Module 3 - Phase Behavior and Fluid Properties

PETE 609 Module 3
Phase Behavior and Fluid Properties

Class Notes for PETE 609 Module 3 Page 1/74
Author: Dr. Maria Antonieta Barrufet - Fall, 2001

Instructional Objectives
After seeing this module the student should be able to:
Understand pure component phase behavior as a function of Pressure, Temperature,
and molecular size.
Understand the behavior of binary and multicomponent mixtures.
Construct pressure-composition diagrams for a fixed temperature.
Construct temperature -composition diagrams for a fixed pressure.
Construct ternary phase diagrams.
Sketch a miscible gas injection using a ternary diagram.
Represent qualitatively phase behavior dependence on compositions using phase
diagrams.
Represent miscible displacement processes using ternary diagrams.

Module 3 Phase Behavior and Fluid Properties
Estimated Duration: 2 weeks

Phase Behavior Fundamentals from Pressure/Temperature and Pressure/Composition
Diagrams
Fluid Properties of Interest to EOR
Qualitative Representation of Phase Equilibria Processes: Gas Injection and
Production
Quantitative: Representation of Phase Equilibria Processes: Gas Injection and
Production
Ternary Diagrams to represent Gas Injection Processes: Miscible and Immiscible
Processes

Suggested reading: MAB, S
PETE 609 Module 3


Except polymer flooding, all of EOR methods rely on the phase behavior of reservoir fluids
and fluids injected into the reservoir. This behavior is used to classify the recovery method
(i.e., thermal, miscible, chemical, etc.), and to design the recovery process.
This section reviews qualitative and quantitative aspects of phase behavior that will be
used through the reminder of the course.

As oil and gas are produced from the reservoir, they are subjected to a series of pressure
and temperature changes. Such changes affect the volumetric and transport behavior of
these reservoir fluids and, consequently, the produced oil and gas volumes.
We need to quantify the real oil and gas volumes under various pressures and
temperatures. There are basically two models to do this.
Black Oil models describe volumetric properties using correlations in terms of measured
macroscopic properties such as API gravity, bubble point pressures, and gas gravities,
pressure and temperature.
Compositional models require compositional information in addition to the primary
variables: pressure and temperature.

Compositional Model
1. Oil and gas are mixtures of several components
2. All components may be present in both phases (liquid and gas)
3. Volumetric properties of the phases are determined as a function of pressure,
temperature, and the phase compositions using the same model an Equation of
State (EOS) for all phases.
PETE 609 Module 3


PETE 609 Module 3


Black Oil Model
The black oil model can be considered a special case of a compositional model with the
restriction that:
1. Has only two components named as the phases: Gas (G) and Oil (O).
2. The G component may be dissolved in the oil phase and this is taken into account
through the solution gas oil ratio (Rs). However the oil component (O), cannot dissolve
in the gas phase.
3. Volumetric properties are determined from separate correlations for gas and oil
phases.

Phase Behavior Diagrams
Pressure versus temperature diagrams can be used to visualize the fluids production path
from the reservoir to the surface, and to classify reservoir fluids according to the location of
its critical temperature with respect to the reservoir temperature.
The phase behavior of crude oil, water, and EOR fluids is a common ground for
understanding the displacement mechanisms of EOR processes. This behavior includes
the two or more phases formed in crude oil miscible solvent injection processes, the
gasoilwater phases of steam flooding, and the two and three phase behavior of
surfactantbrineoil systems.
The main application of Phase Behavior Diagrams is to develop strategies for efficient oil
(petroleum) and gas production.

Major Definitions
SYSTEM: A body of matter with finite boundaries (physical or virtual), which can be
considered as isolated from surroundings if desired.
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CLOSED SYSTEM: Does not exchange matter with surroundings but may exchange
energy (heat).
OPEN SYSTEM: Does exchange matter and energy with surroundings.
ISOLATED (ADIABATIC) SYSTEM: Does not exchange matter or energy with
surroundings.
HOMOGENEOUS SYSTEM: Intensive properties change continuously and uniformly
(smoothly)
HETEROGENEOUS SYSTEM: System made up of two or more phases in which the
intensive properties change abruptly at phase-contact surfaces.
PHASE: A portion of the system which has homogeneous intensive properties and it is
bounded by a physical surface. Homogeneous means that it is possible to move
from one point to another within that region without detecting a discontinuous
change in a property. An abrupt change in a property is observed when an
interface is crossed. An interface separates two or more phases. These phases
are solid, liquid(s), and gas.
PROPERTIES: Characteristics of a system (phase) that may be evaluated quantitatively.
These properties are
Phase density (liquid, gas, solid)
Compressibility
Surface tension
Viscosity (with help from Transport Models)
Heat capacity
Thermal conductivity
COMPONENT: A molecular species defined or hypothetical. Reservoir fluids contain
many components, and we are commonly forced to combine several
components into hypothetical or pseudo-components, to simplify phase behavior
representations and subsequent calculations.
Defined: C
l
, C
2
, H
2
O
Hypothetical: C
7
+

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STATE: Condition of a system at a particular time determined when all intensive
properties are fixed
PHASE BEHAVIOR DIAGRAMS: These diagrams are called phase envelopes. The dew
point curve and the bubble point curve converge at the mixture critical point.

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Characteristic Phase Envelopes (Phase Composition is Fixed)

Critical
Point
Cricondenbar
Cricondentherm
BubblepointCurve
Dew Point Curve
Quality
Lines
Temperature
P
r
e
s
s
u
r
e
75%
50%
25%

Figure 1- Characteristic phase envelope.

Bubble Point Curve: Boundary between liquid phase and 2-phase region
Dew Point Curve: Boundary between gas phase and 2-phase region.
Critical Point: Location where bubble point and dew-point curves meet.
Cricondentherm: Highest T in phase envelope
Cricondenbar: Highest P in phase envelope.
Quality Lines: Lines of constant volumetric or molar percentage of a phase.

PETE 609 Module 3


Classification of reservoirs based on phase diagram
1. Gas Reservoirs (Single Phase ):
Dry Gas (see Figure 2), and
Wet Gas(see Figure 3).
2. Gas Condensate Reservoirs (Dew-Point Reservoirs):
Retrograde or Condensate Gases (see Figure 4).
3. Undersaturated Solution-Gas Reservoirs (Bubble-Point Reservoirs):
Volatile Oil (see Figure 5), and
Black Oil (see Figure 6).

Temperature
P
r
e
s
s
u
r
e
Path of Production
Initial Reservoir
Conditions
Separator Conditions
CP

Figure 2 - Phase diagram of a dry gas reservoir.

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Temperature
P
r
e
s
s
u
r
e
Path of Production
Initial Reservoir
Conditions
CP

Figure 3 - Phase diagram of a wet gas reservoir.
Separator conditions are within the phase envelope, therefore some liquid will be
produced at surface

Temperature
P
r
e
s
s
u
r
e
Initial Reservoir
Conditions
CP
Path of Production
Temperature
P
r
e
s
s
u
r
e
Initial Reservoir
Conditions
CP
Path of Production
Temperature
P
r
e
s
s
u
r
e
Initial Reservoir
Conditions
CP
Path of Production

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Figure 4 - Phase diagram of a retrograde gas (condensate) reservoir.

Temperature
P
r
e
s
s
u
r
e
Initial Reservoir
Conditions
CP
Path of Production
75%
50%
25%

Figure 5 - Phase diagram of volatile oil reservoir.

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Temperature
P
r
e
s
s
u
r
e
Initial Reservoir
Conditions
CP
Path of Production
25%
50% 75%

Figure 6 - Phase diagram of a black oil reservoir.

If we overlap the phase envelopes for all fluid types in one diagram we will have a series of
phase envelopes in which the critical points of the mixtures have the following trend:
Critical Pressures increase from dry gas, to condensate and volatile where they
reach a maximum and drop again for black oils.
Critical Temperatures increase from dry gas to black oil systems.
The concentration of C
1
increases from Black Oil to Dry Gas.
The character of a fluid type is dictated by its composition.

The following plot contains calculated phase envelopes with hydrocarbon mixtures with the
same components but with different proportions.

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0
1000
2000
3000
4000
5000
6000
7000
P
r
e
s
s
u
r
e

(
p
s
i
a
)
-200 -100 0 100 200 300 400 500 600 700 800
Temperature
o
F
Critical Points
Dry Gas
Wet Gas
Condensate
Volatile I
Black Oil
TR
Volatile I
Volatile II

Figure 7 - Calculated phase envelopes of different mixtures of the same hydrocarbon
components at different proportions. (Barrufet, 1999b).

Typical compositions of reservoir fluids are given in the following table.

Component Black Oil Volatile Oil Gas Condensate Wet Gas Dry Gas
C
1
48.83 64.36 87.07 95.85 86.67
C
2
2.75 7.52 4.39 2.67 7.77
C
3
1.93 4.74 2.29 0.34 2.95
C
4
1.60 4.12 1.74 0.52 1.73
C
5
1.15 3.97 0.83 0.08 0.88
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C
6
1.59 3.38 0.60 0.12
C
7
+
42.15 11.91 3.80 0.42
M
w
C
7
+
225 181 112 157
GOR 625 2000 18,200 105,000 -
Tank
o
API 34.3 50.1 60.8 54.7 -
Liquid
Color
Greenish
Black
Medium
Orange
Light
Straw
Water
White
-
Table 1 - Typical compositions mole % of single-phase reservoir fluids

The transition between a volatile and a condensate fluid in terms of characteristic
compositions is not well defined.

Reservoir fluids also contain other chemical species that may complicate the phase
behavior even further. Table 2 provides a general guideline of reservoir fluid compositions.

PETE 609 Module 3


Table 2 - Guideline of reservoir fluid compositions. (Table taken from Mc Cain The
Properties of Petroleum Fluids, Pennwell 1990)
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Classification of Reservoirs Based on
Production and PVT Data

Before we use a certain fluid model (compositional or black oil), we should have some
guidelines about the type of reservoir fluid we are dealing with: volatile oil, black oil, gas-
condensate, etc.
The (PT) envelope can be generated using any EOS graphics based package such as
PVTSIM, PVTi, etc. once the composition of the fluid are provided.

Other guidelines in terms of Production and PVT Data are

BLACK OIL RESERVOIRS:
GOR less than 1,000 SCF/STB
Density less than 45 API
Reservoir temperatures less than 250F
Oil FVF less than 2.00 (low shrinkage oils)
Dark green to black in color
C
7
+
composition > 30%

VOLATILE OIL RESERVOIRS:
GOR between1,000-8,000 SCF/STB
Density between 45-60 API
Oil FVF greater than 2.00 (high shrinkage oils)
Light brown to green in color
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C
7
+
composition > 12.5%

GAS CONDENSATE RESERVOIRS:
GOR between 70,000-100,000 SCF/STB
Density greater than 60 API
Light in color
C
7
+
composition < 12.5%

WET GAS RESERVOIRS:
GOR > 100,000 SCF/STB
No liquid is formed in the reservoir
Separator conditions lie within phase envelope and liquid is produced at surface

DRY GAS RESERVOIRS:
GOR greater than 100,000 SCF/STB
No liquid produced at surface

Additional guidelines to classify reservoir fluid type:

PETE 609 Module 3


Reservoir Surface GOR range Gas specific API Typical composition, mole %
fluid appearance gravity gravity C
1
C
2
C
3
C
4
C
5
C
6
Dry gas Colorless gas Essentially 0.60 - 0.65 96 2.7 0.3 0.5 0.1 0.4
no liquids
Wet gas Colorless gas Greater than 0.65 - 0.85 60
o
-70
o
with small amount 100 MSCF/bbl
of clear or straw
colored liquid
Condensate Colorless gas 3 to 100 0.65 - 0.85 50
o
-70
o
87 4.4 2.3 1.7 0.8 3.8
with significant MSCF/bbl
amounts of light- (900-18000 m
3
/m
3
)
colored liquid
Volatile or Brown liquid About 0.65 - 0.85 40
o
-50
o
64 7.5 4.7 4.1 3.0 16.7
high shrinkage with various 3000 SCF/bbl
oil yellow, red, or (500m
3
/ m
3
)
green hues
Black or low Dark brown 100-2500 SCF/bbl 30
o
-40
o
49 2.8 1.9 1.6 1.2 43.5
shrinkage oil to black (20-450 m
3
/m
3
)
viscous liquid
Heavy oil Black, very Essentially no gas 10
o
-25
o
20 3.0 2.0 2.0 2.0 71
viscous liquid in solution
Tar Black substance Viscosity >10,000cp <10
o
_ _ _ _ _ 90+
There are no definite boundaries between these classifications and usage may vary depending on location. Gravities and GOR are also
dependent on separation conditions.

Behavior of Fluid Properties for EOR
Processes

Oil and Gas Properties

Crude oil is always associated with gas under any condition in the production system. The
pressure-volume behavior of oil is intimately affected by the type and amount of gas in
solution.

PETE 609 Module 3


As the reservoir pressure decreases, the gas evolves from solution to form a two-phase
system. The relative rates of the gas and oil being removed from the reservoir would affect
the oil volume behavior in the reservoir as well as at stock tank conditions.
Likewise, injection of gases, is the reverse process, gas is added in solution.

Some typical pressure, temperature ranges

Location Pressure (psia) Temperature (
o
F)
Reservoir 500-10,000 100-300 (500
+
thermal)
Separator 100-600 75-150
Stock tank 14.7 Ambient
Standard Conditions 14.7 60

The oil and gas properties of interest to reservoir engineers and their typical units are:

oil formation volume factor (B
o
) = [res bbl/STB],
gas formation factor (B
g
) = [cu ft/SCF] or [res bbl/SCF],
total formation volume factor (B
t
) = [res bbl/STB],
solution gas-oil ratio (R
s
) = [SCF/STB]
oil and gas viscosities (
o
,
g
) = [cp],
compressibility and thermal expansion coefficients.

The properties of reservoir fluids will change during production because of
Pressure and/or Temperature changes
Injections of recovery agents (miscible and chemical)

Adding fluids to the reservoir may change compositions and pressures and as a result the
physical properties will change. Additionally, rock-fluid interactions may be changed as will
be seen in future lectures.
PETE 609 Module 3


The fluid properties of interest for EOR processes are those that affect the mobility of fluids
within the reservoirs.
These properties include:
Densities ( B
o
, B
g
, Compressibility and thermal expansion coefficients)
Viscosities
Interfacial Tensions (more about this in future modules)

The following figures sketch the behavior of oil and gas properties as a function of
pressure, temperature, and composition.

Compressibility Factor Charts

The general shape of this chart is indicated in Figure 8.
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T
r
P
r
Z
1

Figure 8 - General shape of compressibility factor.

Only one compressibility factor chart can be used to determine volumetric properties for
any pure hydrocarbon fluid and mixtures. That is accomplished by using the corresponding
states principle and reduced, or pseudoreduced, properties (P
r
& T
r
) , (P
pr
& T
pr
)

The reduced properties are defined as

c
r
c
r
P
P
P
T
T
T = = and (Eq. 1)

The compositional dependence is seen through the evaluation of the critical, or
pseudocritical properties of the mixture (subject from another course). These give rise to
reduced, or pseudoreduced properties.

PETE 609 Module 3


Pseudocritical properties for mixtures are usually evaluated using a linear mixing rule with
the compositions of the mixture as,

=
=
Nc
i
ci i pc
P z P
1
(Eq. 2)

with a similar expression for the pseudocritical temperature.
Here N
c
is the number of components in the mixture, and z
i
s are the mole fractions.

Table 3 contains critical properties for the hydrocarbon pure components, and the most
common non-hydrocarbon components (CO
2
, water) found in reservoir fluids.
(Source Mc Cain Hydrocarbon Phase Behavior).
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Table 3 - Physical constants of pure hydrocarbons.

The following diagram illustrates changes in the phase envelope of a reservoir fluid during
production and/or injection.

Temperature
t
1
Composition Changes Due to Production
and Gas Injection
P
r
e
s
s
u
r
e
t
3
t
2
Gas
Injection
Production
Temperature
t
1
Composition Changes Due to Production
and Gas Injection
P
r
e
s
s
u
r
e
t
3
t
2
Gas
Injection
Production

Figure 9 - Composition changes due to production and gas injection. Review from McCain
(Petroleum Fluids,1990).

The following sketches indicate the behavior of the main fluid properties with pressure and
temperature.

PETE 609 Module 3


Total Formation Volume Factor
B
t
o
r

B
o
Pressure
Pb
B
t
B
o
B
t
=B
o

Figure 10 - Total formation volume factor.

The phase behavior of reservoir fluids (oil and gas) is determined from a laboratory
analysis of a reservoir fluid sample. The pressure-volume-temperature relationship can be
used to evaluate the reservoir oil behavior under different pressure and temperature
conditions.

PETE 609 Module 3


Gas Formation Volume Factor
B
g
Pressure

Figure 11 - Gas formation volume factor.

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Oil Viscosity
V
i
s
c
o
s
i
t
y
Pressure
P
b

Figure 12 - Oil viscosity.

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Gas Solubility
G
a
s

i
n

S
o
l
u
t
i
o
n
Pressure
P
b

Figure 13 - Gas solubility.

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Isothermal Compressibility
S
p
e
c
i
f
i
c

V
o
l
u
m
e
Pressure
T
V
P

Figure 14 - Isothermal compressibility.

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Thermal Expansion
S
p
e
c
i
f
i
c

V
o
l
u
m
e
Temperature
V
P

Figure 15 - Thermal expansion.

These oil properties can either be determined from laboratory tests or from available
correlations.
Two standard methods for measuring the oil and gas behavior under different pressures
and temperatures include
flash vaporization
differential separation (liberation)

Other laboratory tests to determine the feasibility of a gas injection process can also be
performed. These special tests will be seen in the module covering Miscible processes.

PETE 609 Module 3


Flash Vaporization
The flash vaporization is a process of gas-oil separation in which the gas and oil are
always in contact throughout the entire life of the separation. It is conducted at the reservoir
temperature.
The following figure shows the flash separation process.

V
t1
V
t 2
V
t
3
=
V
b
V
t5
V
t 4
oil oil oil
oil
oil
gas
gas
Hg Hg
Hg
Hg
Hg
P
1
>> P
b
P
2
> P
b
P
3
= P
b
P
4
< P
b
P
5
< P
4
1 2 3 4 5
Flash Separation (Liberation)
Flash Vaporization

Figure 16 - Flash vaporization process.

TEMPERATURE OF TEST = RESERVOIR TEMPERATURE

Differential Separation
The differential separation is a gas-oil separation process in which the gas separated at
one stage is removed before the remaining oil is subjected to the next stage of separation.
PETE 609 Module 3


The separation process is conducted at the reservoir temperature and pressure except the
last stage which is conducted at standard conditions (P = 14.7 psia, T = 60
o
F).

The following figure illustrates the differential liberation process.

gas
oil
oil oil
oil
oil
gas
Hg
Hg
Hg
Hg
Hg
P
1
= P
b
P
2
< P
b
P
2
< P
b
P
2
< P
b
P
3
< P
2
< P
b
1 2 3 4 5
Differential Separation (Liberation)
gas
oil
Gas off

Figure 17 - Differential separation (liberation) process.

These oil properties can either be determined from laboratory tests or from available
correlations.

Water in Petroleum Engineering
Water plays a very important role in petroleum engineering. It exists in the reservoir as the
connate water. It is certainly present in the aquifer. It is more often than not comes out from
PETE 609 Module 3


the reservoir with the produced oil and gas. The resistivity of brines (water + dissolved
ions) is used by the log analyst for saturation calculation. For a waterflood expert, it is
certainly an indispensable commodity.

The basic water properties of interest to reservoir engineers are compressibility, formation
volume factor, viscosity, chemical composition, and resistivity. The chemical composition
of the formation water is used to determine the source of reservoir water, the water
resistivity for well log analysis, and the compatibility of the injected water for waterflood.

Presence of Water
Connate Water
Aquifer
Production
Well Log Analysis
Injection
Water Treatment

Formation Water (Brine) Properties
The properties of interest for reservoir engineering are:
Solubility of Gas in Water
Water Compressibility
Water Formation Volume Factor
Water Viscosity
Chemical Properties
Resistivity

PETE 609 Module 3


Chemical Analysis of Water
All formation water contains dissolved ions. The ions may be classified into two groups.
Positively charged, or cations, and negatively charged or anions, these ions proceed from
salts in solution and conduct electricity offering more or less resistance depending upon
the salt concentration (property used in electric logs).

Formation waters are neutral, that is positive and negative charges balance. The following
table shows typical ions in formation waters.

Cations Anions
Na
+

K
+

Ca
++

Mg
++

Fe
++

Cl
-

HCO
3

-

SO
4

- -

CO
3

- -

Table 4 - Typical ions in formation waters.

Stiff diagrams are used to indicate the (+) and (-) ion contents in water following specific
patterns (see McCain 1990).

Electrical Resistivity of Water
Electrical resistivity is property used in well-log analysis to determine rock properties such
as porosity, oil-water contacts etc.

Applications of Fluid Analysis Data
The use of these properties in Reservoir Engineering Calculations include:

Volumetric
Volume Balance - Black Oil
PETE 609 Module 3


Material Balance Equation Black Oils and Gases
Compositional Material Balance Equation - Volatile Oil & Gas Condensates.

Enhanced Oil Recovery
The use of these properties in Production Engineering Calculations include:
Surface Equipment Design
Wellbore Fluid Mechanics
Production Test
Pressure Transient Analysis
Well Completion

Phase Diagrams

To see the effect of compositions in the phase behavior we need to analyze single and
binary systems. The diagrams seen so far do not show any compositional dependence.
Equations of state models are calibrated with properties of pure components and later
generalized to mixtures by using mixing rules and molar compositions.
The most common types of phase diagrams are:

Single: (PT), (PV), (TV)
Binary: (PT)
zi
, (PV)
zi
, (P,x,y)
T
, (T,x,y)
P

The nomenclature (PT)
zi
means: Pressure vs Temperature diagram at a fixed mixture
composition zi

PETE 609 Module 3


P
r
e
s
s
u
r
e

P
c
Temperature
T
c
Liquid
(1 phase)
Vapor (1 phase)
Solid
(1 phase)
Sublimation Curve (2 phases)
Triple Point
(3 phases)
Vapor Pressure
Curve (2 phases)
Critical
Point
Fusion Curve
2 phases

Figure 18 - Single component phase diagram.

The petroleum engineer is usually interested in a smaller region of this phase diagram: The
region covering vapor-liquid-equilibrium (VLE).

PETE 609 Module 3


P
r
e
s
s
u
r
e
Temperature
Vapor
Liquid
Critical Point
l
v
P
c
T
c

Figure 19 - Vapor pressure curve (VLE).

This graph illustrates the vapor pressure curve for a pure component. As the temperature
increases the vapor pressure increases until the critical point. At temperatures higher than
the critical temperature there is no phase transition (from vapor to liquid and vice versa) at
any pressure.
The state of the component (remember: single component) at a P or/and T greater than its
critical values is a fluid state and as pressure increases its density varies smoothly from
low (gas-like) to high (liquid-like).
This graph also illustrates two lines of constant density (isochores) a vapor and a liquid
density. Notice that at a fixed temperature and pressure two densities coexist.

For a single component fluid the vapor pressure curve is a line with dew-point and bubble-
point being identical.

PETE 609 Module 3


Vapor Pressure Models
Vapor pressures are well represented using the Antoine Model

T C
B
A p
sat
+
= ) ln( (Eq. 3)

Where A, B, and C are constants specific for each component (i.e., propane, decane). This
model can be used in thermal simulations.

Density (mass/volume) is the inverse of specific volume (volume/mass). To see the
variation of density (or specific volume) with pressure and temperature another phase
diagram must be used. This is the pressure-specific volume diagram. For a pure
substance this looks like:

PETE 609 Module 3


T
c
2-phase
T
Specific Volume (ft
3
/lbm)
P
r
e
s
s
u
r
e

(
p
s
i
a
)
V
v
V
L
CP

Figure 20 - Pressure vs. specific volume diagram for a pure substance.

The critical point (CP) is the highest temperature and pressure at which a vapor and a
liquid phase can coexist
Gas and liquid volumes become identical at the critical point.
Isotherms are steeper in the liquid region than in the gas region to reflect lower liquid
compressibilities.

Phase Behavior of Single and Binary Systems

The following phase diagrams for single and binary mixtures serve to illustrate the behavior
of multicomponent fluids at different pressures, temperatures, and compositions.

PETE 609 Module 3


(Left) (Right)
Temperature x
1
, y
1
P
r
e
s
s
u
r
e
P
1
v
P
2
v
P
2
v
P
1
v
T = T
a
T
a
CP
1
CP
2
B
u
b
b
l
e

C
u
r
v
e
D
e
w

C
u
r
v
e
2-phases
Liquid
Vapor

Figure 21 - Phase diagrams for single and binary mixture.

The left side of this Figure 21 illustrates two vapor pressure curves for component [1] and
[2]. At T
a
, the vapor pressures are
v v
P P
2 1
, and component [1] is the most volatile.
Heavier components, in general, exhibit high critical temperatures and lower critical
pressures than more volatile components. For example:
C
2
(ethane) T
c
= 89.92
o
F P
c
= 706.5 psia
C
10
(decane) T
c
= 652.0
o
F P
c
= 305.2 psia

The right hand side of Figure 21 illustrates the phase behavior of all possible mixtures
between [1] and [2] at the selected temperature T
a
.
By convention the most volatile component is plotted in the x-axis. The two extremes
indicate the vapor pressures of the pure components.
The two lines enclosing the two-phase region indicate the bubble pressures (above), and
the dew pressures (below) as a function of composition at T = T
a.
Note that bubble point pressures increase as the composition of the most volatile
component increases.
PETE 609 Module 3


Hydrocarbon Composition

The hydrocarbon composition may be expressed on a weight basis or on a molar basis.
For compositional modeling we use a molar basis. The relationship between moles and
mass is given through the molecular weight.

i" " component of weight Molecular
i" " component of Mass
i" " component of Moles =
(Eq. 4)

i
i
i
Mw
M
n =
(Eq. 5)

Molecular weights for pure components are tabulated, and for undefined chemicals are
determined from correlations.

By convention liquid compositions (mole fractions) are indicated with an x and gas
compositions with a y.

Thus

liquid
n n
n
x

+
=
2 1
1
1
(Eq. 6)

PETE 609 Module 3


gas
n n
n
y

+
=
2 1
1
1
(Eq. 7)

And

1
2 1
= + x x
(Eq. 8)

1
2 1
= + y y
(Eq. 9)

The left side of Figure 22 illustrates the two vapor pressures of components [1] and [2] and
two phase envelopes (shaded lines) that result from two different mixtures of components
[1] and [2]. Each phase envelope has a constant overall composition. The envelope closer
to component [1] represents a higher concentration of that component.

(Left) (Right)
Temperature
x
1
, y
1
P
r
e
s
s
u
r
e
T
1
v
T
2
v
T
2
v
T
1
v
P = P
a
P
a
CP
1
CP
2
B
u
b
b
l
e

C
u
r
v
e
D
e
w

C
u
r
v
e
2-phases
Liquid
Vapor

PETE 609 Module 3


Figure 22 - Phase diagrams of a binary mixture.

At a fixed pressure P
a
, the two vapor pressures are intersected at their corresponding
saturation temperatures
v v
T T
2 1
, .

The right side of this Figure shows a temperature composition projection at the selected
pressure P
a
. The state of all mixture combinations between [1] and [2] at P = P
a
are
depicted in this figure.

Supercritical Components

Up to this point, we selected pressures and temperatures such that we could intersect the
vapor pressures of both components. However, there are temperatures and pressures at
which one or both pure components are supercritical (single phase) while certain mixtures
may exhibit VLE.

Figure 23 shows three different temperature projections in the composition space.

PETE 609 Module 3


(Left) (Right)
T
a
T
b
T
g
Temperature
x
1
, y
1
T
a
T
b
T
g
[1]
[2]
P
1
P
2
v

Figure 23 - Phase diagram of a binary mixture, pressure vs. composition.

Note that at T
g
both components are supercritical. However, there may be a region of two-
phase equilibria. Similarly, in Figure 24, we have three different pressure projections that
indicate the same features.

(Left) (Right)
P
a
P
b
P
g
Temperature
x
1
, y
1
P
r
e
s
s
u
r
e
P
a
P
b
Pg
T
2
v
T
1
v
T
1
v
T
2
v
T
e
m
p
e
r
a
t
u
r
e

PETE 609 Module 3


Figure 24 - Phase diagram of a binary mixture, temperature vs. composition.

Depletion Path

All diagrams up to this point indicate the vapor and liquid composition in the same axis.
Next, we will identify three different compositions, of the same component (please note; the
difference between composition and component!) in the same diagram.

z
1
= overall mole fraction of [1]
y
1
= vapor mole fraction of [1]
x
1
= liquid mole fraction of [1]

Figure 25 illustrates an isothermal reservoir depletion process for a reservoir oil with two
components.

(Left) (Right)
Temperature
P
r
e
s
s
u
r
e
P
D
P
B
T = T
a
T
a
CP
M
z
1
= fixed
z
1
P
r
e
s
s
u
r
e
y
1 x
1
1
0
A
B
C

PETE 609 Module 3


Figure 25 - Isothermal reservoir depletion process for a reservoir oil with two components.

At pressure A, the reservoir fluid is undersaturated, at single phase above the Bubble
Point pressure and has a composition z
1
. As production occurs, pressure drops to point B.
At this location, the fluid is at its bubble point, the reservoir fluid is said to be saturated. As
pressure continues to drop to point C, the original reservoir composition changes. Gas
evolves from solution and this gas has a composition indicated by y
1
in the figure. The oil
becomes richer in heavy component and its composition is indicated by x
1
.
The vapor mole fraction is read along the DEW curve, while the liquid mole fraction is read
from the BUBBLE curve.
Relative amounts of [1] and [2] in the two-phase mixture are obtained from a mass balance.
Note that any overall mixture composition bounded by the horizontal line joining x
1
and y
1

has the SAME equilibrium compositions. What changes are the relative amounts of vapor
and liquid.

This is indicated mathematically as:

v l
f y f x z
1 1 1
+ = (Eq. 10)

v v
f y f x z
1 1 1
) 1 ( + = (Eq. 11)

where f
v
is the molar fraction of vapor in the mixture. That is:

( ) ( )
l v
v
v
n n n n
n n
f
2 1 2 1
2 1
) (
+ + +
+
= (Eq. 12)

Or
PETE 609 Module 3


1 1
1
1
x y
x z
f
v

= (Eq. 13)

(Eq. 13) is valid for any number of components, and for all components. That is,

i i
i i
v
x y
x z
f

= (i = 1, 2, 3, Nc) (Eq. 14)

Separator gas and separator oil are recombined to reconstruct the reservoir composition.
When working in a recombination problem, the producing GOR is converted into a molar
basis and thus the reservoir composition can be found. This will be covered later.
Figure 26 shows VLE for a mixture using a temperature-composition projection. All the
concepts are equivalent to those indicated in Figure 25.

Any state in the two phase region requires pressure and temperature to be specified
(Flash calculations). To obtain other physical properties such as: densities,
compressibilities, and interfacial tensions the modeling equation used to predict VLE
(usually a cubic EOS) is solved at the corresponding P, T and set of equilibrium vapor and
liquid compositions. The flash type of calculations is the work-horse in any compositional
reservoir simulation package.

(Left) (Right)
PETE 609 Module 3


Temperature
P
r
e
s
s
u
r
e
T
D
T
B
P = P
a
P
a
CP
M
z
1
= fixed
z
1
y
1 x
1
1
0
T
B
T
D
T
a
T
a

Figure 26 - Representation of a common distillation process (usually isobaric columns).

Figure 27 represents ALL possible states that a reservoir fluid with CONSTANT (or fixed)
overall composition (z
i
) would exhibit at different pressures and temperatures. As
production takes place, when the average reservoir pressure is the bubble point pressure
there will be compositional changes.
Reservoirs with a gas-cap can be illustrated as. Intersecting two phase diagrams for fluids
of different composition, intersecting at a given T
res
, P
res
.

PETE 609 Module 3


Pressure-Temperature Diagram
Multi-Component System
R
e
s
e
r
v
o
i
r

P
r
e
s
s
u
r
e
Reservoir Temperature
B
u
b
b
l
e
-
P
o
i
n
t
D
e
w
-
P
o
i
n
t
60%
20%
0%
2-Phase
1-Phase 1-Phase
CP
1-Phase

Figure 27 - Pressure -Temperature diagram for a multicomponet mixture.

Figure 28 illustrates how compositional changes occur during production shifting the phase
envelope towards a heavier oil.

PETE 609 Module 3


P
r
e
s
s
u
r
e
Temperature
t
1
t
2
t
3
Time increasing

Figure 28 - Dynamic phase envelope of a reservoir fluid as production takes place.

All diagrams seen up to this point are projections of a three-dimensional diagram as can
bee seen in the following figure.

Phase Behavior of Ternary Systems

A general classification of Reservoir Fluids in terms of compositional distribution is
presented in a ternary diagram.

PETE 609 Module 3


Figure 29 - General classification of reservoir fluids in terms of compositional distribution.

PETE 609 Module 3


Ternary Diagram: Review
Conventions
Each corner of a diagram represents 100% of a set component the opposite sites are 0%
of that component.
Binary mixtures are represented on the sides of the triangular diagram, ternary mixtures
(compositions) are represented within the triangle.
A 100% of the lightest component is drawn at the top, the intermediate is at the right, and
the heavy is at the left
A ternary diagram has its pressure and temperature fixed (P,T).

.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
L
H
I

Figure 30 - Ternary diagram of the H, I, and L components.

PETE 609 Module 3


Qualitative Representation of Phase Equilibria
Figure 31 represents the evolution of a mixture of methane (C
1
), propane (C
3
) and n-
pentane (C
5
) at a specific temperature, 160
o
F, and at various pressures (remember that
one ternary diagram represents the equilibrium of the mixture at one pressure and one
temperature). This figure represents actual data, and it has been redrawn from McCains
book.
Following these ternary phase diagrams at the same temperature (160
o
F) and at different
pressures, you can visualize typical phase behavior changes in the mixture as the pressure
changes.

PETE 609 Module 3


nC
5
C
3
C
1
Gas
p=14.7 psia
nC
5
C
3
C
1
G
a
s
2-phase
Liquid
p=200 psia
C
3
C
1
nC
5
G
a
s
2-phase
Liquid
p=380 psia
nC
5
C
1
C
3
G
a
s
2-phase
Liquid
p=500 psia
C
1
G
a
s
2-phase
Liquid
C
3
nC
5
p=1040 psia
C
1
G
a
s
2-phase
Liquid
C
3
nC
5 p=1500 psia
G
a
s
2-phase
Liquid
C
1
C
3
nC
5
G
a
s
p=2000 psia
nC
5
C
3
C
1
Liquid
p=2350 psia

Figure 31 - Evolution of a mixture of methane (C
1
), propane (C
3
) and n-pentane (C
5
) at
160
o
F and at various pressures.

PETE 609 Module 3


Dilution lines
When representing phase behavior relations in a ternary diagram, the compositions of ALL
possible mixtures from mixing two fluids will fall in the straight line connecting the points
indicating the compositions of the two source fluids. For example, ALL mixtures of n-C
4
and bubble point fluid X in the figure are miscible in all proportions, while mixtures of X with
C
1
are miscible at high concentrations of C
1
.

. 9
. 8
. 7
. 6
. 5
. 4
. 3
. 2
. 1
. 1
. 2
. 3
. 4
. 5
. 6
. 7
. 8
. 9
1
. 1 . 2 . 3 . 4 . 5 . 6 . 7 . 8 . 9 0
0
1
C
1
C
1 0
n - C
4
x

Figure 32 - Dilution lines example.

Quantitative Representation of Phase Equilibria
Tie (or equilibrium) lines

Tie lines join equilibrium conditions of the gas and liquid at a given pressure and
temperature.
Dew point curve gives the gas composition.
PETE 609 Module 3


Bubble point curve gives the liquid composition.
Hints: B.P. richer in the heavier component.
D.P. richer in the lighter component.

All mixtures whose overall composition (z
i
) is along a tie line have the SAME equilibrium
gas (y
i
) and liquid composition (x
i
), but the relative amounts on a molar basis of gas and
liquid (f
v
and f
l
) change linearly (0 vapor at B.P., 1 liquid at B.P.).

Relative amounts of gas are,

moles of number total
vapor of moles of number
= =
t
v
v
n
n
f (Eq. 15)

in other words,

3 2 1
3 2 1
t t t
v v v
v
n n n
n n n
f
+ +
+ +
= (Eq. 16)

where,

vi li ti
n n n + = with i=1, 2, 3 (Eq. 17)

v i l i i
f y f x z + = (Eq. 18)

or

PETE 609 Module 3


v i v i i
f y f x z + = ) 1 ( (Eq. 19)

thus,

line tie of length
n compositio gas to n compositio overall from length
=
=
i i
i i
v
x y
y z
f
(Eq. 20)

This is also known as the Lever Rule, and f
v
can be determined graphically as well.

.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
10
n-C
4
CP

Figure 33 - A ternary phase diagram illustrating the phase envelope and tie lines.

PETE 609 Module 3


Uses of Ternary Diagrams - Representation of Multi-
Component Phase Behavior with a Pseudoternary Diagram

Ternary diagrams may approximate phase behavior of multi-component mixtures by
grouping them into 3 pseudocomponents. A frequent way of grouping different
components of a mixture based on similarities of critical and other physical properties is,
light (C
1
, CO
2
, N
2
- C
1,
CO
2
-C
2
, ...)
heavy (C
7
+
)
intermediate (C
2
-C
6
)

The representation of the phase behavior of a solvent/reservoir fluid mixture by
pseudocomponents is a highly useful tool for the conceptual understanding of miscible
processes where a solvent is injected in the reservoir and gets mixed with the reservoir
fluid.

For computational purposes using EOS (Equation of States) a set of critical properties
must be assigned to pseudocomponents. These are usually characterized in terms of their
normal boiling point, molecular weight and/ or density at standard conditions. Several
correlations are available to characterize these fractions.
The following pictures show the relationship among these properties according to Katz and
Firoozabadi.

PETE 609 Module 3


Physical Properties of Alkanes
0
400
800
1200
1600
0 200 400 600 800 1000 1200 1400
Tb (F)

M
w
0.5
0.6
0.7
0.8
0.9
1
D
e
n
s
i
t
y

(
g
/
c
c
)
Mw
Density (g/cc)

Figure 34 - Katz and Firozaabadis relationship among normal boliling point, density at
standard conditions and molecular weight for alkanes.

PETE 609 Module 3


Physical Properties of Alkanes
0
400
800
1200
1600
0 200 400 600 800 1000 1200 1400
Tb (F)
T
c

,

P
c
0
0.5
1
1.5
2
2.5
A
c
e
n
t
r
i
c

F
a
c
t
o
r
Tc /F
Pc (psia)
w

Figure 35 - Katz and Firozaabadis relationship among normal boiling point, critical
pressure, critical temperature, and acentric factor for alkanes.

First Contact Miscible Recovery Processes (FCM)
The simplest and most direct method for achieving miscible displacement is to inject a
solvent that mixes completely with the reservoir oil in all proportions, such that all mixtures
are in single phase. Some examples are: intermediate molecular weight hydrocarbon C
3
-
C
4
or mixtures of LPG.

PETE 609 Module 3


.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
2
-C
6
C
7
+
A
O

Figure 36 - Example of a First Contact Miscible recovery process (FCM).

Reservoir oil with composition "O" could be diluted with methane up to concentration "A"
and still achieve FCM.

Exercise
Find overall composition of mixture made with 100 moles oil "O" + 10 moles of mixture
"A".
________________________________________________
________________________________________________
________________________________________________
________________________________________________
________________________________________________
PETE 609 Module 3


.9
.8
.7
.6
.5
.4
.3
.2
.1
.1
.2
.3
.4
.5
.6
.7
.8
.9
1
.1 .2 .3 .4 .5 .6 .7 .8 .9 0
0
1
C
1
C
2
-C
6
C
7
+
A
O

Figure 37 - Ternary diagram for FCM exercise.

For first contact miscibility to be achieved between solvent and oil, the displacement
pressure must be above the cricondenbar (CB) pressure of all possible combinations
between injected solvent and reservoir oil at the selected temperature. This guaranties that
all solvent/oil mixtures above this pressure are single phase.

As the concentration of methane in the injection fluid increases (moving above point A in
Figure 36), the CB increases and will not have FCM. However, dynamic miscibility can be
achieved by multiple-contact-mechanisms (MCM)
(1) condensing-gas drive
(2) or vaporizing gas drive
(3) condensing-vaporizing gas drive (most likely)

Problems associated with FCM:
PETE 609 Module 3


Intermediate molecular weight hydrocarbon solvents for fixed contact FMC may precipitate
some of the asphalt from asphaltic crudes. Severe asphalt precipitation may reduce
permeability and effect well injectivities and productivities. It may also cause plugging in
producing wells.
Pressure and temperature changes and/or the addition of intermediate molecular weight
hydrocarbons or CO
2
to some reservoir fluids may cause multiple phases to form. Some
of these phases are,
Solid precipitation of asphaltenes and/or waxes (supersaturation achieved due to P,
T, or composition changes).
Two or more liquid phases (i.e. Hydrocarbon-rich, CO
2
-rich)
Gas-liquid -solid-liquid phases.

In the past, LPG solvents that are FCM have been too expensive to inject continuously.
Instead solvent was injected in a limited volume, or slug, and the slug was displaced
miscible with a less expensive fluid such as natural gas or flue gas.

Solvent
Slug
Flue
Gas
Oil

Figure 38 - Compositional grading.

Ideally with such a process scheme, solvent miscible displaces oil while drive gas miscible
displaces the solvent, propelling the small solvent slug through the reservoir.
Miscibility between solvent and driving gas normally determines the minimum pressure
required for miscible displacement in the FCM slug process with LPG solvents.
PETE 609 Module 3


As solvent slug travels through the reservoir, at mixes with oil at the leading edge and with
the drive gas at the trailing edge.
When it reaches the two phases no further displacement miscibility is lost.

PETE 609 Module 3


Practice Ternary Diagrams
Exercises from this module will be based on these diagrams.

Pressure Effect
The following ternary diagrams illustrate the effect of pressure on the phase equilibria. All
diagrams have been calculated using an EOS. The temperature is fixed in all of them
(T=180 F), but p varies from 14.7 to 4000 psia.

T=180F
P=14.7 psia
Pressure Effect
O

Figure 39 -

PETE 609 Module 3


T=180F
P=200 psia
C1-C3-C10
Pressure Effect
O

Figure 40 -

T=180F
P=400 psia
Pressure Effect
O

Figure 41 -
PETE 609 Module 3


T=180F
P=600 psia
Pressure Effect
O

Figure 42 -

PETE 609 Module 3


T=180F
P=1000 psia
Pressure Effect
O

Figure 43 -

T=180F
P=1500 psia
Pressure Effect
O

Figure 44 -
PETE 609 Module 3


T=180F
P=2000 psia
Pressure Effect
O

Figure 45 -
T=180F
P=3000 psia
Pressure Effect
O

Figure 46 -
PETE 609 Module 3


T=180F
P=4000 psia
Pressure Effect
O

Figure 47 -
PETE 609 Module 3


Temperature Effect
The following ternary diagrams illustrate the effect of temperature on the phase equilibria.
All diagrams have been calculated using an EOS. The pressure is fixed in all of them
(p=2000 psia), but T varies from 100 to 450 F.

T=100F
P=2000 psia
Temperature Effect
O

Figure 48 -

PETE 609 Module 3


T=150F
P=2000 psia
Temperature Effect
O

Figure 49 -

T=200F
P=2000 psia
Temperature Effect
O

Figure 50 -

PETE 609 Module 3


T=300F
P=2000 psia
Temperature Effect
O

Figure 51 -

T=350F
P=2000 psia
Temperature Effect
O

Figure 52 -

PETE 609 Module 3


T=400F
P=2000 psia
Temperature Effect
O

Figure 53 -

T=450F
P=2000 psia
Temperature Effect
O

Figure 54 -

Module 3 - Phase Behavior and Fluid Properties

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Module 3 - Phase Behavior and Fluid Properties

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PETE 609 Module 3

Phase Behavior and Fluid Properties

= (i = 1, 2, 3, Nc) (Eq. 14)

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