L9-High Pressure VLE - EOS

4/4/2014 1
Termodinamica de
Hydrocarburos
High Pressure Phase Equilibria
EOS
4/4/2014 2
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.
4/4/2014 3
Petroleum Engineering Applications of
Phase Equilibria
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.
Additional Reading: Selected SPE papers

4/4/2014 4
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.

4/4/2014 5
Instructional Objectives (cont.)
Understand the production mechanism for
a gas condensate or a volatile oil
(Constant Volume Depletion, CVD).
Determine oil and gas in place and
recoveries using CVD compositional data.
Determine oil and gas in place from
recombination.

4/4/2014 6
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.

4/4/2014 7
If the component exhibits phase
equilibrium an additional constraining
equation is placed and only one
variable, either P or T are needed to
specify the STATE of the system.
(Recall phase rule)

4/4/2014 8
For VLE, the constraining equation is
the equality of the Gibbs energy of the
GAS and LIQUID phases.
A CUBIC EOS is one of the many
different models available to evaluate
this ENERGY

4/4/2014 9
The ideal gas EOS was the first mathematical
expression used to describe the PVT behavior
of gases
Its use is limited to low pressures (near
atmospheric)
Since only provides a single volume for a
given pressure and temperature, it cannot
describe phase transitions
4/4/2014 10
Multicomponent Systems
For multicomponent mixtures in addition to
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.
4/4/2014 11
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),
4/4/2014 12
Some of the EOS uses include:
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.
4/4/2014 13
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.

4/4/2014 14
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 + =
4/4/2014 15
The Father of Cubic
Equations of State
4/4/2014 16
One of the most used EOS in
petroleum engineering is the Peng-
Robinson EOS (1975), which is a
three-parameter corresponding
states model.

) ( ) ( b V b b V V
a
b V
RT
P
+ +
o
=
4/4/2014 17
The critical point conditions are used
to determine the EOS parameters

0
0
2
2
=
|
|
.
|
\
|
c
c
=
|
.
|
\
|
c
c
c
c
T
T
V
P
V
P
4/4/2014 18
Solving these two equations
simultaneously for the Peng-
Robinson EOS provides
c
c
a
P
T R
a
2 2
O =
c
c
b
P
RT
b O =
and
4/4/2014 19
Where

07780 . 0
45724 . 0
= O
= O
b
a
( ) ( )
2
1 1
r
T m + = o
2
2699 . 0 54226 . 1 37464 . 0 e e + = m
and

with
4/4/2014 20
PR equation can be expressed as a
cubic polynomial in (V) or (Z).
( )
RT
bP
B
RT
P a
A
=
o
=
2
3 2
2
2 3
( 1)
( 3 2 )
( ) 0
Z B Z
A B B Z
AB B B
+ +

=
with
4/4/2014 21
Cubic EOSs are the simplest
polynomials that can provide an
adequate description of both: liquid
and gas properties
EOSs can describe the state of pure
fluids and mixtures (single or
multiphase) and their properties.
4/4/2014 22
When working with mixtures the
same expressions apply except that
(ao) 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
Linear MR for b
4/4/2014 23
Quadratic MR for a
( )
( ) ( )
0.5
1 1
1
Nc Nc
i j i j i j i
j
m
i j
a x x a a k o oo
= =
=
4/4/2014 24
Linear MR for b

where the kijs are called interaction
parameters and by definition

1
Nc
m i i
i
b x b
=
=
0
ij ji
ii
k k
k
=
=
4/4/2014 25
Example
For a three-component mixture (Nc =
3) the attraction (a) and the repulsion
constant (b) are given by
( ) ( ) ( )
( ) ( ) ( )
( )
1
0.5 0.5
1 2 1 2 1 2 12 2 3 2 3 2 3 23
0.5
2 2
1 3 1 3 1 3 13 1 1 2 2 2
2
3 3 3
2 (1 ) 2 (1 )
2 (1 )

m
a x x a a k x x a a k
x x a a k x a x a
x a
o oo o o
oo o o
o
= +
+ + +
+
1 1 2 2 3 3

m
b x b x b x b = + +
4/4/2014 26
A system may not exist as a SINGLE
PHASE at the specified P, T, and overall
composition zi. 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
).
4/4/2014 27
The overall mixture composition will be
used to evaluate a unique set of liquid
and gas compositions such that
material balance is satisfied.
4/4/2014 28

The overall composition zi 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, 2Nc) which will normally
be evaluated from a flash computation.
4/4/2014 29
Therefore the constants a and b can
be evaluated using

Overall compositions z
i
with i = 1, 2Nc
Liquid compositions x
i
with i = 1, 2Nc
Vapor compositions y
i
with i = 1, 2Nc

4/4/2014 30
The cubic expression for a mixture is then
evaluated using

( )
( )
2

m m
m m
a P
b P
A B
RT
RT
o
= =
4/4/2014 31
Analytical Solution of Cubic
Equations
The cubic EOS can be arranged into
a polynomial and be solved
analytically as follows.
3 2
2
2 3
( 1)
( 3 2 )
( ) 0
Z B Z
A B B Z
AB B B
+ +

=
4/4/2014 32
Equations
Lets write the polynomial in the
following way
3 2 3
1 2
0 x a x a x a + + + =
Note: x could be either the molar
volume, or the density, or the z-factor
4/4/2014 33
Equations
When the equation is expressed in
terms of the z factor, the coefficients
a
1
to a
3
are:

1
2
2
2 3
3
( 1)
( 3 2 )
( )
a B
a A B B
a AB B B
=
=
=
4/4/2014 34
Procedure to Evaluate the Roots
of a Cubic Equation Analytically
2
2 1
3
1 2 3 1
3 2
3
3 2
3
3
9
9 27 2
54
a a
Q
a a a a
R
S R Q R
T R Q R
=

=
= + +
= +
Let
4/4/2014 35
( ) ( )
( ) ( )
1 1
2 1
3 1
1
3
1 1 1
3
2 3 2
1 1 1
3
2 3 2
x S T a
x S T a i S T
x S T a i S T
= +
= + +
= +
The solutions are,
4/4/2014 36
If a
1
, a
2
and a
3
are real and if D = Q
3
+
R
2
is the discriminant, then
One root is real and two complex
conjugate if D > 0;
All roots are real and at least two are
equal if D = 0;
All roots are real and unequal if D < 0.
4/4/2014 37

where
1 1
2 1
3 1
1 1
2 cos
3 3
1 1
If 0 2 cos 120
3 3
1 1
2 cos 240
3 3
x Q a
D x Q a
x Q a
u
u
u
| |
=
|
\ .
| |
< = +
|
\ .
| |
= +
|
\ .
3
cos
R
Q
u =
4/4/2014 38

where x
1
, x
2
and x
3
are the three roots.
1 2 3 1
1 2 2 3 3 1 2
1 2 3 3
x x x a
x x x x x x a
x x x a
+ + =
+ + =
=
4/4/2014 39
The range of solutions that are used
for the engineer are those for
positive volumes and pressures, we
are not concerned about imaginary
numbers.

4/4/2014 40
Solutions of a Cubic Polynomial
Basically, from the
general shape of
the polynomial we
are interested in the
first quadrant.
4/4/2014 41
Solutions of a Cubic Polynomial

http://www.uni-koeln.de/math-nat-
fak/phchem/deiters/quartic/quartic.ht
ml contains Fortran codes to solve
the roots of polynomials up to fifth
degree.

4/4/2014 42
Web site to download Fortran source codes
to solve polynomials up to fifth degree
4/4/2014 43
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.
4/4/2014 44
van der Waals loops showing the
Maxwell Equal Area rule (A
1
= A
2
).
-
1 0
0
0
1 0
0
2 0
0
3 0
0
4 0
0
5 0
0
6 0
0
7 0
0
2 4 6 8 1
0
1
2
1
4
A 1
A 2
P
r
e
s

s
u
r

e

Mo la r V o lu m e
T
c
T
2
T
1
P
1
v
L
2 - P has es
CP
V
L
V
1
2
3
4
7
6
5
0 > |
.
|

\
|
c
c
T
V
~
P
-
1 0
0
0
1 0
0
2 0
0
3 0
0
4 0
0
5 0
0
6 0
0
7 0
0
2 4 6 8 1
0
1
2
1
4
A 1
A 2
P
r
e
s

s
u
r

e

-
1 0
0
0
1 0
0
2 0
0
3 0
0
4 0
0
5 0
0
6 0
0
7 0
0
2 4 6 8 1
0
1
2
1
4
A 1
A 2
P
r
e
s

s
u
r

e

Mo la r V o lu m e
T
c
T
2
T
1
P
1
v
L
2 - P has es
CP
V
L
V
1
2
3
4
7
6
5
0 > |
.
|

\
|
c
c
T
V
~
P
4/4/2014 45
Although the EOS does not provide
viscosities (a transport property), it
gives phase compositions that are
used in the evaluation of viscosities.
4/4/2014 46
Along the production path we will
need to evaluate:
Bubble point pressure (P
b
) at given
reservoir T and overall z
i
.
Properties of gas & liquid, below (P
b
),
through equilibrium computations in
the two-phase region (flash
computations).
4/4/2014 47
For a retrograde fluid, along the
production path we will need to
evaluate:
Dew point pressure (P
d
) at given
reservoir T and overall z
i
.
Properties of gas & liquid, below (P
d
),
through equilibrium computations in
the two-phase region (flash
computations).
4/4/2014 48
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).
4/4/2014 49
Two-phase VLE
For two-phase vapor-liquid-
equilibrium VLE these equations are
expressed as the equal fugacity
constraints

(i = 1, 2, 3, Nc)

v l
i i
f f =
4/4/2014 50
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.
4/4/2014 51
Two-phase VLE
When an EOS is used to evaluate the
fugacities an alternative expression
is using the fugacity coefficients .
( )

,
v l
i i
| |

l l
i i i
v l
i i i i
f x P
y x
|
| |
=
=
where
4/4/2014 52
Dependent and independent variables used
in typical phase equilibrium problems
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
4/4/2014 53
Two-phase VLE
We will present the algorithms for
the: DEW BUBBLE & FLASH
equilibrium calculations which are
general regardless of the EOS and
mixing rule used.
OUR GOAL: Solve phase equilibrium for
binary mixtures and compare our
results from those evaluated with a
commercial package.
4/4/2014 54
Two-phase VLE
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:
l
i i
i
v
i
i
y
K
x
|
|
= =
4/4/2014 55
Dew Point Calculations
Equilibrium is always stated as:

l v
i i i i
x P y P | | =
1 1 1
1, 1, 1
Nc Nc Nc
i i i
i i i
x y z
= = =
= = =

(i = 1, 2, 3 ,Nc)

with the following material balance
constrains
4/4/2014 56
At the dew-point z
i
= y
i
. Therefore
making use of the K-value definition:

l v
i i i i
i i i
x z
x K z
| | =
=
(i = 1, 2, 3 ,Nc)
4/4/2014 57
For a Dew-Point equilibrium
calculation the objective is to find a
unique set of K-values that satisfies,
1
1 0
Nc
i
i
i
z
K
=
=
4/4/2014 58
Bubble Point Equilibrium
Calculations
For a Bubble-point equilibrium
calculation, the objective function is
derived following the same
reasoning as:
1
1 0
Nc
i i
i
z K
=
=
4/4/2014 59
Flash Equilibrium Calculations
The objective is to find the f
v
in a VL
mixture at a specified T and P such
that
1
( 1)
0
1 ( 1)
c
N
i i
i
v i
z K
f K
=
=
+
4/4/2014 60
Flash Equilibrium Calculations
This is also known as the Rachford-
Rice function and it is derived from:
1 1
0
Nc Nc
i i
i i
y x
= =
=

4/4/2014 61
Numerical Behavior of Flash Functions
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
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.
4/4/2014 62
Two-phase VLE
The two-phase equilibria criteria is
that both functions (dew and bubble)
must be greater than one.
1 1
1, 1
Nc Nc
i
i i
i i
i
z
z K
K
= =
> >

4/4/2014 63
Two-phase VLE
The equilibrium GAS compositions
are evaluated as:
1 ( 1)
i i
i
v i
z K
y
f K
=
+
i
i
i
y
x
K
=
with the liquid compositions evaluated
as,
4/4/2014 64
Two-phase VLE - Example
z
i
may indicate the composition of the
reservoir oil fluid above the Bubble-
Point.
Later in production, the pressure in
the reservoir drops and this initial
single-phase fluid separates into two
phases.

4/4/2014 65
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

4/4/2014 66
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
TX diagram for the
behavior of the Dew
Point function at the
boundaries and in
the 2-phase region
4/4/2014 67
Two-phase VLE - Dew Point T
When the objective is to find the DEW
POINT temperature at a fixed pressure
(P
a
) and overall composition:
1
1
Nc
i
i
i
z
K
=
<
1
1
Nc
i
i
i
z
K
=
>
Superheated fluid lower T

Subcooled fluid increase T

If
If
4/4/2014 68
One way of updating the temperature is
1
1
Nc
k k
i
i
i
z
T T
K
+
=
=
1
1
Nc
i
i
i
z
K
=
=
At the dew point

4/4/2014 69
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.
4/4/2014 70
Behavior of the Dew point
function in a PX diagram
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
4/4/2014 71
Two-phase VLE - Dew Point P

Under pressurized fluid
increase P

1
1
Nc
i
i
i
z
K
=
<
1
1
Nc
i
i
i
z
K
=
>
When the objective is to find the DEW POINT

PRESSURE at a fixed temperature (T
a
) and
overall composition,

Over pressurized fluid
lower P

If

If

4/4/2014 72
Two-phase VLE - Dew Point P
One way of updating the pressure is
1
1
Nc
k k
i
i
i
z
P P
K
+
=
=
1
1
Nc
i
i
i
z
K
=
=
At the dew point

4/4/2014 73
Two-phase VLE - Dew Point
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.
4/4/2014 74
Two-phase VLE - Bubble Point P
When the objective is to find the BUBBLE
POINT PRESSURE at a fixed temperature (Ta)
and overall composition, then

1
1
Nc
i i
i
z K
=
<
1
1
Nc
i i
i
z K
=
>
Over pressurized fluid

lower P

Under pressurized fluid
increase P
If

If

4/4/2014 75
Two-phase VLE - Bubble Point P
One way of updating the pressure is
1
1
k
Nc
k
i i
i
P P z K
+
=
=
1
1
Nc
i i
i
z K
=
=
At the bubble point

4/4/2014 76
Two-phase VLE
To ensure the existence of two-
phases both functions (DEW &
BUBBLE) must be:
1 1
1, 1
Nc Nc
i
i i
i i
i
z
z K
K
= =
> >

4/4/2014 77
Behavior of the Bubble Point
function in a PX diagram
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
4/4/2014 78
Behavior
of the
Bubble
function
on a TX
and a PX
diagram.
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= Pa
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= Pa
4/4/2014 79
Dew and Bubble functions
behavior on a PT diagram
.
P b
P d
P
r
e
s
s
u
r
e

Temperature
CP
1
1
>

=
Nc
i i
i
K
z
1
1
<

=
Nc
i i
i
K
z
1
1
=

=
Nc
i i
i
K
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1
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=

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Nc
i
i i
K z
1
1
>

=
Nc
i
i i
K z
1
1
<

=
Nc
i
i i
K z
2-phases
T r
A
B

L9-High Pressure VLE - EOS

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Copyright:

Verfügbare Formate

L9-High Pressure VLE - EOS

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Copyright:

Verfügbare Formate

4/4/2014 1

Superheated fluid lower T

At the dew point

When the objective is to find the DEW POINT

At the dew point

Over pressurized fluid

At the bubble point

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