CHAPTER 4:

PHASE BEHAVIOR
LEARNING OUTCOME:

By the end of the lecture, students must be able to:

a) Determine fluid chemical composition
b) Classify typesof reservoirs with the reservoir fluids
c) Describe phase behaviour of pure substances
d) Describe the multi component hydrocarbon
e) Explain P-T diagram for oil reservoir
f) Explain P-T diagram for gas reservoir
BASIC PHASE BEHAVIOR
Phase defines as homogenous part of a system that is physically
distinct and separated from other parts of the system by definite
boundaries.
 The phase (either solid, liquid or gas ) depends on the temperature and
pressure acting on the substance.
Ice (solid phase) can change to water (liquid phase) by increasing
temperature. By further increasing the temperature can change water
(liquid phase) to steam (vapor phase).
Changes here is what we called phase behaviour.
HYDROCARBON SYSTEM

Display multi phase behaviour over wide ranges of temperature and pressure.
Important phase occurring in petroleum reservoir:
- Liquid phase: crude oil or condensate
- Gas phase : natural gases
SINGLE COMPONENT SYSTEMS
Component -> Number of molecular or atomic present in the
substance.
Often use word pure to describe single component system.
SINGLE COMPONENT SYSTEMS
Curve GC bubble point curve represents the
saturated liquid line
Line FC- dew point curve represents the state of
Component -> Number of saturated gas.
Curve AFCGB is two-phase region
Point C- critical point

Intensive properties; P, T, density, composition

and viscosity
 Line AC- terminates at critical point. Curve
called the vapor pressure curve OR
boiling point curve

Corresponding pressure at any point on

curve is the vapor pressure Pv.
 Line AC- terminates at critical point. Curve
called the vapor pressure curve OR
boiling point curve

Corresponding pressure at any point on

curve is the vapor pressure Pv.

Vapor phase
 Line AC- terminates at critical point. Curve
called the vapor pressure curve OR
boiling point curve

Corresponding pressure at any point on

curve is the vapor pressure Pv.
Liquid phase

REMARKS:
P< Pv system is entirely vapor phase
P> Pv system entirely liquid phase
P= Pv vapor and liquid coexist in
equilibrium
QUICK LOOK METHOD-COX CHARTS

Vapor pressure chart for

hydrocarbon
components
Allows quick estimation
of the vapor pressure Pv
of a pure substance at
specific temperature.
QUESTION

You have a pure n-hexane held in a laboratory cell at 80 deg F and 200 psia. Determine
the state of the substance.
LEE AND KESLER (1975) APPROACH

Accentric factorto to characterize non-spericity of a molecule.

Tr Reduced temperature
QUESTION

Calculate the vapor pressure of n hexane at 80 deg F by using Lee Kesler

correlation.

Steps:
1) Get Tc, Pc,
2) Calculate Tr
3) Solve A and B
4) Solve Pc equation
BINARY SYSTEM
Two phases can exist in equilibrium at various pressures at same temperature.

Point 1-
Point 2-
Point 3-
Point 4-
BINARY SYSTEM
Two phases can exist in equilibrium at various pressures at same temperature.

Point 1 - Initial P an T in vapor state

Point 2 - Pressure increased isothermally
- At dew point, composition vapor phase
= overall composition of binary mixture
Point 3-Bubble point. Composition of liquid phase
identical with whole system
Point 4- Pressure increased significantly with
decrease volume
PHASE RULE

Gibbs derived simple relationship between number of phases in equilibrium, the

number of components and number of independent variables that must be specified
to describe the state of system completely.
Phase rule:
F= C-P+2
F= num of variables required to determine state of system at equilibrium, or number of
DOF
C= number of independent component
P= number of phases
EXAMPLE

For single system, determine number of DOF required for system to exist in single
phase region

Soln:

F= 1-1+2 = 2. Meaning 2 DOF must be specified for system to exist in single phase
region.These must be P and T
EXAMPLE

What DOF allowed for binary system in two phases?

Soln:

Since C=2 and P= 2. F=2-2+2=2. Could besystem pressure and temperature or pressure
and conc or other combinations.
MULTI COMPONENT SYSTEMS

Uses of multi component p-T

diagrams:
-Classify reservoirs
-Classify naturally occurring hydrocarbon
system
-Describe phase behaviour of reservoir
fluid
KEY POINTS ON P-T DIAGRAM
Cricondentherm (Tct)The Cricondentherm
is defined as the maximum temperature
above which liquid cannot be formed
regardless of pressure (point E). The
corresponding pressure is termed the
Cricondentherm pressure pct.
Cricondenbar (pcb)The Cricondenbar is
the maximum pressure above which no gas
can be formed regardless of temperature
(point D). The corresponding temperature is
called the Cricondenbar temperature Tcb.
Phase envelope (two-phase region)The
region enclosed by the bubble- point curve
and the dew-point curve (line BCA), wherein
gas and liquid coexist in equilibrium, is
identified as the phase envelope of the
hydrocarbon system.
KEY POINTS ON P-T DIAGRAM
Critical pointThe critical point for a
multicomponent mixture is referred to as
the state of pressure and temperature at
which all intensive properties of the gas and
liquid phases are equal (point C). At the
critical point, the corresponding pressure
and temperature are called the critical
pressure pc and critical temperature Tc of
the mixture.
Quality linesThe dashed lines within the
phase diagram are called quality lines. They
describe the pressure and temperature
conditions for equal volumes of liquids.
Note that the quality lines converge at the
critical point (point C).
KEY POINTS ON P-T DIAGRAM
Bubble-point curveThe bubble-point
curve (line BC) is defined as the line
separating the liquid-phase region from the
two-phase region.
Dew-point curveThe dew-point curve
(line AC) is defined as the line separating
the vapor-phase region from the two-phase
region.
RETROGRADE CONDENSATION
Consider isothermal decrease .
From point 1, pressure decreased, dew point line
crossed, liquid begins to form.
At point 2, system is 25% liquid by vol and 75% gas
Decrease in pressure causes change from gas to
liquid.-- exactly reverse of behaviour, hence name
retrograde condensation.
From point 2 to point 3, liquid amount decreases,
dew point crossed second time, system again
become gas.
Retrograde condensation occur between critical
temp and the cricondentherm.
PRESSURE COMPOSITION DIAGRAM
FOR TWO COMPONENT MIXTURES
Plot above envelope = mixture
completely liquid
Plot below envelope= mixture is
gas
Plot within envelope= mixture in
two phases; gas and liquid
Line that ties composition of
liquid with gas known as
equilibrium tie lines.
Tie lines always horizontal for
two component mixtures.
DETERMINING QUANTITIES OF GAS
AND LIQUID USING TIE LINES

=

=

TEMPERATURE COMPOSITION
DIAGRAM FOR TWO
COMPONENT MIXTURES
Six saturation envelopes corresponding to 6 diff pressures
Lower line envelope = bubble point line
Upper line envelope = dew point line
Plot below envelope = mixture completely liquid
Tie lines gives composition of liquid and gas in equilibrium
horizontally.
Bubble point line correspond to composition equilibrium
liquid
Dew point line give composition of equilrium gas.
Length of tie line represent quantitities of gas and liquid at
equilibrium.
THREE COMPONENT MIXTURES
Also called ternary diagrams
Each apex correspond to 100% of single
component
Usual convention isplot lightest
component at top and heaviest
component at lower left.
Composition is usually plotted in terms
of mole fraction / mole percent
In thid diagram, T and p cons. Only comp
changes
THREE COMPONENT MIXTURES
At point 1, pure component B . 100%
component B (at apex)
At point 2, is 30 mole % component A
and 70 mole % component C
At point 3, 50 mole % component A, 30
mole% component B and 20 mole %
component C.
THREE COMPONENT PHASE
DIAGRAMS Methane lightest plotted at the top.
Dew point line lies along top of
saturation envelope; bubble point line
lies along the bottom.
Equilibrium tie lines are staright but not
horizontal. Tie lines determined
experimentally and given on diagram.
THREE COMPONENT PHASE
DIAGRAMS Point 1 is mixture of methane, propane
and n-pentane which exhibits
equilibrium gas and liquid at T and p
Point 2 is the composition of
equilibrium gas
Point 3 is composition of equilibrium
liquid.
13
Quantity of gas:
23

12
Quantity of liquid:
23
EXAMPLE

Determine the compositions and quantities of equilibrium gas and liquid

when 6 lb moles of a mixture of 50 mole percent methane, 15 mole
percent propane and 35 mole percent n pentane are brought to
equilibrium at 160 deg F and 500 psia.
USES OF TERNARY DIAGRAM
Used in analysis for miscible
displacement
Roughly define the compositional
boundaries that separate different
types of hydrocarbon systems.
CLASSIFICATION OF RESERVOIR AND
RESERVOIR FLUIDS
Reservoirs conveniently classified on the basis of the location of the
point representing the initial res pressure Pi and temperature T wrt p-T
diagram of the reservoir fluid.
Reservoir can be classified into two types:

a) Oil reservoirs- If the reservoir temperature T < Tc of the reservoir fluid

b) Gas reservoirs- If the reservoir temperature T > Tc of the HC fluid
OIL RESERVOIRS

Depending on the initial reservoir pressure Pi, oil reservoir can be

subclassified into following categories:

1) Undersaturated Oil Reservoir Pi > Pbp of the reservoir fluid

2) Saturated oil reservoir Pi = Pbp of the reservoir fluids
3) Gas cap reservoir Pi < Pbp of the reservoir fluids
 Undersaturated
oil reservoir

Saturated oil
reservoir

Gas cap reservoir

CLASSIFICATION OF CRUDE OILS:

Ordinary black oil

Low shrinkage crude oil Depends
on:
High shrinkage (Volatile) crude oil
Near critical crude oil
1. Physical properties
2. Composition
3. Gas oil ratio
4. Appearance
5. Pressure- temperature
phase diagram
6. Reservoir temperature
ORDINARY BLACK OIL

Equally spaced quality lines

GOR= 200-700 scf/STB
Oil gravities= 15-40 API
Stock tank oil brown to dark
green in colour
ORDINARY BLACK OIL

Liquid shrinkage curve prepared

by plotting liquid vol percent as
function of pressure
This curve approximate staright
line except at very low
pressures.
LOW SHRINKAGE OIL

Quality lines are closely spaced

near to dew point curve
GOR < 200 scf/ STB
Oil gravity < 15 API
Black or deeply coloured
Substantial liquid recovery at
separator condition (Point G)
on 85% quality line
LOW SHRINKAGE OIL

Quality lines are closely spaced

near to dew point curve
GOR < 200 scf/ STB
Oil gravity < 15 API
Black or deeply coloured
Substantial liquid recovery at
separator condition (Point G)
on 85% quality line
VOLATILE CRUDE OIL
This phase diagram for a volatile
(high-shrinkage) crude oil
Quality lines are close together near
the bubble-point and are more
widely spaced at lower pressures.
Oil formation volume factor less
than 2 bbl/STB
Gas-oil ratios between 2,0003,200
scf/STB
Oil gravities between 4555 API
VOLATILE CRUDE OIL
Lower liquid recovery of separator
conditions as indicated by point G
Greenish to orange in color
API gravity of the stock-tank liquid
will increase in the later life of the
reservoirs.
NEAR-CRITICAL CRUDE OIL
If the reservoir temperature T is
near the critical temperature Tc
of the hydrocarbon system
all the quality lines converge at
the critical point, an isothermal
pressure drop (as shown by the
vertical line EF) may shrink the
crude oil from 100% of the
hydrocarbon pore volume at the
bubble-point to 55% or less at a
pressure 10 to 50 psi below the
bubble- point.
NEAR-CRITICAL CRUDE OIL
High GOR in excess of 3,000
scf/STB
An oil formation volume factor
of 2.0 bbl/STB or higher.
The compositions of nearcritical
oils are usually characterized by
12.5 to 20 mol% heptanes-plus,
35% or more of ethane through
hexanes, and the remainder
methane.
NEAR-CRITICAL CRUDE OIL
High GOR in excess of 3,000
scf/STB
An oil formation volume factor
of 2.0 bbl/STB or higher.
The compositions of nearcritical
oils are usually characterized by
12.5 to 20 mol% heptanes-plus,
35% or more of ethane through
hexanes, and the remainder
methane.
LIQUID SHRINKAGE FOR CRUDE OIL
SYSTEM
CLASSIFICATION OF GAS
RESERVOIRS:
Retrograde gas-condensate
Depends
Near-critical gas-condensate on:
Wet gas
Dry gas 1. Physical properties
2. Composition
3. Gas oil ratio
4. Appearance
5. Pressure- temperature
phase diagram
6. Reservoir temperature
RETROGRADE GAS-CONDENSATE
RESERVOIR Reservoir temperature T lies
between the critical temperature
Tc and cricondentherm Tct of
the reservoir fluid

When the pressure is decreased

on these mixtures, instead of
expanding (if a gas) or
vaporizing (if a liquid) as might
be expected, they vaporize
instead of condensing.
RETROGRADE GAS-CONDENSATE
RESERVOIR Point 1- Initial condition of
a retrograde gas reservoir.
(P res > upper dew point,
HC exist as single phase)
Point 2- reservoir pressure
declines isothermally
during production. The
attraction between the
molecules of the light and
heavy components causes
them to move further apart
further apart.
RETROGRADE GAS-CONDENSATE
RESERVOIR Point 2- Attraction between
the heavy component
molecules becomes more
effective; thus, liquid begins
to condense.
Point 3- Process continues
with decreasing pressure
until the liquid dropout
reaches its maximum
RETROGRADE GAS-CONDENSATE
RESERVOIR Further reduction in
pressure permits the heavy
molecules to commence
the normal vaporization
process.
This is the process whereby
fewer gas molecules strike
the liquid surface and
causes more molecules to
leave than enter the liquid
phase.
RETROGRADE GAS-CONDENSATE
RESERVOIR The vaporization process
continues until the reservoir
pressure reaches the lower
dew-point pressure.
This means that all the
liquid that formed must
vaporize because the
system is essentially all
vapors at the lower dew
point.
RETROGRADE GAS-CONDENSATE
RESERVOIR Curve is commonly called
the liquid dropout curve.
Condensed liquid volume
seldom exceeds more than
15%19% of the pore
volume
RETROGRADE GAS-CONDENSATE
RESERVOIR Gas-oil ratios between
8,000 and 70,000 scf/STB.
Condensate gravity above
50 API
Stock-tank liquid is usually
water-white or slightly
colored.
DIFFERENCES BETWEEN OILS WITH
CONDENSATES?
Reservoir fluids that contain heptanes and are heavier in
concentrations of more than 12.5 mol% are almost always in
the liquid phase in the reservoir.

Oils have been observed with heptanes and heavier

concentrations as low as 10% and condensates as high as
15.5%.
NEAR-CRITICAL GAS-CONDENSATE
RESERVOIR
If the reservoir temperature is
near the critical temperature

All the quality lines converge at

the critical point, a rapid liquid
buildup will immediately occur
below the dew point as the
pressure is reduced to point 2.
NEAR-CRITICAL GAS-CONDENSATE
RESERVOIR
Due to isothermal reduction in
pressure, several quality lines
are crossed very rapidly
reservoir goes from the
retrograde region to a normal
vaporization region where the
liquid ceases to build up and
begins to shrink again.
WET-GAS RESERVOIR
Reservoir temperature is above
the cricondentherm of the
hydrocarbon mixture
Reservoir fluid will always
remain in the vapor phase
region as the reservoir is
depleted isothermally, along the
vertical line A-B
Produced gas flows to the
surface, however, the pressure
and temperature of the gas will
decline
WET-GAS RESERVOIR
Gas enters the two-phase
region, a liquid phase will
condense out of the gas and be
produced from the surface
separators.
This is caused by a sufficient
decrease in the kinetic energy of
heavy molecules with
temperature drop and their
subsequent change to liquid
through the attractive forces
between molecules.
WET-GAS RESERVOIR
Gas oil ratios between 60,000 to
100,000 scf/STB
Stock-tank oil gravity above 60API
Liquid is water-white in color
Separator conditions, i.e., separator
pressure and temperature, lie
within the two-phase region
 The hydrocarbon mixture exists
DRY GAS RESERVOIR as a gas both in the reservoir
and in the surface facilities.
The only liquid associate with
the gas from a dry-gas reservoir
is water.
Gas-oil ratio greater than
100,000 scf/STB
Kinetic energy of the mixture is
so high and attraction between
molecules so small that none of
them coalesce to a liquid at
stock-tank conditions of
temperature and pressure.
DRY GAS RESERVOIR
Can be observed that
hydrocarbon mixtures may exist
in either the gaseous or liquid
state
COMPOSITIONAL OF VARIOUS FLUID
TYPES
Many characteristic properties of these individual components (in other
words, pure substances) have been measured and compiled over the
years.
These properties provide vital information for calculating the
thermodynamic properties of pure components, as well as their
mixtures.
The most important of these properties are:
Critical pressure, pc Critical compressibility factor, zc
Critical temperature, Tc Acentric factor, T
Critical volume, Vc Molecular weight, M
COMPOSITIONAL
OF VARIOUS
FLUID TYPES
UNDEFINED PETROLEUM FRACTIONS

These heavy fractions are often lumped together and identified as the
plus fraction, e.g., C7+ fraction
A proper description of the physical properties of the plus fractions and
other undefined petroleum fractions in hydrocarbon mixtures is
essential in performing reliable phase behavior calculations and
compositional modeling studies
UNDEFINED PETROLEUM FRACTIONS

Distillation analysis or a chromatographic analysis is available for this

undefined fraction to measure the molecular weight and specific gravity.
UNDEFINED PETROLEUM FRACTIONS

Riazi and Daubert (1987)

-based on the use of the molecular weight M and specific gravity of the
undefined petroleum fraction as the correlating parameters
UNDEFINED PETROLEUM FRACTIONS
Riazi and Daubert (1980)
-Predicting physical properties of pure compounds and undefined HC
mixtures
-based on normal boiling point and the specific gravity as correlating
parameters.
UNDEFINED PETROLEUM FRACTIONS
Riazi and Daubert (1980)
-Predicting physical properties of pure compounds and undefined HC
mixtures
-based on normal boiling point and the specific gravity as correlating
parameters.
UNDEFINED PETROLEUM FRACTIONS

Riazi and Daubert (1987)

-based on the use of the molecular weight M and specific gravity of the
undefined petroleum fraction as the correlating parameters
UNDEFINED PETROLEUM FRACTIONS

Edmister (1958)
- correlation for estimating the acentric factor T of pure fluids and
petroleum fractions
UNDEFINED PETROLEUM FRACTIONS

Edmister (1958)
- critical compressibility factor is another property that is often used in
thermodynamic-property prediction models.
UNDEFINED PETROLEUM FRACTIONS

Summary of the critical compressibility estimation methods

EXAMPLE

Estimate the critical properties and the acentric factor of the

heptanesplus fraction, i.e., C7+, with a measured molecular weight of
150 and specific gravity of 0.78