Thermodynamics 3

Petroleum Engineering Applications of Phase Equilibria , Colombia, Summer 2000-
Author: Dr. Maria Barrufet - Summer, 2000 Page 1/163

Instructional Objectives
After seeing this module the student should be able to:
Evaluate volume roots from a cubic equation of state when two-phases coexist.
Derive and evaluate fugacity coefficients from cubic EOS.
Evaluate phase boundaries (dew and bubble points) using EOS.
Evaluate flash separations using an EOS.
Understand the production mechanism for a gas condensate or a volatile oil
(Constant Volume Depletion, CVD).
Interpret the results of a simulated CVD test from a commercial simulator.
Determine oil and gas in place and recoveries using CVD compositional data.
Determine oil and gas in place from recombination.
Understand vertical compositional variation due to gravity.
Understand the effects of a porous media upon phase equilibria.
Petroleum Engineering Applications of Phase Equilibria

High Pressure Phase Equilibria Applications (Reservoir).
Equations of State Models (EOS). Cubic EOS. Root Selection.
Evaluation of Fugacity Coefficients from Equations of State.
Evaluation of Phase Boundaries (Dew and Bubble Points) and Flash Equilibrium with
EOS. Tuning of Equations of State (EOS). Miscible Gas Injection. Swelling Tests.
Constant Volume Depletion Studies (Gas Condensates and Volatile Oils).
Determination of Oil and Gas in Place by Recombination.
Areal and Vertical Composition Variation in Hydrocarbon Reservoirs. Estimation of
Compositional Gradients due to Gravity.
Phase Equilibria in Porous Media. The Effect of Curved Surfaces.

Suggested Reading: EL, WM, MAB



Equations of State (EOS)
Single Component Systems
Equations of State (EOS) are mathematical relations between pressure (P) temperature
(T), and molar volume (V). For a pure component in a single phase (i.e. gas or liquid)
given any pair of these variables the third can be evaluated. If the component exhibits
phase equilibrium and additional constraining equation is placed and only one variable,
either P or T are needed to specify the STATE of the system. For VLE the constraining
equation is the equality of the Gibbs energy of the GAS and LIQUID phases. A model is
required to evaluate this ENERGY and a CUBIC EOS is one of the many different
models available.
The ideal gas EOS was the first mathematical expression used to describe the PVT
behavior of gases but its use is limited to low pressures (near atmospheric) additionally,
since it only provides a single volume for a given pressure and temperature, it cannot
describe phase transitions

Multicomponent Systems
For multicomponent mixtures in addition to these variables (P, T & V) , the overall molar
composition and a set of mixing rules are needed.
Modern EOSs are versatile tools for reservoir engineering applications. They can be
used for all states (gas, liquid, and solid), and they can describe phase transition
conditions and properties of the coexisting phases. Some of the EOS uses include:
evaluation of gas injection processes (miscible and immiscible), evaluation of properties
of a reservoir oil (liquid) coexisting with a gas cap (gas), simulation of volatile and gas
condensate production through constant volume depletion evaluations, recombination
tests using separator oil and gas streams, evaluation of paraffin deposition in the
wellbore, etc.

Types of EOS
There are many families of EOS, suitable for different purposes and substances i.e.
hydrocarbons, electrolytes, solids, gas-liquid-solid equilibria, etc. In petroleum
engineering the most commonly used EOS are cubic polynomials in volume. More



complicated EOSs exist but these are not practical (unaffordable in terms of computer
time) for compositional simulations.
Cubic equations are EXPLICIT in pressure and can be written as the sum of a term
indicating repulsion forces and a term indicating attraction forces

attr rep
P P P + (1)

One of the most used EOS in petroleum engineering is the Peng-Robinson EOS
(1975).

) ( ) ( b V b b V V
a
b V
RT
P
+ +
(2)

The critical point conditions are that the first and second derivatives of pressure with
respect to molar volume evaluated at the critical point are equal to zero.

0
0
2
2
,
_
,
_
c
c
T
T
V
P
V
P
(3)

Solving these two equations simultaneously provides different values for the parameters
a and b depending upon the EOS used. For the Peng-Robinson EOS these are,
c
c
a
P
T R
a
2 2
(4)
and
c
c
b
P
RT
b (5)



Where

07780 . 0
45724 . 0

b
a
(6)

and

( ) ( )
2
1 1
r
T m + (7)

with

2
2699 . 0 54226 . 1 37464 . 0 + m (8)

The Peng Robinson EOS is a three-parameter corresponding states model.
In practical petroleum engineering applications we are concerned with the phase
behavior of the hydrocarbon liquid mixture, which at a specified pressure and
temperature, is in equilibrium with a hydrocarbon gas mixture at the same pressure and
temperature (the production path sketched in previous lectures).

Equation (2) can be expressed as a cubic polynomial in (V) or (Z). In terms of
compressibility factor this becomes

0 2 3 1
3 2 2 2 3
+ + ) B B AB ( Z ) B B A ( Z ) B ( Z (9)

with



( )
RT
bP
B
RT
P a
A
2
(10)

Cubic EOSs are the simplest polynomials that can provide an adequate description of
both: liquid and gas properties. They can describe the state of pure fluids and mixtures
(single or multiphase) and their properties.
When working with mixtures the same expressions apply except that (a) and (b) are
evaluated for a mixture using a set of mixing rules. The most commonly used mixing
rules (MR) are:

Quadratic MR for a
( ) ( ) ( )

Nc
i
j i
.
Nc
j
j i j i j i m
k a a x x a
1
5 0
1
1 (11)

Linear MR for b
Nc
i
i i m
b x b
1
(12)

where the k
ij
s are called interaction parameters and by definition

0
ii
ji ij
k
k k
(13)

These MRs are called the van der Waals mixing rules. Many more MRs have been
proposed in the literature, but these are the most popular.

Example - For a three-component mixture (N
c
= 3) expand Eqs. (11) and (12) to
evaluate the attraction (a) and the repulsion constant (b). This gives:



( ) ( ) ( )
( ) ( ) ( )
( )
3 3
2
3
2 2
2
2 1 1
2
13
5 . 0
3 1 3 1 3 1
23
5 . 0
3 2 3 2 3 2 12
5 . 0
2 1 2 1 2 1

) 1 ( 2
) 1 ( 2 ) 1 ( 2
1
+
+ + +
+
a x
a x a x k a a x x
k a a x x k a a x x a
m
(14)

b x b x b x b
m 3 3 2 2 1 1
+ +
(15)

A system may not exist as a SINGLE PHASE at the specified P, T, and overall
composition z
i
. Energy requirements may cause the system to split into two (or more)
phases such that the Gibbs ENERGY of the system (i.e VAPOR + LIQUID) is at a
MINIMUM. These two phases will have different compositions from the original system
(y
i
& x
i
).

To find these gas and liquid compositions such that the Gibbs energy is at a MINIMUM
you need to solve a set of non-linear equations simultaneously. The overall mixture
composition will be used to evaluate a unique set of liquid and gas compositions such
that material balance is satisfied. The overall composition z
i
is normally provided to you,
this composition may coincide with the composition of a phase boundary , or you may
need to evaluate gas and liquid compositions (y
i,
x
i
,

i = 1, 2N
c
) which will normally be evaluated from

Therefore the constants a and b can be evaluated using
Overall compositions z
i
i = 1, 2N
c

Liquid compositions x
i
i = 1, 2N
c

Vapor compositions y
i
i = 1, 2N
c

The cubic expression for a mixture is then evaluated using



( )
( )
RT
P b
B
RT
P a
A
m
m
m
m
2
(16)

In most of the current literature the subscript m is omitted for simplicity, and whether it
refers to the mixture or to a single component is understood from the context.

Analytical Solution of Cubic Equations
The cubic EOS can be arranged into a polynomial as Eq. (9) and be solved analytically
as follows. (Solution taken from standard manuals on mathematical formulas)

Lets write the polynomial in the following way

0
3
2
2
1
3
+ + + a x a x a x (17)

Note: x could be either the molar volume, or the density, or the z-factor, when the
equation is expressed in terms of the z factor as in Eq. (9) the coefficients a
1
to a
3
are:

) B B AB ( a
) B B A ( a
) B ( a
3 2
3
2
2
1
2 3
1

(18)

Analytical solution of a cubic polynomial
The procedure to evaluate the roots of a cubic equation analytically follows. This has
been extracted from a mathematical handbook (Spiegel, Schaum series).



Let

3
2 3
3
2 3
3
1 3 2 1
2
1 2
54
2 27 9
9
3
R Q R T
R Q R S
a a a a
R
a a
Q
+
+ +

(19)

The solutions are,

( ) ( )
( ) ( ) T S i a T S x
T S i a T S x
a T S x
+
+ +
+
3
2
1
3
1
2
1
3
2
1
3
1
2
1
3
1
1 3
1 2
1 1
(20)

If a
1
, a
2
and a
3
are real and if D = Q
3
+ R
2
is the discriminant, then
1. One root is real and two complex conjugate if D > 0;
2. All roots are real and at least two are equal if D = 0;
3. All roots are real and unequal if D < 0.

If D < 0, computation is simplified by use of trigonometry, as follows,

1 3
1 2
1 1
3
1
240
3
1
cos 2
3
1
120
3
1
cos 2
3
1
3
1
cos 2
0 If
a Q x
a Q x
a Q x
D
,
_
,
_
,
_

<
!
!
(21)



where

3
cos
Q
R
(22)

3 3 2 1
2 1 3 3 2 2 1
1 3 2 1
a x x x
a x x x x x x
a x x x

+ +
+ +
(23)

where x
1
, x
2
and x
3
are the three roots.

The range of solutions that are used for the engineer are those for positive volumes and
pressures, we are not concerned about imaginary numbers.
Basically, from the general shape of the polynomial we are interested in the first
quadrant of Figure 1.



Figure 1 - Solutions of a cubic polynomial.

The following web site contains Fortran codes to solve the roots of polynomials up to
fifth degree.

http://www.uni-koeln.de/math-nat-fak/phchem/deiters/quartic/quartic.html



Figure 2 - Web site to download Fortran source codes to solve polynomials up to fifth
degree.

Phase equilibrium for a single component at a given temperature can be graphically
determined by selecting the saturation pressure such that the areas above and below
the loop are equal, these are known as the van der Waals loops (see Figure 3 Maxwell
Equal area rule).



-
10
0
0
10
0
20
0
30
0
40
0
50
0
60
0
70
0
2 4 6 8 1
0
1
2
1
4
A1
A2
P
r
e
s
s
u
r
e
Molar Volume
T
c
T
2
T
1
P
1
v
L
2 - Phases
CP
V
L
V
1
2
3
4
7
6
5
0 >
,
_
T
V
~
P
-
10
0
0
10
0
20
0
30
0
40
0
50
0
60
0
70
0
2 4 6 8 1
0
1
2
1
4
A1
A2
P
r
e
s
s
u
r
e
-
10
0
0
10
0
20
0
30
0
40
0
50
0
60
0
70
0
2 4 6 8 1
0
1
2
1
4
A1
A2
P
r
e
s
s
u
r
e
Molar Volume
T
c
T
2
T
1
P
1
v
L
2 - Phases
CP
V
L
V
1
2
3
4
7
6
5
0 >
,
_
T
V
~
P

Figure 3 - van der Waals loops showing the Maxwell Equal Area rule (A1 = A2).

Although the EOS does not provide viscosities (a transport property), it gives phase
compositions that are used in the evaluation of viscosities.
In practical petroleum engineering applications we are concerned with the phase
behavior of the hydrocarbon liquid mixture, which at a specified pressure and
temperature, is in equilibrium with a hydrocarbon gas mixture at the same pressure and
temperature (production path).
Along this production path we will need to evaluate:
(1) Bubble point pressure (P
b
) at given reservoir T and overall z
i
.
(2) Properties of gas & liquid, below (P
b
), through equilibrium computations in the
two-phase region (flash computations).



For a retrograde fluid, along the production path we will need to evaluate:
(1) Dew point pressure (P
d
) at given reservoir T and overall z
i
.
(2) Properties of gas & liquid, below (P
d
), through equilibrium computations in the
two-phase region (flash computations).

To accomplish this we make use of a set of criteria for thermodynamic equilibrium. To
solve the phase equilibrium problem requires time consuming iterations, often the
bottle-neck in all reservoir compositional simulation package.
To evaluate phase equilibrium requires the simultaneous solution of a set of non-linear
equations.
If two (or more) phases exist in equilibrium, then the equal fugacity criteria must be
satisfied.
The number of equilibrium equations to be solved is equal to the number of components
that make up the mixture times the number of phases minus one. (i.e. 10 components
and three-phases (gas / liquid 1/liquid 2 ! 20 equations).

! Physically, the difference of the fugacities of one component in one
phase with respect to another phase gives a measure of the potential for
transfer of that component between these phases. Equal fugacities of a
component in the two (or more phases) results in zero net mass transfer
across the phases, or equilibrium."

At equilibrium pressure, temperature and compositions within the phases remain
constant.

Two-phase VLE
For two-phase vapor-liquid-equilibrium VLE these equations are expressed as:

l
i
v
i
f f

(i = 1, 2, 3, Nc) (24)



When an EOS is used to evaluate the fugacities an alternative expression is using the
fugacity coefficients
( )
l
i
v
i
. The relationship between fugacity and fugacity

coefficients is

P
x f
l
i i
l
i

(25)
l
i i
v
i i
x y

(26)

Fugacity coefficients will be evaluated from an EOS as will be seen later.

Typical phase equilibrium problems to solve are indicated in Table 1.

Given Variables
(independent)
Unknown Variables
(dependent)
Problem Type Example
Application
P, z
i
=x
i
T, y
i
Bubble Point Distillation
T, z
i
=x
i
P,y
i
Bubble Point
Gas injection,
Production
P, z
i
=y
i
T,x
i
Dew Point Separations
T, z
i
=y
i
P,y
i
Dew Point Gas
Condensates,
Production
P, T, z
i
x
i
, y
i
, f
v
Flash Production
Separation
Table 1 - Dependent and independent variables used in typical phase equilibrium
problems.



We will present the algorithms for the: DEW BUBBLE & FLASH equilibrium
calculations which are general regardless of the EOS and mixing rule used. We will
solve phase equilibrium for binary mixtures and we will compare our results from those
evaluated with a commercial package.
The first objective is to understand the type of calculations involved, next we will know
how to use and interpret the results from software packages that will do the job for us.
The phase equilibria equations are expressed in terms of the equilibrium ratios, or more
commonly called the K-values. The K-value of component i is defined as:
v
i
l
i
i
i
i
x
y
K
(27)

Dew Point Calculations
Equilibrium is always stated as:

P
y P
x
v
i i
l
i i
(i = 1, 2, 3, N
c
) (28)

with the following material balance constrains

1
1

Nc
i
i
x (29)
1
1

Nc
i
i
y (30)
1
1

Nc
i
i
z (31)

At the dew-point the overall composition is identical to the vapor (or gas composition).
Therefore making use of the K-value definition:



v
i i
l
i i
x
i i i
z K x (i = 1, 2, 3 ,Nc) (32)

Rearranging Equation (32) and adding over all components we obtain the Dew-Point
objective function. For a Dew-Point equilibrium calculation the objective is to find a
unique set of K-values that satisfies the following equation,

0 1
1

Nc
i i
i
K
z
(33)

Bubble Point Equilibrium Calculations
For a Bubble-point equilibrium calculation, the objective function is derived following the
same reasoning as:
0 1
1

Nc
i
i i
K z (34)
The objective is to find a unique set of K-values that satisfies the above equation. In
searching for these K-values, we will have to find the correct equilibrium compositions
and bubble point pressure ( when the temperature is specified), or the equilibrium
compositions and the bubble point temperature (when the pressure is specified).

Flash Equilibrium Calculations
Flash calculations are the work-horse of any compositional reservoir simulation
package. In a flash separation calculation the objective is to find the fractional amount of
vapor in a Vapor-Liquid mixture at a specified temperature and pressure such that the
following equation is satisfied.
0
1 1
1
1

+
c
N
i i v
i i
) K ( f
) K ( z
(35)



This is one of the alternative mathematical expressions that can be used and is chosen
because of its good behavior in a Newton-Raphson algorithm. This is also known as the
Rachford-Rice function and it is derived from:

Nc
i
i
Nc
i
i
x y
1 1
0 (36)

Notice that the first derivative of Eq. (35) is monotonic (always has the same sign and it
is negative). Figure 4 shows three different flash functions, notice that the three have
the same solution but only the Rachford Rice function is monotonic and therefore it is
well behaved from a numerical stand point.

Numerical Behavior of Flash
Functions
-6.00
-4.00
-2.00
0.00
2.00
4.00
6.00
0.00 0.20 0.40 0.60 0.80 1.00
Molar Fraction of vapor (fv)
F
(
f
v
)
Sum Xi
Sum Yi
Rachford Rice

Figure 4 - Numerical behavior of flash functions.



The two-phase equilibria criteria is that both functions (dew and bubble) must be greater
than one.

1
1
>
Nc
i
i i
K z (37)
1
1
>
Nc
i i
i
K
z
(38)

The equilibrium GAS compositions are evaluated as:

) K ( f
K z
y
i v
i i
i
1 1 +
(39)

with the liquid compositions evaluated as,

i
i
i
K
y
x (40)

As an example here z
i
may indicate the composition of the reservoir oil fluid above the
Bubble-Point (point t
1
). Later in production the pressure in the reservoir drops and this
initial single-phase fluid separates into two phases. Both, gas and liquid, move within
the reservoir and up to the surface according to their relative permeabilities. As fluids
are produced the composition of the reservoir fluids keep changing and consequently
properties such as: density, viscosity, solution gas-oil-ratios, etc. Figure 5 illustrates the
compositional changes that may occur due to production 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 5 - A sequence of phase envelopes resulting from compositional changes during
production or injection.

The following figures indicate the mathematical behavior of the DEW, BUBBLE, and
FLASH functions when evaluated at different locations of the phase envelopes.
Note that this behavior is for the converged K-values.
The following figures illustrate the behavior of the DEW and BUBBLE functions
projected on a temperature composition diagram at a fixed pressure and on pressure-
composition diagram at a fixed temperature.
The behavior of these functions for multicomponents is the same.



T
D
T
B
T
a
z
1
y
1
x
1
1 0
1
1
>
Nc
i
i
i
K
z
1
1
<
Nc
i
i
i
K
z
1
1

Nc
i
i
i
K
z
P = P
a
T
e
m
p
e
r
a
t
u
r
e

Figure 6 - Behavior of the Dew Point function at the boundaries and in the two phase
region in a TX diagram.

If the objective is to find the DEW POINT TEMPERATURE at a fixed pressure (P
a
) and
overall composition.

If 1
1
<
Nc
i i
i
K
z
! Superheated fluid ! lower T (41)

One way of updating the temperature is

+

Nc
i i
i k k
K
z
T T
1
1
(42)

If 1
1
>
Nc
i i
i
K
z
! Subcooled fluid ! increase T (43)



The same scheme works for updating the temperature that is

+

Nc
i i
i k k
K
z
T T
1
1
(44)

The schemes indicated are secure but slow, there are other well documented numerical
accelerating schemes, but numerical methods is not the main objective of this course.

! At the dew point 1
1

Nc
i i
i
K
z
(45)

1
1
>
Nc
i
i
i
K
z
1
1

Nc
i
i
i
K
z
1
1
<
Nc
i
i
i
K
z
P
r
e
s
s
u
r
e
P
D
P
B
P
a
z
1
y
1
x
1
1 0
T= T
a
-
Figure 7 - Behavior of the Dew point function in a PX diagram.

If the objective is to find the DEW POINT PRESSURE at a fixed temperature (T
a
) and
overall composition.

If 1
1
<
Nc
i i
i
K
z
! Under pressurized fluid ! increase P (46)



+

Nc
i i
i k k
K
z
P P
1
1
(47)

If 1
1
>
Nc
i i
i
K
z
! Over pressurized fluid ! lower P (48)

+

Nc
i i
i k k
K
z
P P
1
1
(49)

! At the dew point 1
1

Nc
i i
i
K
z
(50)

To evaluate a bubble-point pressure or bubble-point temperature we use the same
functions and correction schemes.
These correction schemes can be accelerated by using a larger correction step, but the
directionality is the same provided that the fluid does not exhibit a double dew-point
(Gas Condensates).
For the upper DEW POINT of GAS CONDENSATES we must use other numerical
approaches. When the initial guess is in the two-phase region the approach just
explained will converge to the lower dew point.

For a BUBBLE-POINT calculation



1
1
<
Nc
i
i i
K z
1
1
>
Nc
i
i i
K z
1
1

Nc
i
i i
K z
P
r
e
s
s
u
r
e
P
D
P
B
P
a
z
1
y
1
x
1
1 0
T= T
a

Figure 8 - Behavior of the Bubble Point function in a PX diagram.

If the objective is to find the BUBBLE POINT PRESSURE at a fixed temperature (T
a
)
and overall composition, then

If 1
1
<
Nc
i
i i
K z ! Over pressurized fluid ! lower P (51)

+
Nc
i
i i
k
K z P P
k
1
1
(52)

If 1
1
>
Nc
i
i i
K z ! Under pressurized fluid ! increase P (53)

+
Nc
i
i i
k
K z P P
k
1
1
(54)

! At the bubble point 1
1

Nc
i
i i
K z (55)



To ensure the existence of two-phases both functions (DEW & BUBBLE) must be:

1
1
>
Nc
i i
i
K
z
1
1
>
Nc
i
i i
K z (56)

The following graphs complete the illustration of the behavior of these functions.

1
1
<
Nc
i
i i
K z
1
1
>
Nc
i
i i
K z
1
1

Nc
i
i i
K z
P
r
e
s
s
u
r
e
P
D
P
B
P
a
z
1
y
1
x
1
1 0
T= T
a
T
e
m
p
e
r
a
t
u
r
e
T
D
T
B
T
a
z
1
y
1
x
1
1 0
1
1
<
Nc
i
i i
K z
1
1

Nc
i
i i
K z
1
1
>
Nc
i
i i
K z
P= P
a

Figure 9 - Behavior of the Dew and Bubble functions on a TX and a PX diagram.



.
P
b
Pd
P
r
e
s
s
u
r
e
Temperature
CP
B
u
b
b
l
e
-
C
u
r
v
e
D
e
w
-
C
u
r
v
e
1
1
>
Nc
i i
i
K
z
1
1
<
Nc
i i
i
K
z
1
1

Nc
i i
i
K
z
1
1

Nc
i
i i
K z
1
1
>
Nc
i
i i
K z
1
1
<
Nc
i
i i
K z
2-phases
Tr
A
B

Figure 10 - Behavior of the Dew and Bubble functions on a PT diagram.

As pressure keeps dropping gas and liquid compositions are continuously changing in
the reservoir cells. Describing these changes is an essential part of reservoir
engineering that requires the solution of flash equations million of times (a) at different
locations of the reservoir for a fixed time, and (b) at different times and the same
location within the reservoir. The material balance equation plus the diffusivity equation
pressure (Darcys equation) are solved simultaneously.

Evaluation of Fugacity Coefficients and K-values from
an Equation of State (EOS)
The general expression to evaluate the fugacity coefficient for component i in any
phase (vapor, liquid-I, liquid-II, etc.) from any model is given by the following
expression.



fixed T
P
i
v
i
dP
P
RT
V
ln RT
'
1
]
1
0
(57)

This is not a suitable expression to evaluate fugacity coefficients using a pressure
explicit equation of state. Therefore, the goal is to make a transformation of variables to
transform the integral and use volume as the dependent variable.
We need to follow some algebraic steps involving rules of differentiation and the
thermodynamic identities seen in Module 2.

The partial molar volume of component i is defined as:
i n , P , T
v
v
v
v
j
i
t
i
n
V
V
,
_
(58)

for simplicity, many books omit the superscripts that indicate the phase.

Following the (-1) rule of thermodynamics and rules of differentiation
i n , T
v
n , T
v
i n , P , T
v
v
v
j
i
v
t
t
v
j
i
t
n
P
P
V
n
V

,
_
,
_
,
_
(59)
v
i
n , T
v
n , T
v
i n , P , T
v
v
i n , T
v
V
V
P
V
P
n
V
n
P
v
t
t
v
t
t
v
j
i
t
v
j
i
,
_
,
_
,
_
,
_

(60)
and
v
t
t
v
j
i
n , T
v
i n , T
v
v
i
P
V
n
P
V

,
_
,
_
(61)

(Note that first order partial derivatives can be inverted)



Replacing the partial molar volume into the general expression for the fugacity
coefficient

fixed T
P
n , T
v
i n , T
v
v
i
dP
P
RT
P
V
n
P
ln RT
v
t
t
v
j
i
'
1
1
]
1
,
_
,
_
0
(62)
dP
P
RT
dP
P
V
n
P
ln RT
P
n , T
v
i n , T
v
P
v
i
v
t
t
v
j
i

,
_
,
_
0 0
(63)
dP
P
RT
dV
n
P
ln RT
P
v
t
i n , T
v
V
v
i
v
j
i
v
t

,
_
0
(64)

Note that we have changed the limits of the first integral accordingly.

The second integral in the right hand side can be expanded using the following identity:

V
ZRT
P at constant T
) V / Z ( RT
) V / Z ( RTd
P
dP
t
t
(65)
or
t
V ln d Z ln d P ln d (66)
t
t
V
dV
Z
dZ
P
dP
(67)

Replacing Eqn.(67) into Eqn.(64) the final expression to evaluate the fugacity
coefficient using an EOS is.

v
v
t v
i n , T
v
V
v
i
Z ln RT dV
V
RT
n
P
ln RT
t
v
j
i
v
t
1
1
]
1
,
_
(68)



Alternative expressions can be obtained using the compressibility factor as follows
v
V
n nV T
i
v
i
Z
V
dV
n
nZ
v
j
ln 1
ln
, ,
1
1
]
1
,
_
(69)
Z
V
dV
n
nZ
l
j
V
n nV T
i
l
i
ln 1
ln
, ,
1
1
]
1
,
_
(70)

When using cubic EOS, and linear, or quadratic mixing rules, this expression can be
evaluated analytically.
Equilibrium calculations are expressed in terms of K-values. We will illustrate how to
evaluate these K-values from an EOS using the definitions outlined previously.
Physically, the difference of fugacities of one component in one phase with respect to
another phase gives a measure of the potential for transfer of the component between
the phases. Equal fugacities of a component in the two (or more phases) results in zero
net mass transfer across the phases, or equilibrium. Pressure, temperature and
compositions within the phases remain constant.
For two-phase vapor-liquid-equilibrium VLE these equations are expressed as:

l
i
v
i
f
(i = 1, 2, 3, Nc) (71)

When an EOS is used to evaluate the fugacities an alternative expression is using the
fugacity coefficients
( )
l
i
v
i

l
i i
v
i i
x y

(72)

As seen previously the K-value of component i is defined as:



v
i
l
i
i
i
i
x
y
K

(73)

v
i
l
i
v
i
l
i
i
ln
ln
ln K ln
,
_
(74)

dP
P
RT
dV
n
P
dP
P
RT
dV
n
P
K ln RT
P
t
i n , T
V P
t
i n , T
V
i
j
i
v
t
j
i
l
t

,
_
,
_
0 0
(75)

t
i n , T
V
V
i
dV
n
P
K ln RT
j
i
v
t
l
t
,
_
(76)
Note that to evaluate the K-values we need to evaluate the derivative within the integral
and at the limits we need to evaluate the corresponding molar volumes of gas and
liquid. To do so we will require different compositions for the liquid and the gas which
are evaluated iteratively.
The following example shows the steps to evaluate the fugacity coefficient from a cubic
EOS using the expressions just presented.

Example Evaluation of the fugacity coefficient for van der Waals
EOS
We will illustrate the evaluation of a K-value for species i in a multicomponent
mixture using the Van der Waals EOS. The idea can be easily generalized to other
EOS.
Relations to keep in mind:
Total number of moles:
l v
n n n +
Number of liquid moles - binary:
l l
l
n n n
2 1
+



- multicomponent:
l
i
Nc
i
l
n n

1

Number of vapor moles - binary:
v v
v
n n n
2 1
+
- multicomponent:
v
i
Nc
i
v
n n

1

Mole fraction of component i in liquid:
l
l
i
i
n
n
x
Mole fraction of component i in vapor:
v
v
i
i
n
n
y
Overall mole fraction
n
n n
z
v
i
l
i
i
+

Partial derivatives:

1
,
_
i n
l
l
l
j
i
n
n
, 1
,
_
i n
v
v
v
j
i
n
n

0
,
_
i n
l
l
j
v
j
i
n
n
, 0
,
_
i n
v
v
j
v
j
i
n
n

Recall that the volume used in the EOS is a molar volume:
n
V
V
t

The mixture parameters used in the EOS if linear mixing rules are used are:

Liquid



Nc
i
i l
l
Nc
i
i i
l
a
n
n
a x a
i
1 1

Nc
i
i l
l
Nc
i
i i
l
b
n
n
b x b
i
1 1

Vapor

Nc
i
Nc
i
i v
v
i i
v
a
n
n
a y a
i
1 1

Nc
i
i v
v
Nc
i
i i
v
b
n
n
b y b
i
1 1

The van der Waals EOS is:
2
V
a
b V
RT
P
=
2
2
t t
V
an
bn V
RTn

To evaluate the K-values we need to evaluate the following partial derivative

( ) ( )

,
_
,
_
,
_
,
_
,
_
i n
i t
i n
i t t
i n , V , T
i
j j j
n
a
n a
V
n
n
b
n b
bn V
RTn
bn V
RT
n
P
2 2
2

These partial derivatives are

n
a a
n
a
i
i n
i
j
,
_

n
b b
n
b
i
i n
i
j
,
_

Replacing these expressions into

( ) ( )

,
_
,
_
,
_
,
_
,
_
n
a a
n a
V
n
n
b b
n b
bn V
RTn
bn V
RT
n
P
i
t
i
t t
i n , V , T
i
j
2
2 2



Now put the expression back using the molar volume
n
V
V
t
and replace
ndV dV
t

( ) ( )
ndV
n
a a
V n
n
V n
na
n b V
RTnb
n b V
RT
K ln RT
i
t t
i
V
V
i
v
l
1
]
1
,
_
2 2
2
2 2 2 2
2

After cancellations and integration between the molar liquid and vapor volumes the
final expression for the K-value of species i is

,
_
,
_
+
+
,
_
,
_
l
i
l
v
i
v
l l v v i l l
v v
i
V
a a
V
a a
b V b V
RTb
b V
b V
RT K RT
1 1
ln ln

The same algebraic procedure is used for all EOS. The reason that non-cubic EOS are
not popular in Reservoir Engineering is because of their complexity without gaining
much more accuracy and at the expense or much more CPU time.

Fugacity Coefficients from Cubic EOS
The following expressions, taken from Stanley & Walas, give the results obtained for the
fugacity coefficients using the most popular cubic EOS.
The K-value for component i is obtained just by the ratio of the liquid to the vapor
fugacity coefficient of species i.



Van der Waals
( )
RTV
a a
V
b
z
b V
b
b y b
a y a
V
a
b V
RT
P
i i
i
i i
i i
2
1 ln
ln
2
2
1
]
1
,
_
(77)

Note
For the liquid we have an analogous expression.

! The a and b constants are evaluated using the liquid compositions (x
i
s)

! The molar volume for the liquid V
l
is evaluated from the EOS at the same P, and T
as for the gas, but using liquid compositions.

Equilibrium compositions are the unknown variables in equilibrium problem. This is an
iterative process therefore volumes and fugacity coefficients are evaluated many times
before they converge.

Redlich-Kwong
( )
( )
( )
( ) [ ]
,
_
,
_
,
_
+
1
]
1
+
1
]
1
,
_
z
B
A
A
B
B
B
A
B z z
B
B
V
b
aa
b
ab
bRT V
b
z z
b
b
b y B
a y A
b V V T
a
b V
RT
P
i i i
i
i
i i
i
i i
i i
1 ln 2 ln 1
ln
1 ln 2
1
1 ln 1
ln
)
5 . 1
2
(78)



Soave
( ) ( ) ( ) ( )
( )
( )
( )
( ) ( )
( ) [ ] ( )

,
_
,
_
,
_
+
1
]
1
+
1
]
1
,
_
z
B
a y
a B
B
B
A
B z z
B
B
V
b
a y
a b
b
bRT
a
V
b
z z
b
b
RT
P b
B
RT
bP
B
RT
P a
A
b y b
a y y a
k
a a k a
j
ij j
i i
i
j
ij j
i i
i
i
i
i i
ij j i
ii
jj ii ij ij
1 ln
2
ln 1
ln
1 ln
2
1 ln 1
ln
0
1
2
(79)

When using cubic EOS, and linear, or quadratic mixing rules, this expression can be
evaluated analytically.

Peng-Robinson
( ) ( )
( )
( )
( )
RT
P b
B
RT
P b
B
RT
P a
A
B z
B z
a y
a B
B
B
A
B z z
B
B
i
i
v
v
v
v
v v
v v
j
ij j
v v
i
v
v
v v v
v
i v
i
1
]
1

+ +
1
]
1
+

2
) 1 2 (
) 1 2 (
ln
2
2 2
ln 1
ln
(80)

You will have a homework were you will have to proof Eq. (80) (that is a good algebraic
exercise!).



To evaluate the K-values we just need to ratio the liquid and gas fugacity coefficients.

Tuning of Equations of State (EOS)
For two-phase vapor-liquid-equilibrium VLE, the equilibrium equations were expressed
as:
l
i i
v
i i
x y

(81)

These fugacity coefficients are evaluated from an EOS, in this case we will chose the
Redlich-Kwong EOS (RK).

The phase equilibria equations are expressed in terms of the equilibrium ratios, or more
commonly called the K-values. The K-value of component i is defined as:
v
i
l
i
i
i
i
x
y
K
(82)

Example - Tuning of an EOS to VLE data
Given the experimental VLE data on C
3
-CO
2
reported in Table 2 we wish to
determine k
ij
in the Redlich-Kwong EOS, such that predicted values from the EOS
are as close as possible to the experimental values.
These values chosen for prediction will be saturation pressures and either the
liquid or the gas compositions. If the liquid compositions are selected as
independent the type of calculation will be a bubble point and the vapor
compositions will be evaluated. Likewise if the gas compositions are selected as
independent variable the type of calculation will be a dew point and the liquid
compositions will be evaluated. This choice is arbitrary, but it is normally



constrained by selecting as independent variables those for which one has the
highest precision.

Even though this matching is done for just one set of isothermal data EOS have
the power to be extrapolated with accuracy to other conditions!!

Binary VLE Data on the CO
2
/C
3
System at T =4.4
o
C
Pressure (atm) x(CO
2
) y(CO
2
)
6.81 0.0247 0.2056
10.21 0.0884 0.4676
13.61 0.1602 0.6036
17.01 0.2402 0.6864
20.41 0.3316 0.7431
23.81 0.4361 0.7876
27.22 0.5532 0.8309
30.62 0.6714 0.8688
34.02 0.7956 0.9102
37.43 0.9401 0.9702
Table 2 - Experimental VLE data for CO
2
/C
3
.

A graph of the data is



0
10
20
30
40
P
r
e
s
s
u
r
e

(
A
t
m
)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
x (CO
2
) , y(CO
2
)
T = 4.4
o
C
Liquid
Vapor
2-phases

Figure 11 - Experimental PX diagram for the system Propane/CO
2
at 4.4
o
C.

Mathematically this minimization problem is expressed such that the following
objective function is minimized.

( ) Min P P F
M
j
cal
i
data
i

2
1
(83)

Where;
M = number of data points (here is 10)
data
i
P = experimental saturation pressures
cal
i
P = saturation pressures calculated from the RK EOS.



The Redlich-Kwong EOS is
) b V ( V T
a
b V
RT
P
/
+
2 1
(84)

Step 1.
Evaluate pure component EOS constants (a & b) for all components. The
expressions for these from the RK EOS are,
ci
.
ci
i
P
T R
. a
5 2 2
42748 0 and
ci
ci
i
P
RT
. b 08664 0

The critical properties for CO
2
and C
3
are tabulated and are,

Component T
c
(K) P
c
(Atm)
CO
2
304.19 72.85
C
3
Fill up Fill up

The gas constant to be used in these calculations has the following value and units

K mol
liter Atm
. R 08205 0

Therefore the attraction constants are:

Let (1) be CO
2

2
11 CO
a a



( )
1
]
1
1
]
1

Atm
K
K mol
liter Atm
.
.
. . a
2.5 .
2
5 2
2
11
85 72
19 304
08205 0 42748 0
2
1.5 2
mol
K Atm l
. a 7537 63
11

Likewise for propane :
2
1.5 2
C
mol
K Atm l
. a a 48 180
22
3

The interaction constant of attraction is
( )
12 22 11 12
1 k a a a

And the repulsion constants are:

1
]
1
1
]
1

Atm
K
K mol
l Atm
.
.
. . b
85 72
19 304
08205 0 08664 0
1

mol
l
. b 02968 0
1

and for propane

mol
l
b 006268
2

Equilibrium is always stated as:



P
y P
x
v
i i
l
i i
(i = 1, 2, 3, Nc)

with the following material balance constrains

1
1

Nc
i
i
x
1
1

Nc
i
i
y
1
1

Nc
i
i
z

Step 2.
Evaluate the fugacity coefficients using the RK EOS. These expressions are,
1
]
1
,
_
,
_
+
+
,
_
,
_
,
_
b V
b
V
b V
ln
b RT
ab

RT
PV
ln
V
b V
ln
b RT
a z
b V
b
b V
V
ln
ln
.
.
i
i i
2 5 1
1
5 1
2
1
1
1
1
2

For a vapor phase:
v v

, V V , y z
1
1 1 1

For the liquid phase:
l l

, V V , x z
1
1 1 1

To demonstrate the procedure, we will choose one data point:
( ) T , P , y , x
1 1

For this example:



K . . . T
Atm . P
. y
. x
55 277 15 273 4 4
61 13
6036 0
1602 0
1
1
+

To begin the iterations we will assume the interaction parameter:
06 0
12
. k

And we must select what will be our dependent and our independent variables:

Given Variables
Independent
Unknown Variables
To evaluate
Problem Type
T, z
i
=x
i
T=277.55 K
x
1
=0.1602

P,y
i
Bubble Point

The selection of dependent and independent variables is completely arbitrary. It
will be dictated by the weight or confidence given to the experimental points.
Usually, the Temperature and the liquid compositions are more easily and
accurately measured than the pressure and gas compositions.

To evaluate the fugacity coefficients we need:

Assume an initial guess for the gas composition and pressure. We can use the
experimental data as the initial guess.



Evaluate the interaction constant a
12
, and the mixture parameters for both gas and
liquid phases. We will use quadratic mixing rules for the a parameter and linear for
the b parameter.

Once these are evaluated the EOS must be solved twice to obtain the gas and
liquid molar volumes.
! For the liquid phase using x
i
, a
l
, b
l
, V
l

! For the vapor phase using y
i
, a
v
, b
v
, V
v

( ) ( )

2
1
5 0
2
1
1
i
j i
.
j
j i j i l
k a a x x a ( ) ( )

2
1
5 . 0
2
1
1
i
j i
j
j i j i v
k a a y y a
2
1 i
i i l
b x b
2
1 i
i i v
b y b

The interaction constant of attraction using our initial guess for k
12
= 0.06 is

( )
12 22 11 12
1 k a a a
( )
2
0.5 2
mol
K l Atm
. . . . a 83 100 06 0 1 48 180 754 63
12

12 2 1 22
2
1 11
2
1
2 a x x a x a x a
l
+ +
( )( )
2
0.5 2
l
l
mol
K l Atm
. a
. . . . . . . a
05 156
83 100 8398 0 1602 0 2 48 180 8398 0 754 63 1602 0
2 2
+ +

and



mol
l
. b
. . . . b
l
l
05739 0
0626 0 8398 0 02968 0 1602 0
+

With these constants, we now must solve the cubic EOS for V
l
,

) b V ( V T
a
b V
RT
P
l l l
/
l
l l
data
+
2 1 1

( ) ( ) 05739 0 55 277
05 156
05739 0
55 277 08205 0
61 13
5 0
. V V .
.
. V
. .
.
l l
.
l
+

which is solved for V
l
, and if three real roots are obtained the smallest root is
chosen. If not the real root of the equation. This gives;
mol
l
. V
l
08785 0

Now we can evaluate the fugacity coefficient for CO
2
(component 1) of the liquid.
1
]
1
,
_
,
_
+
+
,
_
,
_
,
_
l l
l
l
l l
l
.
l
l
l
l l
l
.
i
i i
l l l l
l
l
b V
b
V
b V
ln
b RT
b a

RT
PV
ln
V
b V
ln
b RT
a x
b V
b
b V
V
ln
ln
2 5 1
1
5 1
2
1
1
1
1
2

Replacing the results obtained, we obtain:
43228 0 8387 0
7116 2 9975 0
2 2
1 1
.
ln
.
ln
l l
l l

Now, repeat the same procedure for the vapor phase.
12 2 1 22
2
1 11
2
1
2 a y y a y a y a
v
+ +



( )( )
2
0.5 2
v
v
mol
K l Atm
. a
. . . . . . . a
84 99
83 100 3964 0 6036 0 2 48 180 3964 0 754 63 6036 0
2 2
+ +

2 2 1 1
b y b y b
v
+
mol
l
. b
. . . . b
v
v
04276 0
06268 0 3964 0 02968 0 6036 0
+

Now use the RK EOS with b
v
, a
v
, and P
i
data
and solve for the vapor volume. Again, if
three real roots are obtained we must select the largest. This provides;

mol
l
. V
v
4251 1

Calculate the fugacity coefficients for both components in the vapor phase. This
provides.
78483 0
93093 0
2
1
.
v
v

Next we evaluate the K-values and a new set of vapor compositions
v
l
x
y
K
1
1
1
1
1

9128 2
9309 0
7116 2
1
1
1
.
.
.
K
v
l

5508 0
78483 0
43228 0
2
2
2
.
.
.
K
v
l



The new vapor compositions are:
4626 0 5508 0 8398 0
4666 0 9128 2 1602 0
2 2 2
1 1 1
. . . K x y
. . . K x y

the sum is not = 1, Whoops!

The material balance constraint must be satisfied. Therefore we must normalize
the new vapor compositions such that its sum is equal to one.

9292 0 4626 0 4666 0
2 1
. . . y y + +
5022 0
9292 0
4666 0
2
1
1
1
.
.
.
y
y
y
i
i
k ,

4978 0
9292 0
4626 0
2
1
2
2
.
.
.
y
y
y
i
i
k ,

where k is iteration index.

The New pressure is evaluated as

2
1
1
i
i i k k
K x P P
Atm . . . P
k
65 12 9292 0 61 13

Recall the phase envelope and the bubble point criteria to satisfy.



1
2
1

i
i i
K z ! Bubble point - Solution
1
2
1
>
i
i i
K z ! Superheated ! lower T or increase P.
1
2
1
<
i
i i
K z ! Subcooled ! Increase T, or lower P.

Now return to Step 1. And using these new values for P and vapor compositions
repeat the procedure until the bubble point criteria is satisfied.

This is your first answer for k
ij
= 0.06. We have only calculated the saturation
pressure for one composition.
! You must calculate VLE for all the data points provided still using k
ij
= 0.06
! Next you must repeat all of the above for different values of k
ij
. A Newton
Raphson procedure can be followed to select successively better values for k
ij.
This is a minimization problem. The final answer to this exercise gives an optimum
k
ij
of 0.07605.

A flow chart summarizing this procedure is as follows.



Given data:
Temperature
Vapor Compositions
Liquid Compositions
Pressure composition data
M = # of data sets
) ,... ,..., , (
2 1 Nc i
y y y y y
"
) ,... ,..., , (
2 1 Nc i
x x x x x
"
( )
M j y x P
j
,... 1 , ,
" "
Pure fluid propeties
Hydrocarbon Characterization Schemes
...) , , , , ( Mw T T P
b c c

Mixing Rules - EOS
Select dependent and independent variables
(i.e., Dependent: - Independent ) y P
"
,
x T
"
,
For all data sets: k =1,M do
Set initial guesses and interaction parameters (j =1)
( )
k
y y
exp 1
" "
( )
k
P P
exp 1
1
ij ij
k k
1



Evaluate for (i =1,Nc)
k
( )
k
l
i
v
i l v
V V
, ,
Evaluate for (i =1,Nc)
k
k
v
i
l
i
i
K
,
_
Re-evaluate for (i =1,Nc)

k
k
Nc
j
j j
i i
i
K x
K x
y
,
_
1
Is
for (i =1,Nc)
k
?
k
Nc
j
j j
K x

,
_
0 1
1
N
Update
k
Nc
i
i i j j
K x P P
,
_
+
1
1
Y
Print
( )
ij k
k x y T P , , , ,
" "
Is
optimal?
( ) <
M
k
calc
P P
1
2 exp
N
Change interaction parameters
Y
Print
( )
ij k k x y T P
" "
End
1



Evaluation of Reservoir Engineering PVT
Properties from an Equation of State

The material balance equation is one of the most powerful tools for estimating oil and
gas in place by using production data and PVT fluid properties. Accurate oil and gas
properties are needed for making any meaningful estimate of OOIP/OGIP for any type
of reservoir fluid.
Oil and gas formation volume factors (B
o
s and B
g
s), bubblepoint pressure, and solution
gas oil ratios (R
s
s) can be obtained from flash vaporization, differential liberation, and
separator separation tests. These are standard PVT experimental procedures for the oil
industry, although they may not always be economically affordable.
In the flash vaporization experiment, a variable-volume cell is filled with a reservoir
liquid sample and brought to reservoir temperature. The pressure in this cell is changed
by changing the sample volume through a movable piston. Pressure volume pairs are
recorded and the bubblepoint pressure and bubblepoint volume are obtained by
intersecting two lines with different slopes, one very steep within the liquid phase region,
and the other less steep, corresponding to the two-phase region. The cell contents
remain constant throughout the experiment.
Differential liberation experiments are conducted to determine gas and oil formation
volume factors and solution gas oil ratios. The difference with the flash vaporization
experiment is that all the gas formed in the PVT cell is expelled after every pressure
depletion stage, then all these gas volumes are brought to standard conditions and
added. The total volume of gas removed during the entire process is the amount of gas
in solution at the bubblepoint. The solution gas/oil ratio at any given pressure lower than
the bubblepoint pressure is obtained by adding all the volumes of gas released at lower
pressures down to atmospheric conditions. These are converted to the volume at
standard conditions and divided by the volume of residual oil left at the very last
expansion stage.
Properties obtained from this test are indicated as differential vaporization values.
These are time-consuming experiments, prone to errors that accumulate in every
expansion stage. To make matters worse, the R
s
obtained from a differential depletion
experiment will vary depending upon the pressure decrements taken, and if the



expansion from reservoir conditions (above the bubblepoint) to standard conditions is
done in just one or two stages such as a separation process the R
s
obtained at the
bubblepoint will differ from the R
s
obtained from a liberation experiment.
In the Separator tests, the reservoir sample brought to reservoir temperature and
bubblepoint pressure is expanded through two separation stages; the second is in the
stock tank itself. The pressure and temperature of the first separator are selected such
that the stock tank oil has a maximum API gravity, which means that the gas/oil ratio at
the bubblepoint will be at a minimum, and the stock oil will have a maximum volume,
which will yield a minimum oil formation volume factor at the bubblepoint.
For volatile oils, three or more separation stages are usually used to maximize the oil
volume in the stock tank. To optimize this would require various combinations of
pressure-temperature pairs for all the separators used, plus economic considerations.
The underlying assumption for having all these tests is that the reservoir process can be
simulated from a differential vaporization, while the process from the bottom of the well
to the stock tank can be simulated with a separator test. Under these assumptions, fluid
properties at pressures below the bubblepoint pressure can be obtained by some sort of
empirical averaging between the two tests.

( )
oDb
oSb
sD sDb sSb s
B
B
R R R R (85)

and

oDb
oSb
oD o
B
B
B B (86)

The well-known averaging formula for R
s
may provide some unrealistic negative values,
particularly at low pressures. McCain devised a new empirical formula, analogous to the
formula for the oil formation volume factor, that prevents these negative results.

sDb
sSb
sD s
R
R
R R (87)



There are a variety of correlations for these standard PVT properties, although many of
them have been developed for specific data sets, and extrapolation to other fields may
be quite dangerous. Additionally, most of these correlations require as input variables
some experimental information such as bubblepoint pressures, API and/or gas gravities,
or R
s
s.

Equations of State provide an alternative method of estimating these properties
provided that the reservoir fluid composition is known. Simulated PVT experiments
provide simultaneously all liquid and gas properties in a manner that is self consistent.

The Phase Equilibrium Problem
Many petroleum engineering applications deal with the phase behavior of the
hydrocarbon oil liquid mixture, which at a specified pressure and temperature coexists
with a hydrocarbon gas mixture at the same pressure and temperature (i.e. in the
production path). To be able to determine the properties of these two phases,
thermodynamic phase equilibrium is assumed.
To solve phase equilibrium problems, a set of thermodynamic criteria must be satisfied.
The set of equilibrium equations is mathematically presented in terms of compositions
and fugacity coefficients, or in terms of the K-values. If a vapor and a liquid phase exist
in equilibrium, then the equal fugacity criterion for every component in each phase must
be satisfied. For vapor liquid equilibrium, this is equivalent to

P x P y
l
i i
v
i i

(i = 1, 2, 3, Nc) (88)

where by definition y
i
denotes the mole fraction of component i in the gas phase, while x
i

denotes the molar composition of i in the liquid phase, and Nc is the total number of
components in the mixture. The composition of the overall mixture (gas + liquid) is
usually denoted by z
i
.



In terms of K-values

v
i
l
i
i
i
i
x
y
K
,
i i i
x K y (i = 1, 2, 3, Nc) (89)

The following material balance constraints must also be satisfied:

1
1

Nc
i
i
x 1
1

Nc
i
i
y 1
1

Nc
i
i
z (90)

Physically, the difference between the fugacities of a component in one phase with
respect to the other phase gives a measure of the potential, or driving force, for transfer
of the component between these phases. Equal fugacities in both phases results in zero
net mass transfer across the phases, or equilibrium. Pressure, temperature, and
compositions within the phases must remain constant.

Table 3 indicates the governing equations for the most common VLE (vapor-liquid-
equilibrium) computations performed by the petroleum engineer along with examples.
In all these problems the objective is to find the dependent variables that will give a
unique set of K-values that satisfies the governing equation. Once convergence is
achieved, the equilibrium compositions (i.e., gas for a bubblepoint and liquid for a
dewpoint) are evaluated.
In a flash problem, a set of K-values is proposed which is usually evaluated from
correlations as a function of pressure and temperature. The objective is then to find the
fractional molar amount of vapor (f
v
) in a vapor/liquid mixture at the specified
temperature and pressure such that the flash equation is satisfied. At convergence the
equilibrium gas and liquid compositions are evaluated from the equations listed in Table
3
When an EOS is used, K-values are also dependent upon compositions thus the
iteration procedure does not stop here. These equilibrium compositions will provide a
new set of K-values when used with the EOS, and this new set of K-values must be



used to restart the iterations in the flash function. Iterations proceed until the K-values
and all compositions dont change.
Flash calculations are the work-horse of any compositional reservoir simulation
package.

Given
Variables
(independent)
Unknown
Variables
(dependent)
Problem
Type
Governing Equations
Example
Application
P , z
i
=x
i
T, y
i

0 1
1

Nc
i
i i
K z

Separator-
Distillation tests
T, z
i
=x
i
P,y
i

Bubble
Point
i i i
K z y
Gas injection
Production
P, z
i
=y
i
T,x
i

0 1
1

Nc
i i
i
K
z

Gas Condensates
T, z
i
=y
i
P,x
i

Dew
Point
i
i
i
K
y
x
Production
P, T, z
i
x
i
, y
i
, f
v
Flash
0
) 1 ( 1
) 1 (
1

+
c
N
i i v
i i
K f
K z

) 1 ( 1 +
i v
i i
i
K f
K z
y

i
i
i
K
y
x
Production

Separation
Processes

PVT Tests

Evaluation of
B
o
, R
s
, R
v
, B
g

Table 3 - Governing equations for typical VLE problems.

Simulated PVT Experiments



As seen from Table 3, an EOS can be used to evaluate bubblepoint pressures and
flashes provided the overall mixture composition and a choice of independent variables
is given. Use of an EOS to evaluate B
o
and R
s
below the bubblepoint is accomplished
by proper accounting of the fractions of gas and liquid obtained in a sequence of
depletion stages. The liquid compositions from each stage are stored and this mixture is
expanded (flashed) to successively lower pressures. Table 4 indicates the procedure
followed when a fixed amount of mixture (say one mole) is subjected to these depletion
stages. As a result of the flash computations, not only are gas and liquid compositions
obtained, but also liquid and gas volumes which form part of the evaluation of the K-
values.

Depletion
Stage
Starting
Moles
f
v
f
l

Moles of Gas
Produced (n
v
)
Moles of
Liquid in PVT
cell (n
l
)
0 1 0 1 0 1
1 1 f
v1
f
l1
f
v1
*1 f
l1
*1
2 f
l1
*1 f
v2
f
l2
f
v2
*f
l1
*1 f
l2
*f
l1
*1
3 f
l2
*f
l1
*1 f
v3
f
l3
f
v3
*f
l2
*f
l1
*1 f
l3
*f
l2
*f
l1
*1

N
d

1
1
1

d
N
i
li
f

f
vNd
f
lNd
1
1
1

li
N
i
vN
f f
d
d
1
1

d
N
i
li
f
Table 4 - Accounting of fractional molar amounts of gas and liquid produced from a
simulated differential flash vaporization process.

Accounting for the gas produced and liquid remaining after each depletion stage, as
indicated in Table 4, the formation volume factor of the oil from a differential
vaporization test is obtained as:

B
o
at P > P
b



d
N
i
i l SC SC o
R o
o
f P T V
P T V
B
1
,
) , (
~
) , (
~
(91)

where ) , (
~
P T V
R o
is the molar volume of the oil evaluated at reservoir temperature (T
R
)
and P. N
d
is the number of depletion stages and f
l,i
is the liquid molar fraction obtained
in depletion stage i.

B
o
at P< P
b

d
N
i
i , l SC SC o
j
i
i , l j R o
o
f ) P , T ( V
~
f ) P , T ( V
~
B
1
1
(92)

it can bee seen that the depletion stages up to pressure j cancel out leaving the
following expression

d
N
j i
i , l SC SC o
j R o
o
f ) P , T ( V
~
) P , T ( V
~
B
1
(93)

The initial solution gas/oil ratio is evaluated as:

1
]
1
d
d
N
i
i l SC SC o
N
j
j
k
k l j v SC SC g
si
f P T V
f f P T V
R
1
,
1
1
1
, ,
) , (
~
) , (
~
(94)

at a pressure stage E below the bubblepoint pressure



1
]
1
d
d d
N
i
i , l SC SC o
N
E j
N
E k
k , l j , v SC SC g
sE
f ) P , T ( V
~
f f ) P , T ( V
~
R
1
1
1
(95)

where ) , (
~
SC SC g
P T V is the molar volume of the gas evaluated from the ideal gas law at
the standard conditions (T
SC
and P
SC
).

Simulated PVT Properties for a Black Oil and a Volatile Oil
Two reservoir fluids were selected using fluid compositions representative of a black oil
and a volatile oil system. These two fluids were subjected to a differential depletion test
at T =180
o
F using the Soave-Redlich-Kwong EOS. The volatile system was subjected
to various separator tests using one and two separators in addition to the stock tank
itself, with the purpose of maximizing the liquid produced.

Figure 12 indicates the optimization of the pressure in Separator 2 (the low pressure
separator), provided the conditions of the high pressure separator have been fixed at
900 psia and 100
o
F. It can be easily seen that the optimal conditions found for this case
will vary depending upon the choice of temperature and conditions in Separator 1.



3160
3180
3200
3220
3240
3260
3280
3300
S
o
l
u
t
i
o
n

G
a
s

O
i
l

R
a
t
i
o

a
t

P
b

(
R
s
b
)
2.76
2.78
2.80
2.82
2.84
2.86
F
o
r
m
a
t
i
o
n

V
o
l
u
m
e

F
a
c
t
o
r

a
t

P
b

(
B
o
b
)
50 100 150 200 250 300
Separator 2 Pressure (psia)
High Pressure Separator @ 900 psia and
T
Sep2
= 75
o
F
100
o
F

Figure 12 - Optimization of separator 2 conditions for a volatile oil.

Figure 13 shows the effect of pressure in Separator 1 upon the R
sb
and B
ob
, when the
conditions in Separator 2 and the temperature have been fixed. This figure also
illustrates the advantage of having two separators instead of one when producing a
volatile fluid. Again, these two separators are in addition to the stock tank oil.



3360
3380
3400
3420
3440
3460
S
o
l
u
t
i
o
n

G
a
s

O
i
l

R
a
t
i
o

a
t

P
b

(
R
s
b
)
2.90
2.92
2.94
2.96
F
o
r
m
a
t
i
o
n

V
o
l
u
m
e

F
a
c
t
o
r

a
t

P
b

(
B
o
b
)
400 500 600 700 800 900 1000
Separator 1 Pressure (psia)
Low Pressure Separator @ 300 psia and
T
Sep1
= 160
o
F
75
o
F
One Separator Stage

Figure 13 - Comparison between one and two separator stages for a volatile oil.

This is a multiple variable optimization problem.

Figure 14 shows the oil formation volume factor obtained for the black oil and the
volatile system. Additionally, the values obtained from one of the most modern
correlations for the black oil (Kartoadmodjo, T. and Schmidt) correlation is indicated.
This correlation is only indicated for reference purposes, and it requires the API gravity
of the residual oil, the specific gravity of the gas, and the total gas produced from a
separator test. In return it will give bubblepoint pressures, solution gas oil ratios, and
formation volume factors.



1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
F
o
r
m
a
t
i
o
n

V
o
l
u
m
e

F
a
c
t
o
r

(
B
o
)
0 1000 2000 3000 4000 5000
Pressure (psia)
Black Oil
Volatile Oil
Black Oil Correlation
T
R
=180
o
F
P
b
P
b

Figure 14 - EOS simulated oil formation volume factors obtained from a differential
depletion test at T = 180
o
F for a black and a volatile oil.

Figure 15 shows the solution gas/oil ratios obtained for the black oil and the volatile
system. Notice that knowledge of the bubblepoint is crucial for this type of evaluation.



0
1000
2000
3000
4000
S
o
l
u
t
i
o
n

G
a
s

O
i
l

R
a
t
i
o

(
R
s
)
0 1000 2000 3000 4000 5000
Pressure (psia)
Black Oil
Volatile Oil
Black Oil Correlation
T
R
=180
o
F
P
b
P
b

Figure 15 - EOS simulated solution gas oil ratios obtained from a differential depletion
test at T = 180
o
F for a black and a volatile oil.

Figure 16 shows the gas specific gravity as a function of pressure for the two reservoir
systems. It can be seen clearly that the gas produced from the volatile oil is heavier,
and it will likely produce some additional liquid when expanded to standard conditions
(R
v
). Those calculations are not indicated here, though.



0.6
0.8
1.0
1.2
1.4

G
a
s

S
p
e
c
i
f
i
c

G
r
a
v
i
t
y
0 1000 2000 3000 4000
Pressure (psia)
Black Oil
Volatile Oil
T=180
o
F

Figure 16 - Gas specific gravities obtained from a differential depletion test at T = 180
o
F
of a black and a volatile oil.

,
_
scf
ft cu
0282 . 0 . 0
P
ZT
B
g
(96)



0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
B
g

(
c
u

f
t

/

S
C
F
)
0 1000 2000 3000 4000
Pressure (psia)
Black Oil
Volatile Oil
T = 180
o
F

Figure 17 - Gas formation volume factors from a differential depletion test at T = 180
o
F
for a black and a volatile oil.

Figure 17 shows the gas formation volume factors for both fluids evaluated using the
standard formula which assumes that the mass of gas is constant, or that no oil is being
produced from the gas when expanded to standard conditions. The compressibility
factor is obtained from the EOS at the indicated pressure and temperature, using the
gas compositions in equilibrium with the remaining liquid. If the gas releases oil at the
surface, B
g
could be affected by as much as 30%.

The Less Popular Volatized Oil or Solution Oil-Gas Ratio, Rv
Up to this point a systematic evaluation of the standard PVT properties used in black oil
and gas material balance equations was presented. To evaluate B
g
only the Z factor for
the gas phase obtained after each depletion stage is needed. The main assumption



here is that the stock-tank oil (also called surface oil) cannot be volatilized into the gas
phase.
As pressure declines below the dewpoint, gas condensate reservoirs release liquid
within the reservoir pore space, which can be as high as 30 to 35% of the pore volume.
Condensate and volatile reservoirs also produce distillate oil from the vapor phase
produced at surface conditions.
These facts indicate that surface oil is also dissolved in the gas phase. To deal with all
types of reservoir fluids one must take into account the so called volatilized oil, i.e. oil
dissolved in the gas phase.
This not-so-popular PVT property that takes into account the volume of surface
volatilized oil dissolved per unit volume of surface gas is called R
v
. The R
v
of a reservoir
gas at P
1
,T
1
(reservoir pressure and temperature) is obtained by expanding a fixed
volume of this gas from to P
SC
, T
SC
. The volumes of surface gas and stock tank oil
obtained are recorded, and R
v
is calculated as the number of STB of surface oil
obtained per cubic feet of surface gas at standard conditions. This oil that appeared at
surface was volatilized at reservoir conditions. For pressures above the saturation
pressure, R
v
is just the inverse of R
s
. But at pressures P < P
saturation
, it is not the same
because we are considering the oil in the gas phase.

MMSCF
STB
R
v

conditions standard at gas surface of feet cubic of million
conditions standard at oil of barrels
(97)

Figure 18 and Figure 19 sketch how this volatilized oil can be obtained from the gas
phase of a volatile oil and from a retrograde gas respectively. The volatized oil (R
v
) is
used in a generalized compositional material balance formulation that can be used for
volatile and condensate systems. This subject will be described in greater detail in
future lectures.



separator oil

stock tank oil
P > P
b
P, T
P = P
SC
Reservoir Separator Surface
Conditions
Conditions
Conditions
T
R
T= T
SC

Figure 18 - Schematics of the additional distillate oil produced from a volatile oil.

surface oil

P > P
d
P = P
SC
Reservoir
Surface
Conditions
Conditions
T
R
T = T
SC

Figure 19 - Schematics of the distillate oil produced from a gas condensate.



Example - Evaluation of Reservoir Engineering Fluid Properties using
an Equation of State (EOS)
The following example illustrates a set of fluid property calculations using the
Soave-Redlich-Kwong EOS. The fluid is a hypothetical reservoir oil (BigBucks) with
4 components.

Initial Reservoir Composition
Component
Name & Short Cut
Identification
Mole
Fraction
T
c
(K) P
c
(atm) M
w

Methane
Ethane
Pentane
Nonane
C
1

C
2

C
5

C
9

0.3
0.2
0.2
0.3
190.6
305.4
469.6
594.6
48.5
48.2
33.3
22.8
0.008
0.098
0.251
0.440
16.042
30.068
72.146
128.259

PVT Properties of Reservoir Fluid at given reservoir conditions
Given initial reservoir pressure and temperature are:
T = 200.0 F & P = 1800.0 psi
Assume we start with 1 lb-mole of fluid ! upscaling easily done
Properties evaluated from the EOS are

Volume (ft
3
) (one lb-mole)
Z-Factor (liquid)
Density (lb/ft
3
)
Molecular Weight
1.982
0.5041
32.151
63.73



Single phase (above bubble-point pressure).

The gas constant in these units is:
R mole lb
ft psi
732 . 10
o
3
R

The bubble point pressure corresponding to T = 200.0
o
F is P = 1507.5 psi.
Temperature
P
r
e
s
s
u
r
e
P = 1507.5 psi
T=200
o
F
CP
Temperature
P
r
e
s
s
u
r
e
P = 1507.5 psi
T=200
o
F
CP

Fluid properties at the bubble-point are:
Volume (ft
3
/ lbmol)
Z-Factor
Density (lb/ft
3
)
Viscosity (cP) Molecular
Weight
2.018
.4298
31.585
.1273
63.73



Simulated Constant Mass Expansion
(Also called flash liberation - No gas is being produced).
This experiment is used to obtain isothermal compressibilities.

First Expansion T = 200.0
o
F, P = 1500.0 psia
Component
Name
Total
Moles %
z
i

Vapor %

y
i

Liquid %

x
I

C
1
30.000 72.017 29.848
C
2
20.000 22.507 19.991
C
5
20.000 4.499 20.056
C
9
30.000 .977 30.105

Property
Total
Mixture
Vapor Liquid
Mole Fraction 1.000 .004 .996
Volume (ft
3
) 2.027 .014 2.013
Volume (ft
3
/lb mol)
Volume% 100.0 .7 99.3
Density (lb/ft
3
) 31.438 5.713 31.622
Z-Factor .4296 .8465 .4281
Viscosity (cP) .0163 .1278
Molecular Weight 63.73 22.82 63.88
Surface Tension
(dyne/cm)
2.667



Observe the differences between gas and liquid properties (compositions, density,
viscosity, molecular weight).

Verify the evaluation of the liquid and gas molar volumes using the following
formula:
P
RT Z
V
v
v

And use a similar equation for the liquid volume.

Second expansion at T = 200.0
o
F, P = 1200.0 psia
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
I

C
1
30.000 70.211 23.663
C
2
20.000 24.399 19.307
C
5
20.000 4.597 22.427
C
9
30.000 .793 34.603



Property
Total
Mixture
Vapor Liquid
Volume (ft
3
) 2.524 .694 1.830
Volume (ft
3
/lbmol)
Volume% 100.0 27.5 72.5
Density (lb/ft
3
) 25.249 4.499 33.118
Z-Factor .4280 .8643 .3592
Surface Tension
(dyne/cm)
4.008

Verify the evaluation of gas and liquid densities and molecular weights using the
following equations:
Nc
i
i i
Mw y vapor Mw
1
) (
v
v
V
v Mw ) (

Similarly for the liquid phase use liquid compositions (x
i
) and liquid volume.



Another expansion - T = 200.0
o
F, P = 800.0 psia
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
I

C
1
30.000 66.387 15.284
C
2
20.000 27.699 16.886
C
5
20.000 5.246 25.967
C
9
30.000 .669 41.863

Property
Total
Mixture
Vapor Liquid
Volume (ft
3
) 3.897 2.276 1.621
Volume (ft
3
/lb mol)
Volume % 100.0 58.4 41.6
Density (lb/ft
3
) 16.352 2.988 35.115
Z-Factor .4405 .8934 .2574
Surface Tension
(dyne/cm)
6.408



Summary Constant Mass Expansion at 200.0
o
F
Pressure
psi
Relative
Volume
V/V
b

Compressibility
(1/psi)
Y-Factor
1800.0 .9824 .517E-04
Pb = 1507.5 1.0000 .589E-04
1500.0 1.0047 1.07
1200.0 1.2509 1.02
800.0 1.9315 .95

Simulated Differential Depletion Test
Lets suppose that as the pressure drops following the same decrements as in the
previous case the gas that is being generated is produced and the liquid remains in
the reservoir.
This test allows the determination of the oil and gas formation volume factors (B
o

& B
g
) and solution gas-oil ratios (R
s
)
Here we assume that ALL the gas generated from a flash expansion is being
produced.



Depletion Stage # 1 - T = 200.0
o
F, P = 1500.0 psia
Properties as this stage are still the same (no production took place yet).
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
I

C
1
30.000 72.017 29.848
C
2
20.000 22.507 19.991
C
5
20.000 4.499 20.056
C
9
30.000 .977 30.105

Property
Total
Mixture
Vapor Liquid
Volume (ft
3
) 2.027 .014 2.013
Volume (ft
3
/lb mol)
Volume% 100.0 .7 99.3
Density (lb/ft
3
) 31.438 5.713 31.622
Z-Factor .4296 .8465 .4281
Surface Tension
(dyne/cm)
2.667

In the next depletion stage note that the composition using for flashing are
identical to the liquid composition from the previous stage (i.e., ALL gas has been
produced).



o
F, P = 1200.0 psia
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
i

C
1
29.848 70.202 23.661
C
2
19.991 24.407 19.314
C
5
20.056 4.597 22.426
C
9
30.105 .794 34.599

Property Total
Mixture
Vapor Liquid
Volume (ft
3
) 2.515 .678 1.837
Volume% 100.0 27.0 73.0
Density (lb/ft
3
) 25.404 4.499 33.117
Z-Factor .4263 .8643 .3592
Surface Tension
(dyne/cm)
4.008



o
F , P = 800.0 psia
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
i

C
1
23.661 65.493 15.112
C
2
19.314 28.574 17.421
C
5
22.426 5.263 25.934
C
9
34.599 .670 41.533

Property Total
Mixture
Vapor Liquid
Volume (ft
3
) 3.225 1.339 1.887
Volume% 100.0 41.5 58.5
Density (lb/ft
3
) 21.752 3.011 35.048
Z-Factor .3646 .8916 .2568
Surface Tension
(dyne/cm)
6.346

In a differential depletion test a last stage is added at standard conditions to
determine the residual oil volume that will be used to determine the oil formation
volume factor.



Last Depletion Stage - T = 60.0 F, P = 14.7 psia
Component
Name
Total
Moles %
z
i

Vapor %
y
i

Liquid %
x
i

C
1
15.112 40.581 .247
C
2
17.421 44.305 1.731
C
5
25.934 14.901 32.373
C
9
41.533 .212 65.649

Property Total
Mixture
Vapor Liquid
Volume (ft
3
) 139.930 138.367 1.564
Volume% 100.0 98.9 1.1
Density (lb/ft
3
) .569 .082 43.661
Z-Factor .3695 .9915 .0065
Surface Tension
(dyne/cm)
21.432



Summary of Results from Differential Depletion at 200.0
o
F
Pressure
(psi)
B
od
(Bbl/STB)
R
sd
(Scf/bbl)
B
g

o
(lb/ft
3
)
Z

g

1800.0 1.767 32.15
Pb = 1507.5 1.799 1030.1 31.58
1500.0 1.795 1023.3 .010595 31.62 .846 .788
1200.0 1.632 773.3 .013524 33.12 .864 .792
800.0 1.453 496.8 .020934 35.05 .892 .820
14.7/60 1.000 43.66

EXERCISE - Verify the calculation of formation volume factors and solution gas-oil
ratios using the formulas derived in class.



Production Mechanism for Gas Condensates/Volatile
Oils: Constant Volume Depletion
To understand condensate production we must explain what kind of physical processes
take place in the reservoir and in the surface.
None of the routine experimental PVT analysis (flash liberation, constant, differential
liberation, or separator separation tests), mimics the depletion behavior of a condensate
reservoir.
A more realistic (and more expensive) PVT analysis for studying the depletion of a gas
condensate is a constant volume depletion (CVD) test. This test provides not only
volumetric information but also compositional measurements on the gas and the liquid
at equilibrium.
During the laboratory CVD studies, only a certain amount of gas phase is removed from
the PVT cell, and it is subsequently flashed to standard conditions. This gas produces
liquid at standard conditions, the gas and the liquid are separated and quantified for
their mass, volumetric ratios, and compositions. The composition of liquid phase in the
cell is usually calculated from mass balance equations. This method of determination of
liquid phase composition is associated with considerable uncertainties on the quantity
and composition of fluid initially in the cell and quantification of the flashed fluid.
We assume the reservoir to be a cell with a constant pore space filled initially with the
reservoir gas condensate. For simplicity we will not consider water in the analysis, but
this could be easily incorporated. As production begins, the reservoir pressure will drop
causing the reservoir gas to expand. Unlike the differential liberation test in which all
produced gas is taken out from the cell, in the reservoir only a portion of the gas is
produced. This amount is determined by keeping the pore volume constant.
The gas produced is the gas contained in this excess volume with respect to the original
pore volume.
We normally assume that the gas is the mobile phase and that the liquid remains in the
reservoir. This is the actual process in the reservoir since the oil saturation rarely
reaches the critical saturation.
For volatile oils, both the liquid and the gas are mobile. Moving according the relative
permeability saturation relationships. But the rest of the process may be considered
identical.



The following figures (Figure 20 and Figure 21) sketch the CVD production mechanism.
After every depletion stage, we must perform an accounting of:
moles and volume of gas to be produced,
moles and volume of liquid and gas left in the reservoir,
composition of the produced (surface) and the remaining phases inside the
reservoir, and
moles and volume of condensate liquid produced at surface from surface gas.



Constant Volume Depletion (CVD)
Pi
= Initial Reservoir Pressure
T
= Reservoir
Temperature
Vi = Reservoir Pore Volume
zi = Initial Reservoir Fluid Composition
(Gas Condensate)
(1)
1. Mass in place (either in moles or pounds)
Given
Pi =3,000
psia
P
1
= 2,800 P
1
= 2,800 P
2
= 2,500
n
p1
n
p2
V
p1
V
p2
( z
i
)
o ( z
i
)
1
( y
i
)
2
( x
i
)
2
( y
i
)
1
( x
i
) 1
Vi V
1
= Vi + V
p1
Vi V
2
= Vi + V p2
V
1
= V
L1
+ V
G1
V
2
= V
L2
+ V
G2
ni = P iVi/zRT

Figure 20 - Sketch of a production mechanism for a gas condensate.



V
( y
i
)
n
( x
i )
n
( z
i
)
n-1
pn
n
pn
Target for gas
cycling
End of Depletion

Constant Volume Depletion of a Condensate Reservoir (cont.)
At any depletion stage need:
Moles and composition of liquid phase (nl , xi's)
Moles of gas phase formed (nv, yi's)
Compressibility factor of the liquid phase, z
l
Compressibility factor of the gas phase, z
v
n z
i
= y
i
n
v
+ x
i
n
l
From flash calculations
V
G
=
n
v
z
v
RT
P
V
L
=
n
l
z
l
RT
P
From EOS

Figure 21 - Sketch of a production mechanism for a gas condensate.



Simulation of a Constant Volume Depletion (CVD) Test
for a Gas Condensate Using an EOS
The following steps illustrate how a CVD test is simulated using an EOS.

System = gas condensate/ ac-ft reservoir bulk volume
Most of the nomenclature used here has been seen previously, however we must use
several subscripts to identify depletion stage, fluid produced or remaining in the
reservoir, and type of fluid (gas or liquid).
The following nomenclature will be used:
t
n = initial # of moles of condensate gas [lb moles/ac-ft]
G = initial gas in place [SCF/ac-ft]
N = initial oil in place [STB/ac-ft]
G
p
= gas produced [SCF/ac-ft]
N
p
= oil produced [STB/ac-ft]

t l v
V V V
~
,
~
,
~
= vapor, liquid, and total mixture molar volumes
[ft
3
/ lb mole]
Subscripts:
i = component number i = 1, 2, 3,Nc
j = depletion stage j = 1, 2, 3, E
d = property at dew point (d)
R = at reservoir pressure and temperature.
SC = at standard conditions
p = produced
r = remaining



v, l, t = vapor (gas), liquid (oil), and total, respectively
2 = two-phase property

Subscripts are used combined as follows,
j l j v j t
n n n
, , ,
, , = total, gas, and liquid (oil) number of moles at
`the end of depletion stage j
j p
G
,
= gas produced in depletion stage j at P
j
.
n
p,j
= moles of gas produced in depletion stage j

The gas volume expressed in SCF is usually taken as:
G = ) (

4 . 379 mole lb n
mole lb
SCF
t
,
_
(98)

Where 379.4 is the volume in cubic feet occupied by 1 lb-mole of ideal gas at standard
conditions T = 60F, P =14.7 psia -
(Use ideal gas law to derive this conversion factor).

Computational Procedure for Depleting a GAS CONDENSATE
reservoir.
Step 1: Determine the size your reservoir from reservoir chararacterization data
(volumetrics). Or express results in terms of the pore space occupied by the
hydrocarbon in cubic feet per acre -foot.
) 1 ( 560 , 43
wi HC
S V
[RCF/ac-ft] (99)
This will remain fixed throughout the process. Upscaling can be easily accomplished.
Recall EOS works with intensive properties!!



Step 2: Given the composition of the reservoir fluid (z
i
's) i = 1, 2, 3 ... Nc (Nc = total
number of components), and the reservoir temperature T
R
. Estimate the upper dew
point using any EOS with a set of mixing rules.
For the dew point pressure the objective is to find P
d
( using the initial fluid composition
z
i
s at T
R
) that satisfies:

1
1
Nc
i i
i
K
z
( )
6
10 1

(100)
with the equilibrium ratios (K
i
) evaluated from any EOS/MCR.
v
i
l
i
i
i
i
x
y
K
(101)
Recall that one can evaluate the derivative within this integral regardless of the number
of moles the system has.

Step 3: Calculate the gas compressibility factor at the dew point (P
d
, T
d
) (reservoir
temperature = T
R
= T
d
) and the number of moles in the reservoir.
Solve the cubic EOS for the gas compressibility factor.
0
2 3
+ + +
d d d
z z z (102)
Where the polynomial coefficients ( , , ) depend upon pressure, temperature, fluid
composition, and the EOS with mixing rules used.
What if the polynomial gives 3 real roots? choose the largest for gas.
Therefore the initial number of moles of gas per acre-foot in the reservoir is,
d d
HC d
t
RT z
V P
n (103)
(T
d
= T
R
)

Step 4: Evaluate the volume that these n
t
moles will occupy when expanded to a
pressure less that P
d
. For example for depletion stage j = 1, we lower the pressure to a
predetermined value, P
1,
and solve the flash equations as outlined in previous lectures.



For simplicity sometimes we may drop the index j with the understanding that
properties are evaluated at each depletion stage.
{P
1
, T
R
, z
i
} => equation for K
i
= > flash equations.
0
) 1 ( 1
) 1 (
1

+
Nc
i i v
i i
K f
K z
(104)
The equilibrium GAS compositions are evaluated as:
) 1 ( 1 +
i v
i i
i
K f
K z
y (105)
and the equilibrium LIQUID (oil) compositions are evaluated as,
i
i
i
K
y
x (106)
The molar volumes for the gas and the liquid (
l v
V V
~
,
~
) had been already evaluated when
solving the flash problem. They both participate in the evaluation of the equilibrium
ratios (K
i
) from the EOS (see previous notes for the final expression of the K
i
values
using the Peng-Robinson EOS).

For the liquid
l
V
~

Real root of the following polynomial or the smallest root if 3 real roots exist.
0 ) ' , , (
~
) ' , , (
~
) ' , , (
~
1 3 1 2
2
1 1
3
+ + + s x T P a V s x T P a V s x T P a V
i R l i R l i R l
(107)

For the gas
v
V
~

Real root of the following polynomial or the largest root if 3 real roots exist.
0 ) ' , , (
~
) ' , , (
~
) ' , , (
~
1 3 1 2
2
1 1
3
+ + + s y T P a V s y T P a V s y T P a V
i R v i R v i R v
(108)

Calculate total molar volume of mixture as
( )
v l l l t
V f V f V
~
1
~ ~
+ (109)



And the total volume at the end of the depletion stage j is obtained by multiplying Eq.
(109) by original number of moles.
( )
v l t l l t t t
V f n V f n V n
~
1
~ ~
+ (110)
v
t
v
t l
t
l
t t t
V
n
n
n V
n
n
n V n
~ ~ ~
+ (111)
v l t
V V V + (112)

The z-factors for the gas and the liquid at any depletion stage are,
d
j v j
j v
RT
V P
z
,
,
~
and
d
j l j
j l
RT
V P
z
,
,
~
(113)

Note that the number of moles at the end of stage j=1 still is the same as initially.
Production has not started yet.

Step 5: Evaluate oil saturation in the reservoir as
100
1 ,
1 ,

HC
l
l
V
V
S (114)
At any stage j
100 100
~
, ,
,

HC
j l
HC
l j l
j l
V
V
V
V n
S (115)
This value indicates the current fraction of the pore space filled with oil (liquid dropout).

Step 6: Determine the amount of gas to be produced in depletion stage j.
Since the total volume will be larger because of pressure reduction we must produce
the excess gas to restore original volume (V
HC
= V
t,0
).
The produced gas volume at stage j is
0 , , , t j t j vp
V V V (116)
Calculate # of moles of gas produced in V
vp,j



R j v
j vp j
j p
RT z
V P
n
,
,
,
(117)

(Note z
v,j
is an intensive property does not depend on amounts)

Step 7: Evaluate cumulative gas produced as a % of the initial gas in place.
100 %
1
,

t
J
j
j p
p
n
n
G (118)
We have used the property of an ideal gas that volume fraction = mole fraction.
Here J = current number of depletion stages (maximum = E).

Step 8: Evaluate the two-phase gas deviation factor. For stage j =1 is,
R p t
HC
RT n n
V P
z
) (
1 ,
1
2
j = 1 (119)
the denominator has (initial # of moles) (number of gas moles produced after 1
st

expansion)

After 2 expansions

R p p t
HC
RT n n n
V P
z
) (
2 , 1 ,
2
2 , 2

(120)
and after the E
th
expansion.
R
E
j
j p t
HC E
E
RT n n
V P
z
,
_
1
,
, 2
(121)

This equation shows that a plot of (P/z) is proportional to the mass, or volume or gas
production. The only difference is that the z-factor to be used is the two-phase z-factor.



This type of plots using production data is the basis of estimating the original gas in
place as seen in a previous chapter.

Step 9: Evaluate the remaining moles of gas after every depletion stage (n
vr
,j
)
from
mole balance.
j p j v j vr
n n n
, , ,
(122)

Step 10: Calculate a NEW # of total moles and new overall composition from the
mole balance.
j l j v j t
n n n
, , ,
+ (123)
and the new overall composition in the reservoir is
j t
j v j i j l j i
j i
n
n y n x
z
,
, , , ,
,
+
(124)

Step 11: The moles of gas produced after each depletion stage are flashed to
standard conditions to determine the amounts of gas and condensate produced at
surface. This step will be seen in greater detail in a subsequent example.

Step 12: Drop the pressure another step and repeat whole procedure outlined in
steps 2-11.
Note that a plot of gas produced versus the ratio of pressure over the two-phase z-factor
gives a straight line and the ultimate production at abandonment pressure.

Numerical Example of a CVD
The steps outlined previously were followed using an EOS with a gas condensate from
the Simpsons Field. Figure 22 shows pressure over three different z-factors obtained
versus the gas produced. Note that the prediction of original gas in place could have
substantial errors if the wrong z-factors are used.
The data required for the EOS for this calculation are,



initial fluid compositions
reservoir temperature
initial pressure and pressure depletion stage

The production data required are
Pressures and Gp.
This gas condensate has a dew point pressure of 4,055 psi at 205
o
F. The plot shows
three different values of P over z versus the gas produced in MSCF.
Shows a flow chart indicating the steps followed in a simulated CVD test.



z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -1.0578e-05 Gp (Correct two-phase z)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
What's the "two-phase" z-factor?
From the EOS (Equation of state ) will have three roots. The largest V
corresponds to the vapor and the smallest to the liquid.
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2
=
n
v
n
z
v
+
n
l
n
z
l
z
2
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
G p
P
/
z
2
#
Gp (z = z vapor)
Estimation of Reserves: Simpson's Condensate Field
z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2
=
n
v
n
z
v
+
n
l
n
z
l
z
2
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2
=
n
v
n
z
v
+
n
l
n
z
l
z
2
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
G p
P
/
z
2
#
Gp (z = z vapor)
Estimation of Reserves: Simpson's Condensate Field

Figure 22 - Differences in the estimation of reserves using three different compressibility
factors.



Given Reservoir Fluid Composition
Temperature, Dew Point Pressure
Control parameters
Determine Moles of
Gas to be produced
Recombine Remaining
Phases
Calculate initial
number of moles
Drop pressure below Pd
Select Hydrocarbon Pore
Volume
Flow Diagram for simulating a CVD
P = P - P
Calculate Total
Volume
Evaluate Flash
Calculate Volume of
Condensate
Calculate Volume of
Gas
Flash to SC

Figure 23 - Flow chart for a simulated CVD test.

Exercise - Simulation of a CVD Using an EOS
This example will calculate the volumetric depletion performance of a retrograde
gas condensate reservoir using the Soave-Redlich-Kwong EOS. Consider 500 psi as
the abandonment pressure. The reservoir temperature is 195
o
F, and the initial
reservoir pressure is equal to the dew-point pressure. The composition of the
reservoir fluid required for the EOS is given in Table 5.



Software packages have a data base built-in with the critical properties, molecular
weights, and acentric factors of all pure substances required for EOS
computations.

Component Mole %
C
1
75.2
C
2
7.7
C
3
4.4
C
4
3.1
C
5
2.2
C
6
2.3
C
7
2.099
C
8
1.235
C
9
0.727
C
10
+
1.039
Table 5 - Initial gas condensate composition Good Money.

Additional information is
= 0.2
S
wi
= 0.25
T
R
= 195
o
F
T
sc
= 60
o
F
P
sc
= 1.7 psi

Solution



Given the reservoir fluid composition and the reservoir temperature we select a
SATURATION POINT calculation and the SRK EOS gives us the following
information.
DEW-POINT pressure at 195
o
F, molar volume at the dew point, and the z-factor.
This pressure is 2,960 psia, and the z-factor is 0.779.
We select a CVD option using any commercial software (PVTSIM from Calsep, PVTi
from Geoquest, DeskTop PVT from Landmark) software selecting 500 psia
decrements.
The following tables present the results from a CVD experiment simulated with
the SRK (Soave-Redlich-Kwong EOS) EOS, as explained previously.

CVD Results Z - Factor Gas Viscosity
P(psi)
100
,
_
d
l
V
V

100
,
_
t
p
n
n

100
,
_
t
p
n
n

z
g

z
2

) (cP
g

2,960 0 0 0 0.779 0.030
2,500 14.02 14.4 14.4 0.799 0.769 0.023
2,000 14.42 16.6 31.0 0.825 0.763 0.019
1,500 12.96 16.7 47.7 0.855 0.755 0.016
1,000 11.09 16.5 64.2 0.891 0.735 0.015
500 8.93 16.0 80.2 0.933 0.665 0.013
Table 6 - Summary results from a CVD study on condensate Good Money at T =
195
o
F.

100
,
_
d
l
V
V
Percent of liquid dropout left in reservoir. Referred to dew-point
volume (V
d
)



100
,
_
t
p
n
n
Percent of moles produced

100
,
_
t
p
n
n
Cumulative mole percent production
For each depletion stage the gas properties are given in Table 7

P (psi) 2,960 2,500 2,000 1,500 1,000 500
Mole % 100 85.197 83.176 82.484 81.745 80.627
~
V
v
(ft/mol)
1.848 2.246 2.897 4.005 6.259 13.103
V
V
v
t
%
100 88.1 88.6 90.5 92.9 95.8
g
(lb/ft) 14.881 10.924 7.949 5.574 3.557 1.783
Z
g
0.7787 0.7994 0.8249 0.8553 0.891 0.9327
g
(cP) 0.0303 0.0226 0.0186 0.0162 0.0146 0.0135
M
wg
27.50 24.54 23.03 22.33 22.26 23.36
Table 7 - Properties of the gas produced at 195
o
F (Condensate Good Money).

The gas composition after each depletion stage is stored to perform the flash
calculations at standard conditions and is given in Table 8



P (psi) 2,960 2,500 2,000 1,500 1,000 500
C
1
75.2 78.84 80.695 81.403 81.021 78.595
C
2
7.7 7.65 7.697 7.834 8.071 8.406
C
3
4.4 4.153 4.062 4.105 4.322 4.857
C
4
3.1 2.743 2.56 2.518 2.664 3.244
C
5
2.2 1.806 1.576 1.471 1.516 1.943
C
6
2.3 1.731 1.386 1.194 1.159 1.485
C
7
2.099 1.45 1.057 0.832 0.745 0.914
C
8
1.235 0.782 0.521 0.376 0.313 0.364
C
9
0.727 0.41 0.242 0.157 0.118 0.126
C
10
+
1.039 0.435 0.203 0.11 0.071 0.067
Mw
C10
+
153.8 147.7 144.7 142.9 141.6 140.7
Table 8 - Composition of produced gas with pressure at 195
o
F (Condensate Good
Money).

From the EOS information we need to calculate the following terms:
Initial Gross Gas in Place (MSCF/ac-ft)
Initial Residue Gas in Place (MSCF/ac-ft)
Initial Oil in Place (STB/ac-ft)
Increments of Gross Gas Production (MSCF/ac-ft)
Cumulative Gross Gas Production (MSCF/ac-ft)
Residue Gas in Each Increment (MSCF/ac-ft)
Cumulative Residue Gas in Each Pressure Stage (MSCF/ac-ft)
Liquid Produced in Each Pressure Stage (STB/ac-ft)
Cumulative Liquid Produced in Each Pressure Stage(STB/ac-ft)



Average Gross Gas-Oil-Ratio in Each Pressure Stage (SCF/bbl)
Average Residue Gas-Oil-Ratio in Pressure Stage(SCF/bbl)
Cumulative Gross Gas Recovery Percentage
Cumulative Residue Gas Recovery Percentage
Cumulative Liquid Recovered Percentage
These terms will be described as we move along.
Quantities will be evaluated per acre foot of net bulk reservoir rock.

The hydrocarbon pore volume per acre foot is

) 1 ( 560 , 43
wi HC
S V (125)

ft ac
ft
V
HC

3
534 , 6 ) 25 . 0 1 ( 2 . 0 560 , 43

Step 1:
Calculate the initial number of moles (n
t
) based upon the hydrocarbon pore space
per acre foot. Then, evaluate the number of moles and cumulative number of moles
produced at each pressure stage.

Using V
HC
as a base volume.

R
R R t
HC
P
RT Z n
V
The number of moles contained in this hydrocarbon pore volume is



R R
R HC
t
RT Z
P V
n

ft ac
mole lb
RT Z
P V
n
R R
R HC
t

5829 . 532 , 3
655 73 . 10 779 . 0
960 , 2 534 , 6

The number of moles produced at P =2,500 psia is
ft ac
mole lb
n f n
t p p

6919 . 508 5829 . 532 , 3 144 . 0

Step 2:
Calculate the Initial Gross Gas in Place per ac-ft, then evaluate the increments of
Gross Gas Production (MSCF/ac-ft) and Cumulative Gross Gas Production
(MSCF/ac-ft) produced after each pressure stage.

The Initial Gross Gas in Place expressed in MMSCF/ac-ft is

7 . 14
520 73 . 10 5829 . 532 , 3

SC
SC t
P
RT n
G

Note that the term

mol lb / SCF .
.
.
P
RT
V
~
SC
SC
sc

5643 379
7 14
520 73 10



is the standard molar volume of an ideal gas. The standard temperature and
pressure have been taken as 520 R (60 F) and 14.7 psia.

ft ac
MSCF
feet ac
SCF
G
341 , 1 843 , 340 , 1

The Gross Gas Production at each pressure stage is evaluated as

G f G
p p

where f
p
is the fraction of moles produced (see Table 6).

At P = 2,500 psia

ft ac
MSCF
G f G
p p
08 . 193 341 , 1 144 . 0

Proceed with all the other pressures and fill the corresponding columns in the
following table:



P(psi)
n
p

n
p

G
p

G
p

G
RP

G
RP

N
p

N
p

GOR
2960 0 0 0
2500 508.69 508.69 193.08 193.08
2000
1500
1000
500
Table 9 - Calculate results from depletion test.

Step 3:
Evaluate the Initial Residue Gas in place (MSCF/ac-ft) and the Initial Oil in Place
(STB/ac-ft).

N G G
R
+

Note that these terms are usually expressed in different units!

To evaluate these quantities we need to flash the initial number of moles with
initial gas composition to standard conditions.



Property Total Vapor Liquid
Mole % 100 94.983 5.017
V
~
(ft/mol)
358.755 377.573 2.503
(lb/ft)
0.077 0.061 43.706
Z 0.9458 0.9954 0.0066
(cP)
0.0103 0.5083
M
w
27.5 23.18 109.4
Table 10 - Flash results of initial composition of gas condensate Good Money to
14.7 psia and 60
o
F.

The compositions of the gas and liquid phases expressed in moles % are given in the
following table.
Component Initial Vapor Liquid
C
1
75.2 79.147 0.47
C
2
7.7 8.09 0.31
C
3
4.4 4.596 0.688
C
4
3.1 3.168 1.812
C
5
2.2 2.081 4.446
C
6
2.3 1.728 13.123
C
7
2.099 0.86 25.56
C
8
1.235 0.258 19.741
C
9
0.727 0.056 13.428
C
10
+
1.039 0.015 20.423
Mw
C10
+
153.8 137.5 154
Table 11 - Compositions of the gas and liquid phases as a result of flashing the
initial mixture to 14.7 psia and 60
o
F.



From Table 10 we can see that about 5% is transformed into liquid thus the Initial
Residue Gas per acre-feet is:

ft ac
MSCF
G f G
v R
72 . 273 , 1 341 , 1 94983 . 0

and the Initial Liquid in Place is

ft ac
SCF
N
V n f N
o t l

6059 . 443
503 . 2 5829 . 532 , 3 05017 . 0
~

In standard barrels

ft ac
STB
N
0178 . 79
614 . 5
6059 . 443

Step 4:
Evaluate the following properties
Residue Gas produced (G
RP
) in each pressure stage (MSCF/ac-ft)
Cumulative Residue Gas in each pressure stage(MSCF/ac-ft)
Liquid produced (N
p
)

in each pressure stage (STB/ac-ft)
Cumulative Liquid Produced in each pressure stage (STB/ac-ft)



This requires flashing the number of moles of gas produced in each depletion stage
to standard conditions. Use compositions from Table 8.

For example at 2,500 psi,

Mole % 100 97.534 2.466
V
~
(ft/mol)
368.436 377.687 2.553
(lb/ft)
0.067 0.059 44.209
Z 0.9714 0.9957 0.0067
(cP)
0.0104 0.5396
M
w
24.68 22.45 112.88
Table 12 - Flash results to 14.7 psia and 60
o
F from the gas produced at P = 2,500
psia (Condensate Good Money).

The compositions of the gas and the liquid obtained are given in Table 13



Component Total Vapor Liquid
C
1
78.84 80.821 0.477
C
2
7.65 7.836 0.3
C
3
4.153 4.242 0.634
C
4
2.743 2.772 1.584
C
5
1.806 1.757 3.753
C
6
1.731 1.489 11.306
C
7
1.266 0.741 22.039
C
8
0.745 0.26 19.936
C
9
0.439 0.064 15.27
C
10
+
0.627 0.018 24.701
Mw
C10
+
153.8 137.5 154.3
Table 13 - Compositions of the gas and the liquid obtained from flashing the gas
produced at 2,500 psia (Condensate Good Money).

The residue gas and the liquid produced are evaluated as

p v RP
G f G
o p l p
V n f N
~

at P = 2,500 psia is

ft ac
MSCF
G
RP
3196 . 188 081 . 193 97534 . 0

and
ft ac
SCF
N
p
0256 . 32 553 . 2 69 . 508 02466 . 0



in barrels

ft ac
STB
N
p
7046 . 5
614 . 5
0256 . 32

Cumulative values are obtained just by adding the results obtained from each stage
(left as an exercise).

Step 5:
Evaluate the following
Average Gross Gas-Oil-Ratio in Each Pressure Stage (SCF/STB)
Average Residue Gas-Oil-Ratio in Pressure Stage(SCF/STB)
Gross Gas and Cumulative Gross Gas Recovery Percentage
Residue Gas and Cumulative Residue Gas Recovery Percentage
Liquid Recovery and Cumulative Liquid Recovery Percentage

The Average Gross Gas-Oil-Ratio, and the Average Residue Gas-Oil-Ratio in Each
Pressure Stage (SCF/STB) are evaluated as

p
p
N
G
GOR
p
RP
R
N
G
GOR

The Gross Gas and Residue Gas Recovery Percentages are



100
G
Gp
Gross 100
R
RP
G
G
Gresid

The liquid recovery in each stage is

100
N
N
Nrec
p

for example at P = 2,500 psia

STB
SCF
GOR 55 . 846 , 33
7046 . 5
0 . 081 , 193

STB
SCF
GOR
R
9 . 011 , 33
7046 . 5
6 . 319 , 188

4 . 14 100
341 , 1
081 . 193
Gross

78 . 14 100
72 . 273 , 1
3196 . 188
Gresid

22 . 7 100
0178 . 79
7046 . 5
Nrec

Steps 1 to 5 are repeated for all the depletion pressures, and the cumulative
values are calculated. This will be left as an exercise.



From a CVD simulated test properties of the liquid remaining in the reservoir are
also reported. These can be used for gas cycling projects.
These properties are in the following tables.

P (psi) 2,960 2,500 2,000 1,500 1,000 500
Mole % 100 14.803 16.824 17.516 18.255 19.373
~
V
o
(ft/mol)
1.848 1.75 1.852 1.982 2.149 2.381
V
V
l
t
%
100 11.9 11.4 9.5 7.1 4.2
o
(lb/ft) 14.881 25.476 28.402 31.069 33.657 36.364
Z
o
0.7787 0.6229 0.5273 0.4232 0.3059 0.1695
o
(cP) 0.0303 0.0718 0.092 0.1158 0.1462 0.1891
M
wo
27.50 44.59 52.6 61.57 72.32 86.57
Table 14 - Properties of the liquid (oil) remaining in the reservoir at 195
o
F after
every depletion stage (Condensate Good Money).

Table 15 contains the overall composition of the fluid remaining in the reservoir
after every depletion stage. This composition is obtained by recombination of the
liquid and gas remaining in the reservoir after every depletion stage from Equation
(124).



P (psi) 2,960 2,500 2,000 1,500 1,000 500
C
1
75.2 75.2 74.586 73.118 70.465 65.611
C
2
7.7 7.7 7.709 7.711 7.672 7.488
C
3
4.4 4.4 4.442 4.533 4.67 4.83
C
4
3.1 3.1 3.16 3.304 3.556 3.967
C
5
2.2 2.2 2.267 2.432 2.74 3.303
C
6
2.3 2.3 2.396 2.639 3.101 3.994
C
7
2.099 2.099 2.208 2.485 3.014 4.058
C
8
1.235 1.235 1.312 1.501 1.862 2.574
C
9
0.727 0.727 0.78 0.909 1.151 1.625
C
10
+
1.039 1.039 1.141 1.366 1.769 2.55
Mw
C10
+
153.8 153.8 154.2 154.5 154.7 154.9
Table 15 - Overall Composition changes with pressure at 195
o
F.



P (psi) 2,960 2,500 2,000 1,500 1,000 500
C
1
75.2 54.252 44.382 34.107 23.195 11.576
C
2
7.7 7.99 7.766 7.133 5.883 3.671
C
3
4.4 5.823 6.322 6.547 6.228 4.717
C
4
3.1 5.153 6.128 7.007 7.553 6.973
C
5
2.2 4.47 5.679 6.961 8.222 8.963
C
6
2.3 5.573 7.389 9.439 11.798 14.435
C
7
2.099 5.836 7.899 10.268 13.175 17.143
C
8
1.235 3.842 5.22 6.799 8.797 11.772
C
9
0.727 2.548 3.44 4.454 5.775 7.865
C
10
+
1.039 4.515 5.777 7.285 9.374 12.885
Mw
C10
+
153.8 157.2 155.8 155.3 155.2 155.2
Table 16 - Reservoir liquid composition changes with pressure at 195
o
F.

Suggested Exercises - The following exercises may be assigned in
the exam or in a homework.

Suggested Exercise 1.
Complete Table 9 from this example using the information from the example plus
the following EOS results from flashing the produced gas at the different
depletion stages to standard conditions.

Plot N
p
and GOR versus pressure.



Mole % 100 98.705 1.295
V
~
(ft/mol)
372.906 377.763 2.608
(lb/ft)
0.062 0.058 44.788
Z 0.9831 0.9959 0.0069
(cP)
0.0104 0.5763
M
w
23.18 21.95 116.83
Table 17 Flash Results from gas produced at P =2,000 psi to 15 psia and 60
o
F

C
1
80.695 81.747 0.479
C
2
7.697 7.794 0.297
C
3
4.062 4.107 0.612
C
4
2.56 2.574 1.47
C
5
1.576 1.553 3.317
C
6
1.386 1.277 9.693
C
7
0.833 0.607 18.048
C
8
0.49 0.248 18.988
C
9
0.288 0.07 16.917
C
10
+
0.412 0.022 30.179
Mw
C10
+
153.8 137.6 154.7
Table 18 Gas and liquid compositions from gas produced at P =2,000 psi and
flashed to 15 psia and 60
o
F



Mole % 100 99.228 0.772
V
~
(ft/mol)
374.903 377.801 2.657
(lb/ft)
0.06 0.057 45.318
Z 0.9884 0.996 0.007
(cP)
0.0104 0.6125
M
w
22.46 21.7 120.42
Table 19 -Flash Results from Gas Produced at P =1,500 psia to 15 psia and 60
o
F

C
1
81.403 82.033 0.478
C
2
7.834 7.893 0.3
C
3
4.105 4.132 0.615
C
4
2.518 2.526 1.441
C
5
1.471 1.458 3.113
C
6
1.194 1.136 8.618
C
7
0.607 0.497 14.757
C
8
0.357 0.225 17.287
C
9
0.21 0.074 17.74
C
10
+
0.301 0.025 35.654
Mw
C10
+
153.8 137.7 155.2
Table 20 - Gas and liquid compositions from gas produced at P =1,500 psi and
flashed to 15 psia and 60
o
F



Mole % 100 99.411 0.589
V
~
(ft/mol)
375.577 377.785 2.679
(lb/ft)
0.06 0.058 45.589
Z 0.9902 0.996 0.0071
(cP)
0.0104 0.6313
M
w
22.39 21.8 122.14
Table 21 Flash Results from Gas Produced at P =1,000 psia to 15 psia and 60
o
F

C
1
81.021 81.498 0.473
C
2
8.071 8.117 0.308
C
3
4.322 4.344 0.645
C
4
2.664 2.671 1.522
C
5
1.516 1.506 3.213
C
6
1.159 1.116 8.457
C
7
0.513 0.439 13.029
C
8
0.302 0.209 16.014
C
9
0.178 0.074 17.733
C
10
+
0.254 0.027 38.607
Mw
C10
+
153.8 137.8 155.7
Table 22 Gas and liquid compositions from gas produced at P =1,000 psi and flashed
to 15 psia and 60
o
F.



Mole % 100 99.587 0.413
V
~
(ft/mol)
376.045 377.594 2.317
(lb/ft)
0.062 0.061 43.372
Z 0.9914 0.9955 0.0061
(cP)
0.0103 0.4492
M
w
23.39 23.07 100.48
Table 23 Flash Results from Gas Produced at P = 500 psia to 15 psia and 60
o
F

C
1
78.595 78.919 0.45
C
2
8.406 8.44 0.317
C
3
4.857 4.874 0.719
C
4
3.244 3.25 1.844
C
5
1.943 1.934 4.112
C
6
1.485 1.446 10.906
C
7
0.267 0.238 7.339
C
8
1.2 0.9 74.3
C
9
1.2 0.9 74.3
C
10
+
1.2 0.9 74.3
Mw
C10
+
1.2 0.9 74.3
Table 24 Gas and liquid compositions from gas produced at P = 500 psi and flashed
to 15 psia and 60
o
F



Prove that the following expression is equivalent to Equation (121).
( )
E l v v v E
z f z f z ) 1 (
, 2
+

The identity is valid for any depletion stage.

The following information has been obtained from a simulated CVD test on Jeffs
gas condensate reservoir. The average reservoir temperature is 240
o
F. From
geological data the estimated hydrocarbon pore volume is:

RB V
HC
7
10 1
The standard molar volume in Jeffs state is

mole lb
SCF
V
g
00 . 375
~

Properties at Jeffs Condensate at the Dew Point:
2,714 psia and 240.0
o
F

Molar Volume 2.073 ft/lb-mol
Density 15.859 lb/ft
Z-Factor 0.7495



Component Pressure z
i
% y
i
% x
i
%
C
1
75.000 80.090 66.562
C
5
15.000 12.551 19.060
C
7+

2,600
10.0 7.4 14.4
C
1
74.790 84.634 54.792
C
5
15.101 10.378 24.696
C
7+

2,200
10.1 5.0 20.5
C
1
73.191 86.467 44.952
C
5
15.868 9.559 29.288
C
7+

1,800
10.9 4.0 25.8
C
1
70.640 87.109 35.295
C
5
17.080 9.415 33.533
C
7+

1,400
12.3 3.5 31.2
C
1
66.749 86.523 25.379
C
5
18.892 10.073 37.342
C
7+

1,000
14.4 3.4 37.3
C
1
60.642 83.427 14.992
C
5
21.615 12.478 39.923
C
7+

600
17.7 4.1 45.1
Table 25 Constant Volume Depletion at 240.0
o
F

Determine:
The number of moles and SCF of gas produced at each pressure stage.
The cumulative number of moles and SCF produced at each pressure stage.
The number of moles of liquid remaining in the reservoir at each pressure stage.
The fractional gas recovery at each pressure depletion stage.



The following information has been obtained from a simulated CVD test on Jeffs
gas condensate reservoir. The average reservoir temperature is 240
o
F and the
initial number of gas moles in this reservoir is,

9
10 1
t
n lb moles

Assuming that production starts at the Dew-Point pressure and that the
abandonment pressure is 400 psia.

Determine: the fraction of moles recovered at that pressure.

Pressure
(psi)
z-factor
z-factor
(2phase)
3,000 0.777
2,800 0.757
2,714 0.750 0.750
2,600 0.789 0.748
2,200 0.831 0.735
1,800 0.856 0.717
1,400 0.878 0.690
1,000 0.899 0.645
Table 26 - Z-factor of the Jeffs gas condensate.



The conventional material balance equation works well for dry gas and black oil.
However, if the reservoir fluid is a volatile oil or a gas condensate, a substantial error
may occur due to neglecting compositional effects.

Gas Condensates and Volatile Oils
Gas Condensate/Volatile Oil - Production Facts
As pressure declines below the dew point gas condensate reservoirs release liquid
within the reservoir pore space (liquid dropout can be as high as 30 - 35% of the pore
volume).
Dry gas viscosity correlations cannot reproduce the viscosity variation of gas
condensates due to compositional effects.
Condensate and volatile reservoirs produce distillate oil from the vapor phase produced.
As the hydrocarbon composition becomes richer in intermediate components (C
4
- C
8
),
R
s
, B
g
, and B
o
become more and more dependent upon the composition in addition to
pressure and temperature.
These facts indicate that surface oil is also dissolved in the gas phase. One of the
approaches to deal with these types of reservoir fluids will take into account the so
called volatilized oil i.e. oil dissolved in the gas. Still this approach is simplistic and it
can be considered as an improved black oil formulation.
Equations of State (EOS) can handle this problem provided that the initial reservoir fluid
is known.
We will define a new PVT property that takes into account the volume of surface
volatilized oil dissolved per unit volume of surface gas. This property is called R
v
.
The R
v
of a reservoir gas at P
1
,T
1
(reservoir pressure and temperature) is obtained by
expanding a fixed volume of this gas from to P
SC
, T
SC
. The volumes of surface gas and
stock tank oil obtained are measured. And R
v
is calculated as the number of STB of
surface oil obtained per cubic feet of surface gas at standard conditions. This oil that
appeared at surface was volatilized at reservoir conditions. For pressures above the
saturation pressure R
v
is just the inverse of R
s
. But at pressures P < P
saturation
it is not the
same because we are considering the oil in the gas phase.



MMSCF
STB
R
v

conditions standard at gas surface of feet cubic of million
conditions standard at oil of barrels
(126)

Reservoir Fluid R
v
(STB / MMSCF)
Heavy and Black Oils 0 10
Volatile Oils 10 200
Near Critical Oils 150 400
Gas Condensates 50 250
Wet Gases 20 100
Dry Gases 0 2
Table 27 - Typical values of R
v
.

Gas Condensate Description
Gas condensates are complex mixtures of hydrocarbons which behave more like a
vapor phase at the conditions of high pressure and temperature found in petroleum
reservoirs. When such gas condensate reservoirs are brought on production, the
reservoir pressure falls and the hydrocarbon phase behavior changes continuously. The
successful exploitation of gas condensate reservoirs depends on knowledge of the
vapor-liquid equilibrium composition of the phases and their volumetric behavior.
The phase envelope of these fluids shows that the reservoir temperature is located
between the critical temperature and the cricondentherm temperature.
The producing gas oil ratios of gas condensates range from 4,000 to 150,000 SCF/STB.
A sharp increase in GORs during production indicates that the reservoir pressure fell
below the dew-point pressure and liquid is accumulating in the reservoir. Recycling of
gases into gas condensate reservoirs at the beginning of production or after the
pressure depletion is a potential method of enhanced condensate recovery.
Heavy hydrocarbon components with carbon numbers higher than C
7
have a large
influence on the phase behavior of the hydrocarbon mixtures. The magnitude of liquid
dropout and the dew point pressure in gas condensates are both increased by the



amount of heavy hydrocarbons. Typically these fluids have a mole percentage of C
7
+
<
12.4%. (For more rules of thumb identification procedures see McCain, 1990).
The way gas condensate fields are depleted gives rise to significantly different recovery
factors. Simple blowdown, full or partial pressure maintenance strategies are used
depending on the nature of the fluid, the reservoir temperature and initial pressure and
the reservoir geology. Efficient and economic production of gas condensates is of great
importance and must be considered before deciding the production method in the
development of new fields.
Condensate banking (or buildup) near the wellbore acts as a mobile skin. It lowers the
gas relative permeability thereby the gas flow rates.
Gas condensate fields are a significant portfolio of most major oil producing companies.
However, the planning of the development of such needs reliable predictions of the
physical processes of the multiphase flow of the fluids in the porous medium. The
prediction of flow profiles and the development of expressions in terms of relative
permeability and phase saturation are needed for reservoir simulation.
The relative permeability of condensate fluids is a function of many parameters
including viscosity ratio, wettability and most importantly interfacial tension. In general
the effect of low interfacial tension is to increase flow rates and lower the residual
saturations, creating conditions for improved hydrocarbon recovery.

Volatile Oils Description
Volatile oils are complex mixtures of hydrocarbons which behave more like a liquid
phase at the conditions of high pressure and temperature found in petroleum reservoirs.
Using density, or typical compositions as dividing lines between gas condensate and
volatile oils is very subtle. The phase envelope of volatile oils shows that the critical
temperature is located to the right of the reservoir temperature. When volatile oils are
brought on production and the reservoir pressure falls below the bubble point, the gas
phase may become mobile.
The producing gas oil ratios of volatile oils range from 2,000 to 4,000 SCF/STB. A sharp
increase in producing GORs (Rs) indicates that the reservoir pressure falls below the
bubble-point pressure.
Volatile oils are also called high-shrinkage oils (B
o
s can be > 4) and should be
produced through three or more separator stages to minimize this shrinkage.



Field data indicates that solution GORs (R
s
s) generally increase with depth, therefore
the probability of a hydrocarbon accumulation to contain gas condensates or volatile oils
usually increases with depth.
Typically volatile oils have a mole percentage of C
7
+
between 12 to 30%. (For more
rules of thumb identification procedures see McCain, 1990).
PVT data is essential for gas condensate and volatile oil field evaluation and
development. PVT data consists of volumetric measurements and compositional
information on gas and liquid at equilibrium. Routine PVT analysis normally consists of
constant mass and differential liberation studies. A more realistic (and more expensive)
PVT analysis for studying the depletion of a gas condensate (or a volatile oil) is a
constant volume depletion (CVD) which will be discussed later.
The following table illustrates some typical compositions of the 5 different types of
reservoir fluids.

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
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
Greeni
sh
Black
Medium
Orange
Light
Straw
Water
White
-
Table 28 Typical compositions of single-phase reservoir fluids (undersaturated).



The following graphs show property changes that take place in a condensate reservoir
(Simpons Field) as production takes place. The data have been simulated with an EOS.
The reservoir temperature is 190
o
F.
The condensate field SIMPSON is at 190
o
F and exhibits the phase behavior illustrated
in the following pages.

0
1000
2000
3000
4000
P
r
e
s
s
u
r
e

(
p
s
i
)
0 100 200 300 400
Temperature (F)
Critical Point
Tc = 103.7 F
Pc=2952.5 psi
Retrograde Condensate - CVD Depletion
EOS-Simulation

Figure 24 Initial phase envelope for Gas Condensate Simpson.



0
10
20
30
40
50
60
70
M
o
l
e

%
0
10
20
30
40
50
M
o
l
e

%
0 1000 2000 3000 4000
Pressure (psi)
C7+
C6
C1
Compositional Variation of The Liquid Phase
PETE 420 Condensate Simpson's Field at 190 F

Figure 25 Changes taking place in the liquid remaining in the reservoir during
production by depletion.



62
64
66
68
70
72
M
o
l
e

%
0
1
2
3
4
5
6
7
M
o
l
e

%
0 1000 2000 3000 4000
Pressure (psi)
C6
C7+
C1
Compositional Variation of The Gas Phase

Figure 26 Changes taking place in gas produced as pressure declines below the dew-
point pressure for a gas condensate reservoir.

Gas condensates and volatile oils show a greater change in composition and behavior
during the production when compared with black oil and dry gas.
The following plot shows the liquid dropped out in the reservoir as a function of
pressure. This liquid is expressed as a percent of the volume occupied at the dew-point
(V
d
).



0
10
20
30
40
L
i
q
u
i
d

D
r
o
p
o
u
t

(
%
)

V
d
0 1000 2000 3000 4000 5000
Pressure
Liquid Dropout for
Dew Point Pressure

Figure 27 Liquid dropout for Simpson gas condensate.

A problem associated with gas condensates is the formation of retrograde condensation
when production is by pressure depletion. Therefore, it is extremely important to
understand the compositional variation and phase behavior of gas condensate at wide
range of temperature and pressure.
Pressure/ Z vs Moles of Gas Produced. The more common plot of P vs SCF of gas
produced is obtained by converting moles to SCF, using the ideal gas law and the
standard conditions applied for the state (TX, CO, LA, etc.).



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

/

Z
0 10 20 30 40 50 60 70 80 90 100
Percent Production (Moles)
P/Z (2 phases)
P/Z (L))
P/Z (2 phases)
P/Z (V))
Pressure / Z vs Production

Figure 28 - P/Z plots for condensate Simpson.

0.0
0.2
0.4
0.6
0.8
1.0
Z

f
a
c
t
o
r
0 1000 2000 3000 4000 5000
Pressure (psi)
Z (liquid)
Z (vapor)
Z (total)
Dew Point Pressure
Z Factors vs Pressure

Figure 29 - Different z-factors in condensate Simpson.



0
10
20
30
40
50
D
e
n
s
i
t
y

(
l
b
m

/

f
t
3
)
0 1000 2000 3000 4000 5000
Pressure (psi)
Gas Density
Liquid Density
Liquid and Gas Densities for
PETE 420 Condensate - Simpson's Field at 190 F

Figure 30 -Liquid and gas densities for condensate Simpson.

10
-2.0
10
-1.0
10
0.0
V
i
s
c
o
s
i
t
y

(
c
p
)
0 1000 2000 3000 4000 5000
Pressure (psi)
Liquid Viscosity
Two Phase Viscosity
Gas Viscosity
Viscosities for

Figure 31 - Liquid and gas viscosities for condensate Simpson.



Note the peculiar shape of gas viscosity versus pressure. This is entirely due to
compositional effects. Dry gas viscosity correlations can not reproduce this behavior.

0.01
0.02
0.03
0.04
0.05
0.06
0.07
V
i
s
c
o
s
i
t
y

(
c
p
)
0 1000 2000 3000 4000 5000
Pressure (psi)
Viscosity vs Pressure

Figure 32 - Gas Viscosity for condensate Simpson.



0
1
2
3
4
5
6
7
8
9
R
e
l
a
t
i
v
e

V
o
l
u
m
e
0 1000 2000 3000 4000 5000
Pressure (psi)
Relative Volume for
Dew Point Pressure

Figure 33 - Relative volume for condensate Simpson.
0
1000
2000
3000
4000
P
r
e
s
s
u
r
e

(
p
s
i
)
-100 0 100 200 300 400 500 600
Temperature (F)
Critical Point (initial)
Critical Point (when Pr = 1500 psi)
Compositional Changes due to Production
Initial Reservoir Pressure = 5000 psi
Actual Reservoir Pressure = 1500 psi

Figure 34 Initial phase envelope and phase envelope when the average reservoir
pressure dropped to 1500 psia for condensate Simpson.



The phase envelopes indicated in Figure 34 correspond to the fluid remaining in the
reservoir.

Conceptual questions
All the questions refer to Figure 24 through Figure 34.

Conceptual Question 1. Based upon the phase envelope indicated in Figure 24.
Indicate which condensate fluid would give drop more liquid in the reservoir
during production up to P = 1000 psia and why. The reservoir temperatures are,
T
R
= 150 F
T
R
= 200 F
T
R
= 300 F
Conceptual Question 2. What causes the compositional variation of gas and liquid
phases during production.
Conceptual Question 3. What type of error would you have in the predicted
performance of your reservoir if you use either the gas or the liquid z-factor?
Conceptual Question 4. What causes the changes in gas and liquid viscosity during
pressure depletion?
Conceptual Question 5. Explain what happened in Figure 34.
Conceptual Question 6. What is the major difference between a volatile oil and a
condensate gas?

Suggested Exercise - Simulated CVD Test
The following output corresponds to a simulated CVD test for Lees condensate
reservoir.



Z -Factor
P
(psia)
Liquid
Dropout
% V
d

Moles % of
Gas
Produced
z-gas z-two-phase
Viscosity
(cp)
4,000 0.886 0.044
3,500 0.829 0.040
3,000 0.777 0.036
2,714 0.750 0.750 0.033
2,500 34.46 7.3 0.804 0.745 0.024
2,000 28.25 24.0 0.844 0.727 0.019
1,500 23.64 40.6 0.873 0.697 0.017
1,000 19.64 57.1 0.899 0.644 0.015
500 15.10 74.2 0.925 0.536 0.014
V
d
= volume at the dew point in ft
3
.
Table 29 - Constant Volume Depletion at 240.0
o
F of Lee's condensate reservoir.

R = 10.73 psia ft
3
/
o
R lb-mole
T
sc
= 60
o
F
1 barrel = 5.614 ft
3
P
sc
= 14.7 psia

Based upon the given information.
Plot Pressure vs. the gas z-factor, and the two-phase z-factor.
Determine the molar volume for this condensate at the dew point (in ft
3
/
lb-mole).
If Lees reservoir hydrocarbon pore volume is estimated to be V
HC
= 1x10
7

RB. How many moles of gas condensate fit into this volume?



Determine the total volume of liquid dropout in the reservoir at 2,500 psi.
How many standard cubic feet of gas would be produced at 1,750 psi?



Evaluation of Gas and Oil in Place Using Surface
Separation Data and EOS.
The estimates of oil and gas in place from gas condensate fields using surface
separation data and an EOS requires a series of accounting steps consisting of:
1. Flash calculations using different fluid compositions
2. Recombination of produced gas and liquid to determine the initial oil composition
3. Determination of fluid (gas and liquid) properties at standard, reservoir, and
separator conditions.
This will be best presented through an example.

Example
Evaluate Oil and Gas in place using the following separator, production, and
reservoir data.

Given:
P
R
= 4,000 psi
T
R
= 195
o
F
= 0.2
S
wc
= 0.3
T
sc
= 60
o
F
P
sc
= 15.025 psia
Stock Tank Production (STB)
2
= 30 STB/day
Separator Gas Production (SCF)
1
= 179,030 SCF/day



Separator 1
y
i1
(STB)
2
Well Head
Reservoir
x
i1
x
i2
y
i2
?
?
(SCF)
1
(SCF)
2
?
Separator 2

Figure 35 - Sketch illustration two separator stages.

Additional information provided is the composition of the produced gas (from the
separator) and the composition of the oil from the separator.



Component y
i1
x
i1

N
2
0.160 -
CO
2
0.220 -
C
1
75.310 7.780
C
2
15.080 10.020
C
3
6.680 15.080
i-C
4
0.520 2.770
C
4
1.440 11.390
i-C
5
0.180 3.520
C
5
0.240 6.500
C
6
0.110 8.610
C
7
+
0.060 34.330
mole lb lb
mole lb lb Mw
C
C
/ 70 . 0 and
/ 103
7
7

+
+

mole lb lb
mole lb lb Mw
C
C
/ 79 . 0 and
/ 143
7
7

+
+

Table 30 - Gas and oil compositions from Separator 1.

Note that N
2
and CO
2
are not part of the liquid stream.

Step 1:
Determine the number of moles of gas and oil produced in the stock tank
(separator 2).
We use an EOS and flash the liquid composition from separator 1 to T
SC
and P
SC
.



Mole % 100.000 42.446 57.554
V
~
(ft/mol)
160.564 374.993 2.427
V % 100.0 99.1 0.9
(lb/ft) 0.516 0.111 46.659
z-Factor 0.4217 0.9849 0.0064
(cP) 0.00 0.0086 0.6044
Table 31 - Flash results of liquid from separator 1 at T=60
o
F and P = 14.7 psia.

Component
Total
Mole (%)
Vapor
Mole (%)
Liquid
Mole (%)
C
1
7.78 8.196 0.098
C
2
10.02 22.514 0.806
C
3
15.08 29.866 4.176
i-C
4
2.77 4.398 1.569
C
4
11.39 15.56 8.315
i-C
5
3.52 2.8 4.051
C
5
6.5 4.151 8.232
C
6
8.61 1.953 13.52
C
7
+
4.33 0.562 59.234
Table 32 - Liquid and gas compositions from flashed Separator 1 liquid at T=60
o
F
and P = 14.7 psia.

The daily number of moles of gas (n
v2
) and liquid (n
o2
) produced in the stock tank is,



2 2 2 2 1 o i v i i
f x f y z +

day
mole lb
n
STB
SCF
day
STB
SCF
mole lb
V
V
n
o
o
STO
o

3943 . 69
614 . 5 30
427 . 2
1
~
2
2
2
,
_

Since
2 2
2
2
v o
o
o
n n
n
f
+

Then

,
_

2
2
2 2
1
o
o
o v
f
f
n n

day
mole lb
n
v

1782 . 51
57554 . 0
57554 . 0 1
3943 . 69
2

,
_

Step 2:
Using the ideal gas law convert the daily number of moles of gas produced in the
stock tank (n
v2
) to SCF.
Convert the (SCF)
1
obtained in separator 1 to moles (n
v1
)

The molar volume of the gas produced at the specified standard conditions is:



lb mole
SCF
psia
R
R lb mole
SCF psia
P
RT
V
o
o
sc
sc
g
35 . 371
025 . 15
520
73 . 10
~

lb mole
SCF
V
g
35 . 371
~

Alternatively, we can use the volume at these standard conditions but evaluated
from the EOS. Note that these are pretty close (374.994 SCF/lb mole).

And the SCF produced are

mole lb
SCF
day
mole lb
V n
day
SCF
g v

35 . 371 1782 . 51
~ ) (
2
2

day
SCF
day
SCF
25 . 005 , 19
) (
2

( )
day
mole lb
SCF
mole lb
day
SCF
V
SCF
n
g
v

11 . 482
35 . 371
030 , 179
~
1
1

,
_

Step 3:
Determine the recombination ratio from moles of oil and gas produced and using
this determine the initial gas composition (z
i
).

1 1
1
v o
v
v
n n
n
f
+
but
2 2 1 o v o
n n n +



8 . 0
1782 . 51 11 . 482 3943 . 69
11 . 482
2 1 2
1
+ +
+ +
v v o
v
v
n n n
n
f

Thus the initial gas (z
i
) compositions are

o i v i i
f x f y z
1 1
+ i= 1, 2, Nc

Example for methane

61804 . 0 0778 . 0 2 . 0 75310 . 0 8 . 0
1
+ z

Component z
i
(%)
N
2
0.128
CO
2
0.176
C
1
61.804
C
2
14.068
C
3
8.36
i-C
4
0.97
C
4
3.43
i-C
5
0.848
C
5
1.492
C
6
1.81
C
7
+
6.915
Table 33 - Overall overhead compositions.



Some round off error is inevitable therefore you will have to normalize all z
i
s to
make sure that their sum is equal to 1.

Note:
Many commercial software codes do this step for you given that you provide
(a) the recombination ratio expressed as number of moles the gas per number of
moles of liquid.
4
1782 . 51 3943 . 69
10 . 482
1
1
+

o
v
n
n
ratio

or

(b) The producing gas oil ratio expressed as SCF/STB

Step 4:
Using the initial gas composition obtained from Step 3 use the EOS to determine
the z-factor at the reservoir P
R
and T
R
. You can also verify, by calculating the
phase envelope, that the initial fluid is a condensate gas.

The calculated fluid properties at P
R
= 4,000 psia and T
R
= 195
o
F are



V
~
(ft/lb- mole)
1.487
(lb/ft) 22.605
z-Factor 0.8468
Viscosity (cP ) 0.0531
Mw (lb / lb mole) 33.62

Step 5:
Evaluate the total number of moles per ac-ft (1 ac-ft = 43,560 ft
3
)
) 1 ( 560 , 43
wi HC
S V
ft ac
mole lb
n
zRT
S P
zRT
V P
n
t
R
wi R
R
HC R
t

77 . 099 , 4
) 460 195 ( 73 . 10 8468 . 0
) 3 . 0 . 1 ( 2 . 0 560 , 43 000 , 4
) 1 ( 560 , 43

Step 6:
Flash these initial number of moles with the initial composition obtained in Step 3
to standard conditions, and determine the number of moles and (MSCF) and (STB)
of gas and oil in place per acre-foot.
The total number of moles is:

o g t
n n n +



Mole % 100.000 92.327 7.673
V
~
(ft/mol)
348.497 377.231 2.739
V % 100.0 99.9 0.1
(lb/ft) 0.096 0.067 48.788
z-Factor 0.9188 0.9945 0.0072
(cP) 0.0101 0.8583
Table 34 - Flash results at T= 60
o
F and P=15.025 psia.

Therefore
ft ac
mole lb
n f n
t v g

27 . 784 , 3 77 . 4099 92327 . 0
and
ft ac
mole lb
n n n
g t o

49 . 315 27 . 784 , 3 77 . 099 , 4

Step 7:
Translate the number of moles of gas to SCF and the number of moles of liquid to
STB.
ft ac
MSCF
mole lb
SCF
ft ac
mole lb
V n G
g g
,
_

,
_
76 . 404 , 1

21 . 371 27 . 784 , 3
~

The initial oil in place in standard stock tank barrels is evaluated using the molar
volume obtained in step 6
ft ac
STB
N
ft
STB
mole lb
SCF
ft ac
mole lb V n
N
o o
,
_
,
_
92 . 153
614 . 5
739 . 2 49 . 315
614 . 5
~
3



Step 8:
Evaluate the daily reservoir voidage and the daily condensate production.
The daily reservoir voidage is
( )
day
SCF
V
P
RT z
n n n
P
RT z n
V
R
R R
o v v
R
R R p
97 . 896
000 , 4
655 73 . 10 8468 . 0
) 1782 . 51 3923 . 69 29 . 482 (
2 2 1

+ +
+ +

day
STB
V 77 . 159
614 . 5
97 . 896

And the daily condensate production is
p p p
N G G +
( )
day
SCF
z T P
P T V
G
R R sc
R sc
p
874 , 223
8468 . 0 655 025 . 15
000 , 4 520 97 . 896

Suggested Exercise
Determine the initial composition of a condensate reservoir that is producing
40 STB/day with a separator daily gas production of 200,000 SCF day. The gas
and oil compositions for the separator are the same as those used in this Example.



The Effect of Gravity and Porous Media on the
Phase Equilibria of Hydrocarbon Reservoirs
Generally, when calculating phase equilibria of reservoir fluid systems, the effects of a
gravitational field and the curvature of the phase interface are neglected. Under certain
conditions, compositional variation due to gravitational field, and the effect of capillarity
on phase behavior may become important. In this chapter, the criteria of phase
equilibrium both in a gravitational field, and for curved surfaces, will be derived. In the
first part, the theory of phase equilibria of flat surfaces in the absence of the gravity field
will be reviewed.

Equilibrium Conditions Under the Influence of Gravity
Closed System
The work term in the first law of thermodynamics included only the compression
expansion (PdV ) contribution. Now consider a mass m (either single or
multicomponent) undergoing both expansion (or compression) and a change in position
(Figure 36). To raise m to some height h, a certain amount of work must be done.
Therefore, the expression for dW should include both expansion/compression and
gravity contributions.

( )dh mg PdV dW
t

(127)



dQ
dW
dW
dQ
(mg)dh positive
upwards
2
1
m
m
dQ
dW
dW
dQ
(mg)dh positive
upwards
2
1
dQ
dW
dW
dQ
(mg)dh positive
upwards
2
1
m
m

Figure 36 - Work to lift mass from position 1 to 2 including gravitational effects.

Substituting Eq. (127) into the first law equation provides.

( )dh mg PdV TdS dU
t t t
+ (128)

( )
,
_
c
t
N
i
i i
t
V S
t
g Mw n mg
h
U
1 ,
(129)

Equation (128) indicates that the internal energy is a function of the independent
variables S
t
, V
t
, and h.

( ) h V S U U
t t t t
, ,
(130)

Similar expressions can be found for the other state properties.



Let's examine the criterion of equilibrium for a single or multi-component closed system
in a gravitational field. The Gibbs free energy should be a minimum, therefore, dG
t
should vanish subject to the constraint of constant temperature.

( ) 0 + dh mg dP V dG
t t

(131)

gdh dP (132)

This is the equation for a hydrostatic head. Note that in a gravitational field

t t
TdS dH (133)

Open System
Recall that the system can exchange matter and energy with surroundings. For an open
system in the normal gravity field,

( ) h n n n V S U U
c
N t t t t
, ..., , , ,
2 1
(134)

The differential form of Eq. (134) can be written as:

dh
h
U
dn
n
U
PdV TdS dU
t t j
j t t
c
V S n
t
i
i n h V S
N
i i
t
t t t
, ,
, , ,
1

,
_
,
_

(135)

But,

T
S
U
h n nV
t
t
,
_
, ,
(136)



and

P
V
U
h n nS
t
t

,
_
, ,
(137)
( )
,
_
c
N
i
i i
h nV nS
t
g Mw n mg
h
U
1 , ,

(138)
gh Mw
n
U
i i
i n h V S
N
i i
t
j t t
c
+
,
_
, , ,
1
(139)

Combining Eqs. (135) through (139)

( ) mgdh dn gh Mw PdV TdS dU
i
N
i
i i t t t
c
+ + +

1
(140)

Similar expressions for dH
t
, dG
t
, and dF
t
can be derived.

The expression for dG
t
is:
( ) mgdh dn gh Mw dP V dT S dG
i
N
i
i i t t t
c
+ + + +

1

(141)

We have already seen that in a normal gravity field the hydrostatic head for a single
component single-phase fluid could be derived from the criteria of equilibrium. Now we
would like to derive equilibrium criteria for a multicomponent single phase (i.e., dn
i
= 0, i
= 1, . . . n
c
). Let's apply the criteria of equilibrium to Eq. (140); dG
t
should vanish at
equilibrium. Therefore following the same arguments as before, for arbitrary dn
i
.

0 + gh Mw
i i
(142)
and



0 + mgdh dP V
t
(143)

and the process should be isothermal. We can write Eq. (142) in a differential form and
noting that the process is isothermal,

( ) 0 +
T i i
gdh Mw d (144)

Both Eqs. (142) and (144) indicate that in a gravitational field the chemical potential in
the same phase is not constant but varies with depth. Eq. (143) represents the
hydrostatic head.

Conditions for Pronounced Compositional Variation in Hydrocarbon
Reservoirs
At constant temperature,
( )
Nc i i
n n n P ,..., , ,
2 1
(145)
k
h V S n
Nc
k k
i i
i
dn
n
dP
P
d
t t j
, , ,
1

,
_
,
_

(146)

i
T n
i
V
P

,
_
(147)

k
h V S n
Nc
k k
i
i i
dn
n
dP V d
t t j
, , ,
1
,
_

+ (148)

Combining Eqs.(144) and (148) and rearranging,

( )g Mw V
dh
dn
n
i i
k
h V S n
Nc
k k
i
t t j

,
_
,
_
, , ,
1
(149)



The above equation shows that compositional variation in a hydrocarbon reservoir could
be expected when the term

( )g Mw V
i i
(150)
is large and when the following term becomes singular

P T n
k
i
j
n
, ,
,
_

(151)

Equation (150) for a component of a reservoir fluid system can be large if the molecular
weight of one of the components is much larger than the average molecular weight of
the reservoir fluid. This could be the case if asphalt materials with a molecular weight of
500 to 5000 are present in the crude residue.
The term in Eq. (151) become singular around the critical point. Therefore, we expect
compositional grading and bubblepoint variation in an oil column when asphalt materials
are present in the oil. Compositional variation in a gas column is enhanced when a gas
condensate fluid is in the vicinity of the critical point.

Figure 37 shows schematically the variation of saturation pressure with depth in both
the oil leg and the gas cap. Saturation pressure variation of Figure 37 are due to
compositional grading. Kingston and Niko report considerable bubblepoint pressure
variation for the Brent and Statfjord reservoirs of the North Sea.

The bubblepoint pressure gradient in the oil zone is reported to be 3.6 and 4.0 psi/ft for
the Brent and Statfjord reservoirs, respectively.



D
e
p
t
h
GOC
Pressure
WOC
Dew Point
Bubble Point
Reservoir Pressure
Saturation Pressure

Figure 37 - Variation of saturation and reservoir pressure due to compositional
gradients.

Next we will present some figures indicating the evaluated gravitational gradients effects
on a Volatile Oil (Cuisiana Oil). Compositions of the C
7
+
and C
1
show the most
pronounced differences.



0
10
20
30
40
50
60
70
80
C
o
m
p
o
s
i
t
i
o
n
s

(
%
)
12000. 12500. 13000. 13500.
Depth (feet)
C1
C2-C6
C7+
Compositional Gradient for Volatile Oil MAB1
at T = 256 F

Figure 38 - Compositional gradient for Volatile Oil MAB1.

12000
12200
12400
12600
12800
13000
13200
13400
13600
D
e
p
t
h

(
f
e
e
t
)
5000. 5500. 6000.
Pressure (psia)
Reservoir Pressure
Saturation Pressure
Reservoir Pressure and Saturation Pressure
Gradient for Volatile Oil MAB1 at T = 256
o
F
Oil
Gas

Figure 39 - Reservoir pressure and saturation pressure gradient for Volatile Oil MAB1.



Figure 38 shows the variation of the C
1
, C
2
-C
6
, and C
7
+

content as a function of depth
for a Cuisiana Reservoir Fluid (Colombia). Figure 39 shows the variation of the
saturation pressure (Dew or Bubble point) as a function of depth.
We will know describe a procedure to calculate compositional grading in hydrocarbon
reservoirs.

Procedure for the Calculation of Compositional Grading
Eq. (144) gives the condition of equilibrium under the influence of gravity in terms of
chemical potential. It is more convenient to express the condition of equilibrium in terms
of fugacity. The fugacity of a component " i" in a mixture is defined by,
( )
T i i
dP V f RTd
ln
i=1,2, .Nc
(152)
1 lim
lim
0

,
_
P y
f
f
i
i
i
P
(153)
( )
T i i
dP V d (154)

Combining Eqs.(144), (152), and (154)
( )
T i i
gdh Mw f RTd
ln

(155)

Integrating Eq. (155) from a reference depth of zero to h
,
_
gh
RT
Mw
f f
i o
i i
exp

i=1, 2,.., N
c
(156)

This equation states that the fugacity of component "i" in a given phase is a function of
position. In other words, given composition and pressure at the reference point, one
should be able to calculate both the composition and pressure at any point. Variation of
pressure with depth is automatically accounted for by Eq (155) Note that the phase rule
in the presence of a gravity field is given by

3 +
p c
N N F (157)



Given the composition and pressure at a reference point, the following equations are
used to calculate pressure and composition at a desired depth.

( )
c
i o
i Nc i i
,...N , i gh
RT
Mw
f y y y P T f F 2 1 0 exp
,..., , , ,
2 1

,
_
(158)

Subject to the constraint equation
Nc
i
i
y
1
1 (159)

The unknowns are pressure and composition at the desired depth. The elements of the
Jacobian matrix in terms of composition need special care to be evaluated. As an
example,

, , j y P T
j
i
k
y
F
,
_
(160)

may have no physical meaning if all mole fractions with the exception of y
j
are held
constant. One way to resolve this problem is to express mole fractions in terms of moles
in the equation for fugacity Then,

( )
c
i o
i Nc i i
,...N , i gh
RT
Mw
f n n n P T f F 2 1 0 exp
,..., , , ,
2 1

,
_

(161)

In the calculation of Jacobians

n n
Nc
i
i

1
(162)



1
,
_
i n
l
l
l
j
i
n
n
, 1
,
_
i n
v
v
v
j
i
n
n
(163)
0
,
_
i n
l
l
j
v
j
i
n
n
, 0
,
_
i n
v
v
j
v
j
i
n
n
(164)

will be needed.
Further details will be discussed in the example problem.

Suggested Exercise Evaluation of a Gravitational Gradient
Consider a mixture of methane (C
1
) and normal butane. (n-C
4
) in a gravitational
field. Use the PR-EOS to compute the composition of C
1
and n-C
4
system at
intervals of 1000, 2000, 3000, 4000, 5000, and 7000 ft. below the reference
depth for the following cases:
a. At the reference depth, C
1
and n-C
4
compositions are 27.27 and 72.73 mole
percent, respectively. Pressure at the reference depth is 1300 psi. Temperature
throughout the liquid column is assumed to be 220 F.
b. At a given reference depth, C
1
and n-C
4
compositions are 88.88 and 11.12
percent, respectively. Pressure at the reference depth is 514 psi. Temperature
throughout the gas column is assumed to be 160 F.



Equilibrium Conditions for Curved Surfaces
The interface between phases (say, gas and oil) in a porous media is not flat. Therefore,
in the derivation of equilibrium conditions the influence of interface curvature should be
taken into account. Our approach to account for the effect of interface curvature would
be to modify the expression for the work term in Eq. (128) Consider a bubble of vapor in
Figure 40 In the course of expansion process d expression for the bubble would be,

dA PdV dW
t
(165)

1 2 1 2

Figure 40 - Two stages of a growing bubble.

In the above equation, PdV is the contribution from expansion (or compression), and
dA is the work required to increase the surface area by dA.
Substituting Eq. (165) into Eq. (128) the expression for dU
t
for a curved interface is
obtained.



dA PdV TdS dU
t t t
+

(166)

Therefore,
( )
c
N t t t t
n n n V S U U ..., , , ,
2 1
(167)
( ) A V S U U
t t t t
, , (168)

Similar expressions for the enthalpy, Helmholtz, and Gibbs's energy and are provided
below;
dA dP V TdS dH
t t t
+ + (169)
dA PdV dT S dF
t t t
+ (170)
dA dP V dT S dG
t t t
+ + (171)

Surface Effects on Phase Equilibria
In this section, the criteria of equilibrium for a multicomponent two-phase system with a
curved interface will be derived. The case of a single-component two-phase system is a
special case.
Consider a gas bubble surrounded by a liquid phase in a constant volume, closed
system of constant temperature. In each phase n
c
components will be present. The
pressure inside the bubble is P' and the liquid phase pressure is P" (as indicated in
Figure 41). The volume of the gas bubble and liquid phase are V' and V", respectively.
For the multicomponent system, the expression for the differential of total internal
energy is,



P'
P
P
P'
P
P

Figure 41 - A bubble with pressure P surrounded by a liquid at P.

" '
t t
dU dU dUt + (172)

dA dn dV P TdS dn dV P TdS dU i
N
i
i t t i
N
i
i t t
t
c c
+ + + +

' '
1
' ' ' ' ' ' ' ' '
1
' ' ' '
(173)

and the expression for the total Helmholtz free energy is,

( ) dA dn dn dV P dV P dT S S dF i
N
i
i i
N
i
i t t t t
t
c c
+ + + +

' '
1
' ' '
1
' ' ' ' ' ' ' ' ' '
(174)

The necessary condition for the system to be in equilibrium is that dF
t
should vanish
subject to the constraints of constant temperature and,

constant
constant
" '
" '
+
+
i i
t t
n n
V V
(175)

Therefore,



( ) ( ) ( ) 0
'
1
' ' ' ' ' ' ' ' ' '
+ + +

dA dn dV P P dT S S dF i
N
i
i i t t t
t
c
(176)

Previously we found that at equilibrium the chemical potentials must be the same, then:

( )
t dV
dA
P P
'
" '
(177)

If we assume the gas bubble has a spherical shape, then,

2
4 r A and rdr dA 8 (178)
3
3
4
r Vt and dr r dVt
2
4 (179)

Combining Eqs. (177), (178) and (179),
( )
r
P P

2
" '
(180)

In the case of a curved interface, in addition to equality of chemical potentials, phase
pressures are related by Eq. (180). The chemical potential should be evaluated at the
corresponding phase pressures. Eq. (180) is the famous equation for capillary pressure
(Young-Laplace).
In the following, we will discuss reservoir fluids phase equilibrium in porous media. A flat
interface has an infinite radius of curvature, therefore the capillary pressure is zero.



Effect of Porous Media on Phase Behavior
Several authors have studied the effect of porous media on the phase behavior of
reservoir fluid systems. Russian authors Trebin and Zadora reported a strong influence
of the porous media on the Dewpoint pressure and VLE of gas condensate systems.
The porous media used by these authors was a silica sand mixture (0.300 to 0.215 mm
diameter) grinned by a special cutter-pulverizer. Three different packings with
permeabilities of 5.6, 0.612, and 0.111 darcy and porosities of 34, 31.4, and 29.8
percent were used. The calculated surface areas for these packings were 563, 1,307,
and 3,415 cm
2
/cm
3
, respectively. Fig. 10 shows the effect of the type of porous media
on the liquid content of the produced fluids. This figure shows that as the surface area
of the porous media increases, the Dewpoint pressure increases. Tribune and Zadora
state a 10 to 15 percent increase in the Dewpoint pressure in the porous media of the
type that was used in their work. When these authors increased the temperature, the
effect of porous media on VLE was decreased.
Tint and Raynal

measured the bubble-point pressure of two reservoir crudes in both an
open space (PVT cell) and a porous media with grain sizes in the range of 16-200
microns. The bubblepoint pressure of these two crudes were higher in porous media
than in a PVT cell by 7 and 4 kg-cm. As an example, the bubblepoint pressure of one of
the two crudes measured at 80C in a PVT cell was 121 kg/cm
2
and the bubblepoint
pressure at the same temperature in a porous media of 160-200 microns was 128
kg/cm
2
.
On the other hand, when these authors used a mixture of methane and n-
heptane they observed no differences in the saturation pressure. Sigmund and co-
authors have also investigated the effect of porous media on phase behavior of model
fluids. Their measurements on dewpoint and bubblepoint pressures showed no effect of
porous media. The fluid systems used by these authors were C1

/n-C
4
, and C
1
/n-C
5
.
The smallest bead size used was 3-40 US mesh.
Since these results seem quite controversial. In the example problem to be presented
next, the effect of surface curvature on dewpoint pressure and equilibrium phase
composition will be discussed.

Example Effect of Curvature Radius on Saturation Properties
Consider a binary system of C1/n-C
10
with the following composition at 100F.



x
1
= 99.894%
x
10
= 0.106%
a. Compute the dewpoint pressure of the above system in a PVT cell (measured Pd
# 1450 psi)
b. What would be the dewpoint pressure of the above fluid system for a mean
radius of curvature of 10,1, 0.1, and 0.01 microns?
c. What are the equilibrium liquid phase composition of the above cases?

Data
(
C1/n-C10
) at 100F & 1500 psi = 9.76 dynes/cm.

In conclusion, we would like to state that the effect of porous media on phase
behavior should be attributed to:
1) interface curvature (i.e., capillarity), and
2) adsorption on the solid surface.

The effect of surface curvature has been taken into account in the derivation of Eqs.
(176) through (179). The effect of adsorption is difficult to quantify and we may not be
able to separate adsorption phenomena and capillarity. If only interface curvature is
taken into account, one may expect that VLE will not be affected by the presence of
porous media unless the radius of curvature becomes of the order of 0.1 microns and
less (which is equivalent to permeabilities less than 1 darcy)

The following figures show the computed results for this exercise using PR EOS.



Figure 42 - Dewpoint pressure as a function of interface curvature for C1/nC10 system.

Figure 43 - Liquid phase composition at the dewpoint as a function of interface
curvature.



Note that both: bubble point & dew point will change with curvature.



Nomenclature
A = surface area
F
t
= Helmholtz free energy
G
t
= Gibbs free energy
i
f
= fugacity of component "i"

g = acceleration of gravity
H
t
= enthalpy
m = mass of the system
M
wi
= molecular weight component "i"
n = moles - with subscript is for component; without is total,
n
t
= number of components
P = pressure
Q = heat
R = universal gas constant
r = radius of a gas bubble
S
t
= entropy
T = temperature
U
t
= internal energy
i
V = partial molar volume component "i"
V = volume
W = work
h = elevation
x
i
,y
i
= mole fraction
= surface tension
= mass density



= number of phases

Subscripts
i,j,k = component index
Superscripts
', '' = phase index
,,..= phase index



References
McCain, W. D. Jr. The Properties of Petroleum Fluids, 2
nd
Edition Penn Well Books
(1990).
McCain, W. D. Jr. Calculation of Fluid Properties from Black Oil PVT Reports
Revisited SPE 36017 (1996).
Barrufet, M.A., Habiballah, W. A., Liu K., and Startzman, R., A Warning on the Use
of Composition Independent K-Value Correlations to Solve Reservoir Engineering
Problems. J. of Petroleum Science and Engineering 14, (1995), pp. 25-34.
Kartoadmodjo, T. and Schmidt, Z., Large Data Bank Improves Crude Physical
Property Correlations, Oil and Gas Journal (July 1994), 51-55.
Walsh P. M., New Improved Equation Solves for Volatile, Condensate Reserves.
Oil and Gas Journal, Aug. 22, 1994, pp. 72-76.
Walsh P. M., New Improved Equation Solves for Volatile, Condensate Reserves. Oil
and Gas journal, Aug. 22, 1994, pp. 72-76
Havlena, D., and Odeh A. S., The Material Balance as an Equation for a Straight
Line, JPT, August 1963, pp. 896-900.
Spivak, A., and Dixon, T. N. Simulation of Gas Condensate Reservoirs, SPE 4271,
1973, SPE Symposium of Reservoir Simulation, Houston, Jan. 10-12, 1973.
McCain W. D., The Properties of Petroleum Fluids. PennWell Books. (1990).
Thermodynamics of Hydrocarbon Reservoirs Abbas Firoozabadi. McGraw Hill 1.
(1999).
"The Collected Works of J. Willard Gibbs," Vol. I- Thermodynamics, Yale University
Press, New Haven, 1957.
Kingston, P.E., and Niko, H.: "Development Planning of the Brent Field," JPT (Oct.
1975) 1190-98.
Creek, J.L., and Schrader, M.L.: "East Painter Reservoir: An Example of a
Compositional Gradient from a Gravitational Field," SPE 14411, paper presented at
the 60e Annual Technical Conference and Exhibition of the Society of Petroleum
Engineers, Las Vegas, Nevada, Sept. 22-25, 1985.



Tribune, F.A., and Zadora, G.I.: "Experimental Study of the Effect of a Porous Media
on Phase Changes in Gas Condensate Systems," Neft'i Gaz (1968) Vol. 81, No.
8,37-41.
Tint, R., and Raynal, M.: "Are Test-Cell Saturation Pressures Accurate Enough?"
The Oil and Gas Journal (Dec. 1966) 128-139.
Sigmund, P.M., e a.: "Retrograde Condensation in Porous Media," SPEJ (April
1973) 93-104.
Stegemeier, G.L., e a.," Interfacial Tension of the Methane-Normal Decane System,"
SPEJ (Sept. 1962) 257-260.

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Petroleum Engineering Applications of Phase Equilibria , Colombia, Summer 2000-

Author: Dr. Maria Barrufet - Summer, 2000 Page 1/163

. The relationship between fugacity and fugacity

Re-evaluate for (i =1,Nc)

341 , 1 843 , 340 , 1

08 . 193 341 , 1 144 . 0

72 . 273 , 1 341 , 1 94983 . 0

3196 . 188 081 . 193 97534 . 0

0256 . 32 553 . 2 69 . 508 02466 . 0

= fugacity of component "i"

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