Chapter 3b:

PHASE BEHAVIOUR OF BINARY

AND MULTICOMPONETS FLUIDS
Lesson Learning Outcome
At the end of the session, students should be able to:

1) Interpret isothermal pressure- composition

diagram.
2) Interpret ternary diagrams.
3) Relate reservoir fluids properties with surface fluids
properties.
Two Component Systems

Such a system is called “binary system”

One component more volatile than the
other

Components are miscible

Example: methane-ethane, propane-
pentane, benzene-ethanol, ethanol-water
Degree of freedom for binary system

- Example: CO2- water system

Representation in
π Ø Example F
P,T, x surface

1 0 I, LW, V, LV 3 volume

2 0 I-LW, H-V, H-LW 2 region, surface

3 0 H-LW-V, I-H-V, H-LW-LV 1 curve, line

4 0 I-H-LW-V, H-LW-LV-V 0 point

 Schematic T-x cross sections of the phase
behaviour in the binary system water + gas at
pressures P1 (a) and P2 (b)

P-T diagram for CO2-water in hydrate forming

region
Schematic P-x cross-sections of the phase
behaviour in the binary system water + gas at
temperatures T1 (a) and T2 (b)
 Two Component Systems: Pressure -Volume diagram

Isotherm similar to pure

component

Pressure decreases as
system goes from bubble
point to dew point

Composition of liquid and

vapor phases change from
bubble point to dew point

Physical properties
function of composition
e.g. density
Pressure volume diagram for specific two component
mixture.

The diagram is for a

52.4 mole% mixture of
N-heptane and
N-pentane

A ‘finger print’ of
the mixture
 Schematic Pressure - Temperature Diagram of a Binary
Mixture B  The phase rule indicates that in a
binary vapor - liquid system, both the
C temperature and the pressure are
independent variables
Critical
Point  The phase envelope - bounded by the
bubble point and dew point curve
D

Two Phase  The two curves meet at the critical

Pressure

Region (C), where all differences between

and two phases vanish and the
phases become indistinguishable

 Two phase can coexist at some

conditions above critical point

 The highest pressure (B) and the

highest temperature (D) on the phase
Temperature envelope are called the cricondenbar
and cricondentherm, respectively
Pressure- Temperature Diagram for a Binary System

Critical
Point Cricondenbar
Vapor Pressure
Curve for pure
Component A

Cricondentherm
Pressure

Bubble point

Two phase
envelope for
mixture A+B

Dew point
Vapor Pressure
Curve for pure
Component B

Temperature
Pressure - Temperature Diagram for a Binary System

A1
Critical
Bubble Point Point
≈ 0% vapour, Cricondenbar
≈ 100% liquid
Pressure

A2

Two phase
region
Cricondentherm

Dew point
≈100 % vapour, ≈ 0% liquid

Temperature
Pressure- Volume Diagram of Binary Mixture

T >Tc
T <Tc T =Tc

C, Critical Point

T3
Pressure

Vapour

Liquid Two Phase Region

Volume
Variation of Saturated Fluid Density With Temperature

 The densities of vapour and

liquid phases approach each
Saturated
other as the temperature
Liquid increases

 At critical point, they

become equal
Density

Critical Point
 All the differences between
the phases are reduced as
Saturated the system approaches the
Vapour critical point

Temperature  The phases become the

same and indistinguishable
at the critical point
Multi- Component Hydrocarbon
 Reservoir fluids contain hundreds of component -
multicomponent system

 The phase behaviour of multicomponent hydrocarbon

systems in the liquid- vapour region however is very
similar to that of binary system : more complex the
mathematical and experimental analysis

 Understanding the phase behavior of a binary system

allows appreciation of the more complex multi-component
systems.

 crude oils also contain appreciable amount of relatively

non- volatile constituents which affect the systems phase
behavior
Phase Diagram For Multicomponent
System
Phase Diagram of Segregated Oil & Gas in the Vicinity
of Gas/Oil Contact
Critical
Point
C Gas Phase Envelope
Res. Critical
Pres. Point
C
Pressure

Oil Phase Envelope

Reservoir
Temp.

Temperature
Schematic Diagram of Stabilising Produced Oil As Stock
Tank Oil & Gas at Standard Condition

Gas Gas

Separator Stock Tank

Oil
Reservoir
Oil

 The reservoir fluid is produced and measured at the

surface as the stock tank oil and gas at standard
conditions, as shown schematically.
Sources of Reservoir Thermodynamic
Engineering Data
 Physical properties are needed accurately to describe the
fluids:
– pressures up to 1500 bar ( 22000psia),
– high temperatures (up to 250°C)
- corrosive fluids (water more saline than sea water,
which is approximately 35000ppm)

 Empirical relationships

 Laboratory measurements
 The data required include:
•density,
• compressibility
•formation volume factors
•Gas:oil ratios for determination of recovery factors
•Viscosity
•gas: oil ratios for production rates
• interfacial tension for recovery efficiency, as it has a major
influence on oil trapping
The Thermodynamic Path From Reservoir To Stock Tank

separators
Up to 35 bar, 0 - 60°C
gas
To sell
Stock tank oil
Ambient conditions
Well
bore

water
T&P
FVF
GOR
Reservoir Density
Shrinkage
Up to 1500 bar, 250°C Bubble/ dew points
Flash/ differential
Viscosity
Flow rates
Pressure- Volume Diagram For A
Two- Component Mixture
Pressure decreases as the process
passes from the bubble point to the
dew point
 The line from bubble point is not
horizontal and is not necessarily
straight
 The decrease in pressure is caused
by the changes in the compositions
of the liquid and the gas as the
Pressure

process passes through the two-

phase
 At the bubbles point, the
composition of the liquid is
Bubble Point essentially equal to the overall
composition of the mixture, but the
infinitesimal amount of gas is richer
in the more volatile component
Dew Point
 At the dew point the composition of
the vapor is essentially equal to the
overall composition of the system
Specific Volume and the infinitesimal amount of
liquid is richer in the less volatile
Typical pressure-volume diagram of a two- component
component mixture showing one isotherm  The changes in slope of the line at
below the critical temperature the bubbles point and dew point are
not as sharp as for a pure substance
Pressure- Composition Diagram for
Two- Component Mixtures  Combination of the composition
and pressure which plot above
the envelope indicate conditions
at which the mixture is
completely liquid
 Combinations of composition
Pressure, psia

and pressure which plot below

the envelope indicate conditions
at which the mixture is gas
 Any combinations of pressure
Liquid and composition which plot
Tie line within the envelope indicate that
the mixture exists in two phases,
2 1 3 gas and liquid
 The bubble- point line is also the
locus of compositions of the
liquid when two phases are
Gas present
 The dew- point line is the locus
of composition of the gas and
0 50 100 liquid are in equilibrium
Composition, mole % component A  The line which ties the
composition of the liquid with
the composition of gas in
Typical pressure-composition diagram of a equilibrium is known as an
two-component mixture with one tie line, 123 equilibrium tie- line
 Tie-lines are always horizontal
for two- component mixtures
Pressure- Composition Diagram
for Two- Component Mixtures
 Consider that a mixture of
composition represented by
point 1 is brought to
equilibrium at the indicated
Pressure, psia

pressure and the temperature

of the diagram
 The composition of the liquid
Liquid
is indicated by point 2, and
Tie line the composition of the
2 1 3 equilibrium gas is given by
point 3
 The tie- line can also be used
to determine the quantities of
Gas gas and liquid present at 1
 The length of line 12 divided
0 50 100 by the length of the tie- line
Composition, mole % component A 23, is the ratio of moles of gas
to total moles of mixture
Typical pressure-composition diagram of a  The length of line 13 divided
two-component mixture with one tie line, 123 by 23 is the ratio of moles of
liquid to total moles of mixture
Isothermal pressure- composition
diagram of mixtures of methane
and ethane
 There are four saturation envelopes
corresponding to four different
temperatures
 The edge of the diagram labeled
100 mole percent methane
represents vapor pressure of
methane
 The edge of the diagram labeled
zero mole percent methane gives
vapor pressures of ethane
 When the temperature exceeds the
critical temperature of one
component, the saturation envelope
does not go all the way across the
diagram; rather, the dew point and
bubble point lines join at a critical
point
 E.g., when the critical temperature
of a mixture of methane and ethane
is minus 100°F, the critical pressure
is 750 psia, and the composition of
the critical mixture is 95 mole
percent methane and 5 mole
percent ethane
Three- Component Mixtures
Component A  Compositional phase
diagram for three-
component mixtures must
be plotted in such way that
the compositions of all
three components can be
displayed
 Diagrams formed from
equilateral triangles are
convenient for this purpose
 These are called ternary
diagrams
Ternary Diagrams
Ternary Diagrams
 Each apex of the triangle corresponds to
Component A 100% of a single component
 The usual convention is to plot the lightest
component at the top and the heaviest
component 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 the heavy
components
 Point within the triangle represents three-
component mixtures
 Composition is usually plotted in terms of
mole fraction or mole percent
 For a single diagram, both pressure and
temperature are constant; only composition
change
 Exercise
Define the following terms:
 Phase
 Bubble point
 Cricondentherm
 Cricondenbar
 Critical state
 Dew point
 Pseudo- critical pressure and temperature
 Reduced pressure and temperature
 Saturated liquid
 Saturated vapour
 Saturated pressure
 Stock tank oil
 Undersaturated fluid