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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

– Phase Behavior Fundamentals and Review of


Thermodynamics

Concepts and Definitions.


Oil and Gas Properties.
Hydrocarbon Phase Behavior. Classification of reservoir fluids based on phase
diagrams and PVT and production data. Standard PVT tests: Differential
Liberation, Constant Composition Expansion, Separator Tests.
Volumetric and phase behavior of pure substances, binary and multicomponent
systems. Phase diagrams (P-V, P-T, P-x, y-x).
Ternary Diagrams. Phase Equilibria Representation.

Suggested reading: MAB, McCain

Instructional Objectives
After seeing this module the student should be able to:

• Classify reservoir fluid using PVT and production data.

• Understand the differences and limitations among standard PVT tests (CCE,DL,
etc.)

• Establish the difference between a black oil and compositional model.

• Select the appropriate fluid model based upon fluid characteristics and production
data.

• Represent quantitatively phase behavior dependence on compositions using phase


diagrams.

• Understand pure component phase behavior as a function of Pressure,


Temperature, and molecular size.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

• 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.

• Represent miscible displacement processes using ternary diagrams.

• Sketch a miscible gas injection using a ternary diagram.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Concepts & Definitions

Phase behavior is the study of changes of the intensive properties of fluids (either
single component or mixtures) as a function of changes in pressure, temperature and
compositions. These properties include:

• Phase density (liquid, gas, solid)

• Compressibility

• Surface tension

• Viscosity (with help from Transport Models)

• Heat capacity

We will concentrate in property and phase changes of Hydrocarbon Species and fluids
used for EOR purposes.

The main applications of phase behavior studies include:

• To assist in strategies for efficient oil and gas production,

• To support enhanced oil recovery processes by miscible gas injection and by


thermal processes, and

• To help in the design and operation of surface facilities, multiphase pumps,


etc.

Definitions
Before beginning this course we must become familiar with certain 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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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

• 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). Examples:

Gas reservoir, oil above the saturation pressure (bubble point


pressure).

Density increases gradually as pressure increases and vice-versa.

• Heterogeneous System: System made up of two or more phases in which the


intensive properties change abruptly at phase-contact surfaces. Examples:

System including oil and a gas cap.

Density changes abruptly at the interface (gas-oil contact).

Fluids within a separator (gas-liquid). Emulsions.

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. A
phase can be a system by itself since the selection of a system is arbitrary. Examples:

Reservoir brine, gas cap, oil reservoir above bubble point.

Properties: Characteristics of a system (phase) that may be evaluated quantitatively.


These properties are

• Phase density (liquid, gas, solid)

• Compressibility

• Surface tension

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

• Viscosity (with help from Transport Models)

• Heat capacity

• Thermal conductivity

Extensive Properties: Depend upon system's mass. Additive. Examples:

Caloric content (BTU value), saturations (oil, gas, water).

Intensive Properties: Independent of system's mass. Cannot be added. Examples:

Caloric content per unit mass (BTU/lbm), density, compressibility,


viscosity, composition, pressure, temperature.

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: Cl, C2, H2O


+
Hypothetical: C7

State: Condition of a system at a particular time determined when all intensive


properties are fixed.

Equilibrium State: When all intensive properties remain unchanged with time. In
thermodynamics it is taken to mean not only the absence of change but the absence of
any tendency toward change on a macroscopic scale. At equilibrium, there are not
driving forces:

Mechanical driving force = 0 ! Pressure is constant

Thermal driving force = 0 ! Temperature is constant

Chemical driving force = 0 ! Chemical potential of each species ‘i’ is


constant

Non-Equilibrium State: Properties change with time. Can be modeled as a sequence


of equilibrium states.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Phase Behavior Diagrams: These diagrams are called phase envelopes. The dew
point curve and the bubble point curve converge at the mixture critical point.

Process: Any change of a system is called a thermodynamic process which may occur
with no restrictions or under arbitrarily prescribed conditions ( i.e. T constant, P
constant, V constant)

Mathematical Concepts
The following is a list of the mathematical concepts required for this course.

Variables: Understand the difference between dependent and independent variables.


Many times these can be interchanged, and they are to facilitate computations.

“Space” Coordinates: Here we will not deal with space coordinates but the axes will
be: P, V, T, and the composition of a selected component (pseudocomponent).

Graphical and Analytical Tools Required


• 3-D plots, 2-D projections i.e Pressure versus Tempearture at fixed composition.

• Slopes (analytical, numerical & graphical)

• Differentials (analytical & numerical)

• Partial Derivatives (numerical & analytical)

• Integration

• Solution of non linear equations

• Root finding routines

• A great deal of abstraction

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Oil and Gas Properties


Petroleum reservoir fluids are made up of mainly hydrocarbon components, and in
lesser proportion some non-hydrocarbon components such as CO2, N2, and sulfur
compounds. Water is also present in oil and gas reservoirs, although most of the time
the effect of water upon the physical properties of the hydrocarbons can be neglected
since water and oil may be considered nearly immiscible at the pressures and
temperatures found normally in reservoirs. This is not the case at the high temperatures
used in steam injection processes to recover heavy oil, therefore a small portion of this
course will cover the concepts of water-hydrocarbon phase equilibrium.

The phase behavior of reservoir fluids at surface and at reservoir conditions is


determined primarily by their chemical composition, pressure, and temperature. Phase
behavior and phase properties are indispensable for the development and managing of
any reservoir and affect all aspects of petroleum production, exploration, and of
processing.

Although reservoir fluids are composed of many different compounds, sometimes


impossible to determine quantitatively, the fundamentals of phase behavior can be
explained by describing the behavior of single, binary and ternary systems.

To model the behavior of multicomponent hydrocarbon mixtures we need to


characterize the oil using a limited number of components. The success of a phase
behavior match depends on the characterization procedure used.

The overall objectives of this course are to understand and to be able to predict the
phase behavior and fluid phase properties using a variety of methods, mainly equations
of state (EOS). This requires a sequence of steps which will be covered along the

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

course, beginning with pure substances and extending to binary and multicomponent
systems.

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.

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.

o
Location Pressure (psia) Temperature ( F)

Reservoir 500-10,000 100-300

Separator 100-600 75-150

Stock tank 14.7 Ambient

Standard Conditions 14.7 60

Table 1 - Some pressure & temperature ranges.

The oil and gas properties of interest to reservoir engineers from a Black Oil model
perspective are:

• oil formation volume factor (Bo),

• gas formation factor (Bg),

• total formation volume factor (Bt),

• solution gas-oil ratio (Rs)

• oil and gas viscosities (µo, µg)

• compressibility and thermal expansion coefficients.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

From a compositional perspective these properties are replaced as shown in Figure 1.

Black Oil Model Compositional Model


Bo ρo, xi (i = 1, 2...Nc)
Bg,Rs ρg, yi (i = 1, 2...Nc)
Bt ρm, zi (i = 1, 2...Nc)
µo µo
µg µg
... ...
..
Figure 1 - Properties in Black Oil and Compositional models.

Viscosities, compressibilities, and thermal expansions are also used in compositional


formulations, but they are evaluated from a compositional model.

The sketch in Figure 2 indicates the behavior of volumetric properties, as expressed in


a black oil formulation, with pressure and temperature.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Definition of Oil & Gas PVT Properties

Separator gas
Separator gas
Rv =
Standard

Separator gas
Conditions

Bg =
STB
gas

P4 P3 Reservoir
P2 P1
gas gas
oil oil
oil oil

Decreasing Pressure
Separator gas

Separator gas
Standard oil
Conditions
STB Bo= Rs=
STB STB

Figure 2 - Definition of oil and gas PVT properties based on their volumetric behavior.

Classification of Reservoirs Based Upon 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. Some guidelines in terms of production and PVT data are

BLACK OIL RESERVOIRS:

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

GOR less than 1,000 SCF/STB

Density less than 45° API

Reservoir temperatures less than 250°F

Oil FVF less than 2.00 (low shrinkage oils)

Dark green to black in color


+
C7 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


+
C7 composition > 12.5%

GAS CONDENSATE RESERVOIRS:

GOR between 70,000-100,000 SCF/STB

Density greater than 60° API

Light in color
+
C7 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

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

DRY GAS RESERVOIRS:

GOR greater than 100,000 SCF/STB

No liquid produced at surface

PVT Properties for Reservoir Engineering

Gas Formation Volume Factor


By definition the gas formation volume factor is the ratio of the volume of gas at
reservoir conditions (Tres,Pres) required to produce one cubic feet at standard conditions.

The standard conditions are defined as,


o
T=520 R and P=14.65 psia.

Its main use is for converting reservoir gas volume to surface gas volume, and vice
versa. The mathematical expression is:

Volume Occupied by a given mass of gas at reservoir Temperature & Pressure


Bg =
Volume Occupied by the same mass at Standard Temperature & Pressure

VR
Bg = (1)
V SC
… mathematically using the real gas EOS …

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

ZnRT
Bg = P
Z SC nRTSC
(2)
PSC

Replacing values for the standard pressure and temperature and considering that the
compressibility factor at standard conditions is essentially equal to one we have:

ZRT  RCF 
Bg =  
380 .7 P  SCF  (3)

This property is expressed in terms of the gas compressibility factor (Z) as follows

where SCF = standard cubic feet & RCF = reservoir cubic feet

Other common units for the gas formation volume factor are (reservoir barrels /
standard cubic feet). In that case:

ZRT  RB 
Bg = 0.00502   (4)
P  SCF 

The key is how to determine the compressibility factor “Z” for the gas in question, at
different pressures, & at different temperatures and gas compositions.

The general shape of a Z factor chart is

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Z Tr

Pr

Figure 3 - Compressibility factor shape.

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 properties (Pr & Tr)

Isothermal Compressibility

1 dV g
Cg = − (5)
V g dP
Numerically can be evaluated as …

(B g1 − B g 2 )
Cg = −=−
B g1 (P1 − P2 )
(6)

-1
The units for isothermal compressibility are: psia

The following figures show the typical behavior of reservoir engineering properties such
as Bo, Rs, Bg, Co, etc. with pressure. The student should review these properties and
their definitions from McCain book.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Oil Formation Volume Factor

B
t
Bt, Bo

B =B
t o

Bo
Pb

Pressure
Figure 4 - Oil 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. It can also be used to classify the type of reservoir and the reservoir fluid.

Gas Formation Volume Factor


Bg

Pressure
Figure 5 - Gas formation volume factor.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Oil Viscosity
Viscosity

Pb

Pressure
Figure 6 - Oil viscosity.

Gas Solubility
Gas in Solution

Pb
Pressure
Figure 7 - Gas solubility.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Isothermal Compressibility
Specific Volume

ry
da
un
Bo
ase

T
Ph

∆V

∆P Pressure

Figure 8 - Isothermal compressibility.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Thermal Expansion
Specific Volume

DV

∆Τ Temperature
Figure 9 - Thermal expansion.

Laboratory PVT Experiments


There are three gas-oil separation models used in measuring the oil and gas behavior
under different pressures and temperatures. These are:

• flash vaporization or constant composition expansion tests

• differential separation (liberation) tests

• separator tests

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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

The following figure shows the flash separation process in which the temperature of the
test equals the reservoir temperature.

Flash Vaporization
Flash Separation (Liberation)
1 2 3 4 5

gas gas

Vt3=Vb
V t1 V t2
V t4 V t5
oil oil oil oil
oil

Hg Hg Hg
Hg
Hg

P 1 >> P b P2 > Pb P3 = Pb P4 < Pb P5 < P4

Figure 10 - Flash vaporization PVT analysis.

This test is used to determine bubble point pressures by intersecting the lines
representing volume variations in the liquid and two phase regions.

This test is used to determine relative oil volumes as well.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Pressure

Pb

Vb
Volume
Figure 11 - Bubble point determination.

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

The following figure illustrates the differential liberation process:

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Differential Separation (Liberation)


Gas off
1 2 3 4 5

gas gas
gas
oil
oil oil oil

oil
Hg Hg oil
Hg
Hg
Hg
P1 = P b P2 < P b P2 < P b P2 < P b P3 < P2 < Pb
Figure 12 - Differential liberation process.

These tests are used to determine formation volume factors and solution gas oil ratios.

Equations of state are usually calibrated to these data.

SEPARATOR TESTS

The separator separation process is essentially a two-step gas-oil separation process.


The bubble point oil is flashed through a separator and stored at the stock tank
condition. The purpose of this separation test is to obtain data for converting the flash
and differential separation data to stock tank oil basis.

The following figure illustrates the separator process:

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Separator-Separation
Separator

Reservoir
Standard
Conditions
Gas
Oil

Pb Stock tank oil


Tres VSTO Oil
Pseparator
Tseparator

Figure 13 - Separator tests.

Other oil properties of interest are oil compressibility, thermal expansion, and viscosity.
These oil properties can either be determined from laboratory tests or from available
correlations.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Production System

Water Gas Sales


Knockout Separator

Stock Tank
Well Head

Water

Oil Sales
Lab Tests
Reservoir

Figure 14 - Production system representation.

Applications of Fluid Analysis Data


The use of these properties in Reservoir Engineering Calculations include:

• Volumetric

• Volume Balance - Black Oil

• 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

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Hydrocarbon Phase Behavior


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.

The major characteristics of each method are:

Compositional Model
• Oil and gas are mixtures of several components

• All components may be present in both phases (liquid and gas)

• 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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Black Oil Model


The black oil model can be considered a special case of a compositional model with the
restriction that:

• Has only two components named as the phases: Gas (G) and Oil (O).

• 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.

• 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 gas–oil–water phases of steam flooding, and the two – and three –
phase behavior of surfactant–brine–oil systems.

The main application of Phase Behavior Diagrams is to assist in the development of


strategies for efficient oil (petroleum) and gas production.

Figure 15 is a sketch of a typical phase diagram for a reservoir fluid.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Cricondenbar
Bubblepoint Curve
Critical

Dew Point Curve

Quality
Pressure

75% Lines

50%

Cricondentherm
25%

Temperature

Figure 15- Characteristic phase envelope.

The description of this diagram is indicated in Table 2.

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.

Table 2 - Description of a typical phase diagram.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Classification of reservoirs based on phase diagram


1. Gas Reservoirs (Single Phase):

• Dry Gas (see Figure 16), and

• Wet Gas (see Figure 17).

2. Gas Condensate Reservoirs (Dew-Point Reservoirs):

• Retrograde or Condensate Gases (see Figure 18).

3. Undersaturated Solution-Gas Reservoirs (Bubble-Point Reservoirs):

• Volatile Oil (see Figure 19), and

• Black Oil (see Figure 20).

Initial Reservoir
Conditions
CP
Pressure

Path of Production

Separator Conditions

Temperature

Figure 16 - Phase diagram of a dry gas reservoir.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

CP Initial Reservoir
Conditions
Pressure

Path of Production

Separator Conditions

Temperature

Figure 17 - Phase diagram of a wet gas reservoir.

Separator conditions are within the phase envelope, therefore some liquid will be
produced at surface

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Initial Reservoir
Conditions

CP
Pressure

Path of Production

Separator Conditions

Temperature

Figure 18 - Phase diagram of a retrograde gas (condensate) reservoir.

Initial Reservoir
Conditions

CP
Path of Production
Pressure

Separator Conditions

75%
25%
50%

Temperature

Figure 19 - Phase diagram of volatile oil reservoir.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Initial Reservoir
Conditions

Path of Production
CP
Pressure

75% 50%
25%

Separator Conditions

Temperature

Figure 20 - 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 C1 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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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

7000
TR Critical Points

6000
Volatile I

5000
Condensate Volatile II
Pressure (psia)

4000

3000

2000 Wet Gas


Black Oil
1000

Dry Gas
0
-200 -100 0 100 200 300 400 500 600 700 800
o
Temperature F

Figure 21 - 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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Component Black Oil Volatile Oil Gas Condensate Wet Gas Dry Gas

C1 48.83 64.36 87.07 95.85 86.67

C2 2.75 7.52 4.39 2.67 7.77

C3 1.93 4.74 2.29 0.34 2.95

C4 1.60 4.12 1.74 0.52 1.73

C5 1.15 3.97 0.83 0.08 0.88

C6 1.59 3.38 0.60 0.12


+
C7 42.15 11.91 3.80 0.42
+
MwC7 225 181 112 157

GOR 625 2000 18,200 105,000 -


o
Tank API 34.3 50.1 60.8 54.7 -
Liquid Greenish Medium Light Water
-
Color Black Orange Straw White
Table 3 - 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 3 provides a general guideline of reservoir fluid
compositions, while Table 4 contains information about typical petroleum gases and
heavy oil fractions.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Table 4 - Typical compositions of petroleum gases and heavy crude oil fractions.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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.

Based upon this classification one may decide to use a black oil model or a
compositional model.

The following diagram indicates the region of applicability for a black oil model.

Figure 22 - Pressure Temperature diagram of a typical reservoir fluid and areas of


application for a Black Oil model.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Pressure versus temperature diagrams are called phase envelopes. The dew point
curve and the bubble point curve converge at the mixture critical point.

The region of application for a compositional model is indicated in the following figure.

Compositional

Figure 23 - Pressure Temperature diagram of a typical reservoir fluid and areas of


application for a Compositional model.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Compositional Effects on Phase Behavior


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’.

Single Component

Fusion Curve
2 phases Critical
Point
Pc
Solid Liquid
(1 phase)
Pressure

(1 phase)
Vapor Pressure
Curve (2 phases)

Triple Point Vapor (1 phase)


(3 phases)

Sublimation Curve (2 phases)

Tc
Temperature

Figure 24 - Pressure vs. Temperature diagram for a Single Component.

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

Vapor Pressure Curve

Pc Critical Point
ρl
Pressure

Liquid
ρv

Vapor
Tc
Temperature
Figure 25 - Vapor pressure curve for a single component.

Figure 25 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 not a phase transition (from
vapor to liquid and vice versa) at any pressure.

The state of the 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.

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

The phase envelope represents ALL possible states that a reservoir fluid with
CONSTANT (or fixed) overall composition (zi) 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 Tres,Pres.

The following diagram illustrates how compositional changes occur during production
shifting the phase envelope towards a heavier oil, or gas injection shifting the envelope
towards a lighter oil.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Composition Changes Due to Production


and Gas Injection
t1
Production

t2
Pressure

Gas
Injection

t3

Temperature
Figure 26 - Composition changes due to production and gas injection. Review from
McCain (Petroleum Fluids,1990).

Some Characteristic Physical Properties for Pure


Components
The following graph indicates the behavior of the main fluid properties with pressure
and temperature for hydrocarbon families such as alkanes (the main constituents of
reservoir fluids.)

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Figure 27 - Behavior of some molecules with temperature.

Typically gas and oil are both mixtures made up of alkanes which impart to them
distinct physical properties (densities, viscosities, heat capacities, color, smell, etc.)
Gases contain mainly C1 to C3, while oil includes higher hydrocarbon numbers, usually
+
denoted as C7 .

On a more elementary basis crude oils are made of … (Table from McCain)

Table 5 - Elemental analysis of typical crude oils.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Composition may be expressed on a weight basis and on a molar basis. The


relationship between moles and mass is:

M
n= (7)
Mw

where M is the mass expressed in grams or pounds and Mw is the molecular weight of
the component which is tabulated.

For example one kilogram of water is equivalent to

1 lbm
n= =
18lbm / lb − mol (8)

We cannot say that one pound of water contains the same amount of moles as a pound
of gasoline (C8 mainly).

The following tables (taken from McCain book) contain physical property data for pure
substances.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Heat Effects Accompanying Phase Changes of Pure


Substances

When a pure substance is isobarically liquefied from the solid state or vaporized from
the liquid state, there is no change in temperature but there is a definite transfer of heat
from the surroundings to the substance. These heat effects are the latent heats of
fusion for the solid-liquid transition and the latent heat of vaporization for the liquid-
vapor transition.

The characteristic feature of such processes is the coexistence of two phases;


therefore the state of the system is determined from the specification of just one
intensive property. That is, if pressure is given and we know that 2 phases coexist there
is a unique corresponding temperature at which this may happen. The (P, T) pair
defines the saturation point and belong to the vapor pressure line.

The fundamental relationship between the latent heat accompanying the phase change
and PVT data for the system is provided by the Clapeyron equation.

sat
∆ H vap = T∆ V dP
dT (9)

Where

∆V = Vv - Vl at (Psat, Tsat) [=] ft /lbmol or cm /g-mol


3 3

∆Hvap = latent heat of vaporization [=] BTU/lbmol or cal/g-mol.

dP sat/dT = rate of change of the vapor pressure with temperature (slope).

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Thus latent heats of vaporization can be calculated from vapor pressure and volumetric
data.

For vaporization processes at low pressures one may introduce a reasonable


approximation into the Clapeyron equation by assuming that the gas phase is an ideal
gas and that the molar volume of the liquid phase is negligible compared to the vapor
(or gas) volume. In that case:

∆ V ≈ V v = RT
P (10)

And the Clapeyron equation becomes:

dP sat = ∆ H vap P sat


dT RT 2 (11)

This approximate equation is known as the Clausius-Clapeyron equation.

Integration of Equation (11) assuming that the heat of vaporization is temperature


independent gives:

ln (P sat ) = A - B
T (12)

This equation is useful for many purposes, but not sufficiently precise. The Antoine
equation, is more widely used and it has the form:

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

ln (P sat ) = A - B
C+T (13)

Where A, B, and C are constants specific for each component (i.e propane,
cycloheptane, benzene etc.)

An even more accurate equation is the Riedel equation (obviously, with more
parameters):

B
ln P sat = A − + D ln T + FT 6
(14)
T

Two-Phase Properties (Single Component)


Properties of mixtures of the two phases are related to the property of each phase and
the amount of that phase. Let f be the mole fraction of the gas phase (usually called
quality).

n
f = n +g n
g l (15)

Then for a given saturation point provided by the coordinate pair (P sat, T sat):

V = f V g + (1 - f )V l @ P sat, T sat (16)

Vapor pressures can also be read from the COX charts in the following figures.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Notice that the temperature scale in the horizontal coordinate in neither linear nor
logarithmic. Made up such that, curves are essentially straight.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Figure 28 - Vapor pressures of normal paraffins. (From Handbook of Natural Gas


Engineering by Katz et al.)

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Figure 29 - Vapor pressures of isomeric paraffins. (From Handbook of Natural Gas


Engineering by Katz et al.)

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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:

T
Pressure (psia)

CP
Tc

2-phase

VL Vv

Specific Volume (ft3/lbm)


Figure 30 - Pressure-specific volume diagram for a pure substance.

• The CP is the highest temperature and pressure at which a vapor an 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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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.

Left Right
CP1 T = Ta
Liquid
P1v P1v
urve
C
Pressure

b ble
Bu 2-phases
CP2 rve
Cu
P2v w
De
P2v
Vapor
Ta Temperature x1, y1

Figure 31 - Vapor pressure curves (left) and (Px)T diagram (right).

The left side of Figure 31 illustrates two vapor pressure curves for component [1] and
v
[2]. At Ta, the vapor pressures are P1 , P2v 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:
o
C2 (ethane) Tc = 89.92 F Pc = 706.5 psia
o
C10 (decane) Tc = 652.0 F Pc = 305.2 psia

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

The right hand side of Figure 31 illustrates the phase behavior of all possible mixtures
between [1] and [2] at the selected temperature Ta.

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 = Ta..

Note that bubble point pressures increase as the composition of the most volatile
component increases.

Hydrocarbon Composition
May be expressed on a weight basis and on a molar basis. For compositional modeling
we use a molar basis. The relationship between moles and mass is given through the
molecular weight.

Mass of component " i"


Moles of component " i" = (17)
Molecular weight of component " i"

Mi
ni = (18)
Mw i

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

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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

Thus

 n1 
x1 =   (19)
 1
n + n 2  liquid

 n1 
y1 =   (20)
 n1 + n2  gas

And

x1 + x 2 = 1 (21)

y1 + y 2 = 1 (22)

The left side of Figure 32 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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Left Right
P = Pa
T2v De Vapor
wC
CP1 urv
e
Pressure

Bu 2-phases
bb
CP2 le
Cu
Pa rve T1v
Liquid

T1v Temperature T2v x1, y1

Figure 32 - Vapor pressure curves (left) and (Tx)P diagram (right).

At a fixed pressure Pa, the two vapor pressures are intersected at their corresponding
saturation temperatures T1v , T2v .

The right side of Figure 32 shows a temperature composition projection at the selected
pressure Pa. The state of all mixture combinations between [1] and [2] at P = Pa 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 33 shows three different temperature projections in the composition space.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Left Right
Ta Tb Tg
Tg
Tb P1
[1]
Ta

[2]
P2v
Temperature x1, y 1
Figure 33 - Vapor pressures (left) and (Px)T diagram (right) showing supercritical
behavior.

Note that at Tg both components are supercritical. But there may be a region of two-
phase equilibria.

Similarly, in the following figure, we have three different pressure projections that
indicate the same features.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Left Right
Pg
Pg
Pb
Pb T2v
Pressure

Temperature
Pa Pa

T1v
T1v Temperature T2v x1, y1

Figure 34 - Vapor pressures (left) and (Tx)P diagram (right) showing supercritical
behavior.

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 in the same diagram.

z1 = overall mole fraction of [1]

y1 = vapor mole fraction of [1]

x1 = liquid mole fraction of [1]

Figure 35 illustrates an 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 z1. 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

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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 ‘y1’ in
the figure. The oil becomes richer in heavy component and its composition is indicated
by ‘x1’.

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.

Left Right
z1 = fixed T = Ta A
CPM
PB B

C
Pressure

Pressure

PD

Ta Temperature 0 x1 z1 y1 1

Figure 35 - Depletion path for a hypothetical 2 component reservoir fluid.

Note that any overall mixture composition bounded by the horizontal line joining x1 and
y1 has the SAME equilibrium compositions. What changes are the relative amounts of
vapor and liquid.

This is indicated mathematically as:

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

z1 = x1 f l + y1 f v (23)

z1 = x1 (1 − f v ) + y1 f v (24)

where fv is the molar fraction of vapor in the mixture.

That is:

( n1 + n2 ) v
fv =
(n1 + n2 )v + (n1 + n2 )l (25)

Or

z1 − x 1
fv = (26)
y1 − x1

Equation (26) is valid for any number of components, and for all components. That is:

zi − xi
fv = (i = 1, 2, 3, … Nc) (27)
yi − xi

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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Figure 36 shows VLE for a mixture using a temperature-composition projection. All the
concepts are equivalent to those indicated in the previous Figure.

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
z1 = fixed P = Pa
CPM
TD
TB
Pa
TD Ta
Pressure

TB

Ta Temperature 0 x1 z1 y1 1

Figure 36 - Phase equilibrium compositions at Ta, Pc are x1 for the liquid and y1 for the
gas.

This Figure represents a common distillation process (usually isobaric columns).

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Ternary Diagrams

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).

.1 .9

.2 .8

.3 .7

.4 .6

.5 .5

.6 .4

.7 .3

.8 .2

.9 .1

1 0
H0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 I

Figure 37 - Ternary diagram of the H, I, and L components.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Qualitative Representation of Phase Equilibria

Figure 38 represents the evolution of a mixture of methane (C1), propane (C3) and n-
o
pentane (C5) at a specific temperature, 160 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
McCain’s book.

o
Following these ternary phase diagrams at the same temperature (160 F) and at
different pressures, you can visualize typical phase behavior changes in the mixture as
the pressure changes.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

C1 C1

Ga
s
Gas
2-phase

Liquid
nC5 C3 nC5 C3
p=14.7 psia p=200 psia

C1 C1
Ga

Ga
s

s
2-phase 2-phase

Liquid Liquid
nC5 C3 nC5 C3
p=380 psia p=500 psia

C1 C1
Ga
Ga

s
s

2-phase 2-phase

Liquid Liquid
nC5 C3 nC5 p=1500 psia C3
p=1040 psia

C1 C1
G
Gaas
s

2-phase

Liquid

Liquid

nC5 C3 nC5 C3
p=2000 psia p=2350 psia

Figure 38 - Evolution of a mixture of methane (C1), propane (C3) and n-pentane (C5) at
o
160 F and at various pressures.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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-C4 and bubble point fluid X in the figure are miscible in all proportions, while
mixtures of X with C1 are miscible at high concentrations of C1.

C1

.1 .9

.2 .8

.3 .7

.4 .6

.5 .5

.6 .4

.7 .3

.8 .2

.9 x .1

1 0
C10 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 n-C4

Figure 39 - 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.

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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 (zi) is along a tie line have the SAME equilibrium
gas (yi) and liquid composition (xi), but the relative amounts on a molar basis of gas and
liquid (fv and fl) change linearly (0 – vapor at B.P., 1 – liquid at B.P.).

Relative amounts of gas are,

nv number of moles of vapor


fv = = (28)
nt total number of moles

in other words,

nv 1 + nv 2 + nv 3
fv = (29)
nt 1 + nt 2 + nt 3

where,

nti = nli + nvi with i=1, 2, 3 (30)

z i = xi f l + yi f v (31)

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or

zi = xi (1 − f v ) + yi f v (32)

thus,

z i − y i length from overall composition to gas composition


fv = = (33)
yi − xi length of tie line

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

C1

.1 .9

.2 .8

.3 .7

.4 .6

.5 .5
CP
.6 .4

.7 .3

.8 .2

.9 .1

1 0
C10 0 .1 .2 .3 .4 .5 .6 .7 .8 .9 1 n-C4

Figure 40 - A ternary phase diagram illustrating the phase envelope and tie lines.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

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 (C1, CO2, N2- C1, CO2-C2, ...)

• heavy (C7+)

• intermediate (C2-C6)

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.

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Phase Behavior of Ternary Systems


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

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Phase Behavior Fundamentals & Review of Thermodynamics - Colombia – Summer 2000

Figure 41 - General classification of reservoir fluids in terms of compositional


distribution.

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