbar can be defined as the pressure above which no

gas can be formed regardless of temperature or as the maximum
pressure at which two phases can exist in equilibrium
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Phase Diagram Showing Conditions for Retrograde Considerations

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We now consider the constant temperature

decrease in pressure, 1-2-3.

• As pressure is decreased from 1 the dew

point is reached and liquid forms.

• At 2 the system is such that 5% liquid and

95% vapour exists, i.e. a decrease in
pressure has caused a change from gas to
liquid, opposite to the behaviour one would
expect.

• The phenomena is termed Retrograde

Condensation. From 2 - 3, the amount of
liquid decreases and vaporisation occurs
and the dew point is again reached where
the system is gas
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Multi-component hydrocarbon
• Using two component systems we have examined various aspects of
phase behaviour. Reservoir fluids contain hundreds of components and
therefore are multicomponent systems

• The phase behaviour of multicomponent hydrocarbon systems in the

liquid-vapour region however is very similar to that of binary systems
however the mathematical and experimental analysis of the phase
behaviour is more complex.

• Figure 15 gives a schematic PT & PV diagram for a reservoir fluid

system. Systems which include crude oils also contain appreciable
amounts of relatively non-volatile constituents such that dew points
are practically unattainable.
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Figure 15 Phase Diagrams for Multicomponent Systems

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We will consider the behaviour of several examples of

typical crude oils and natural gases:

• Low-shrinkage oil (heavy oil - black oil)

• High-shrinkage oil (volatile oil)

• Retrograde condensate gas

• Wet gas

• Dry Gas
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Figure 16 Phase diagram for reservoir fluids

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Oil Systems ( Black Oils)

In figure below the line 1-2-3 represents the constant reservoir
temperature pressure reduction that occurs in the reservoir as crude oil is
produced for a black oil
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• As the pressure is dropped from the initial condition as a result of

production of fluids, the fluids remain in single phase in the reservoir
until the bubble point pressure corresponding to the reservoir
temperature is reached.

• At this point the first bubbles of gas are released and their
composition will be different from the oil being more concentrated in
the lighter ( more volatile) components

• When the fluids are brought to the surface they come into the
separator and as shown on the diagram, the separator conditions lie
well within the two phase region and therefore the fluid presents itself
as both liquid and gas

• The pressure and temperature conditions existing in the separator

indicate that around 85% liquid is produced, that is a high percentage
and as a result the volume of liquid at the surface has not reduced a
great amount compared to its volume at reservoir conditions
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• As the pressure is further reduced as oil is removed from the reservoir,

point 3 will be reached and 75% liquid and 25% gas will be existing in
the reservoir

• The summary characteristics for a black oil sometimes termed a heavy

oil or low shrinkage oil are as follows:

• Broad-phase envelope

• High percentage of liquid

• High proportion of heavier hydrocarbons

• GOR < 500 SCF/STB

• Oil gravity 30˚ API or heavier

• Liquid - black or deep colour

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Volatile Oil
• Volatile oil contains a much higher proportion of lighter and
intermediate hydrocarbons than heavier black oil and therefore they
liberate relatively large volumes of gas leaving smaller amounts of
liquid compared to black oils

Figure 18 Phase Diagram for

a Volatile Oil
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• Points 1 and 2 have the same meaning as for the black oil. As the
pressure is reduced below 2 a large amount of gas is produced
such that at 3 the reservoir contains 40% liquid and 60% gas.

• At separator conditions 65% of the fluid is liquid, i.e. less than

previous mixture

• The summary characteristics for a volatile sometimes termed a

heavy oil or high shrinkage oil when compared to black oils are as
follows:

 Not so broad phase envelope as black oil

 Fewer heavier hydrocarbons
 Deep colored
 API < 50˚
 GOR < 8000 SCF/STB
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Retrograde Condensate Gas

• If the reservoir temperature lies between the critical point and the
cricondentherm a retrograde gas condensate field exists and Figure
19 gives the PT diagram for such a fluid

Figure 19 Phase Diagram for

a Retrograde Condensate Gas
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• Before production the fluid in the reservoir exists as a single phase and is
generally called a gas. It is probably more accurate to call it a dense
phase fluid (point 1)

• As the pressure declines to 2 a dew point occurs and liquid begins to

form in the reservoir. The liquid is richer in heavier components than the
associated gas

• As the pressure reduces to 3 the amount of liquid increases. Further

pressure reduction causes the reduction of liquid in the reservoir by re-
vaporisation
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• One of the development options for such a field therefore is to set in place
a pressure maintenance procedure whereby the reservoir pressure does
not fall below the saturation pressure.
• Water could be used as for oils but gas might be trapped behind the water
as the water advances through the reservoir. Gas injection, called gas
cycling ( Figure 20 ), is the preferred yet very expensive option
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The summary characteristics for a retrograde gas condensate fluid are as

follows:

• Contains more lighter HC’s and fewer heavier HC’s than high-shrinkage

oil

• API up to 60˚ API

• GOR up to 70,000 SCF/STB

• Stock tank oil is water-white or slightly colored

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Wet Gas

• The reservoir conditions always remain outside the two-phase

envelope going from 1 to 2 and therefore the fluid exists as a gas
throughout the reduction in reservoir pressure

Figure 21 Phase Diagram for

a Wet Gas
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• For a wet gas system, the separator conditions lie within the two-
phase region, therefore at surface heavy components present in
the reservoir fluid condense under separator conditions and this
liquid is normally called condensate.

• The summary characteristics for wet gas are as follows:

GOR < 100,000 SCF/STB

Condensate liquid > 50˚ API

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Dry Gas
• The phase envelope of the dry gas, which contains a smaller fraction of
the C2-C6 components, is similar to the wet gas system but with the
distinction that the separator also lies outside the envelope in the gas
region

• The term dry indicates

therefore that the fluid does
not contain enough heavier
HC’s to form a liquid at
surface conditions
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The summary characteristics for a dry gas are as follows:

GOR > 100,000 SCF/STB

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Thank you
Any questions??