EOS
TEAM:
Marianella Luces
Izarra
Soath Karime Parra
Javier Zozaya Pineda
Introduction
The PengRobinson (PR) has become the most popular equation
of state for natural gas systems in the petroleum industry.
Place and date of discovery: during the decade of the 1970’s, D.
Peng was a PhD student of Prof. D.B. Robinson at the University
of Calgary (Canada). In 1976 they developed The Peng and
Robinson (PR) EOS, specifically focused on natural gas systems.
Mean contribution: initially was found to calculate the volume of
100% methane gas as a function of pressure and temperature.
This equation expresses fluid properties in terms of the critical
properties and acentric factor of each species involved.
Nowadays it is applied to the representation of properties of
mixtures as well.
Preceding Correlations
Van der Waals (1873):
Is the simplest EOS and this equation is capable to describe the
continuity between the liquid phase and vapor phase, to use it only
needs the knowledge of Tc and Pc, which are used to calculate the
constants a and b, as show the following equations:
Where:
a = Attraction parameter and b = Repulsion Parameter
2
v
a
b v
T R
P ÷
÷
·
=
C
C
P
T R
a
2 2
421875 , 0
·
=
c
c
P
T R
b
·
· = 125 , 0
Preceding Correlations
Redlich and Kwong – (RK) (1949) :
RK modified the term of force attraction from the Van der Waals equation
for a term dependent on the temperature:
5 , 0
) ( T b v v
a
b v
T R
P
· + ·
÷
÷
·
=
c
c
P
T R
a
5 , 2 2
42747 , 0
·
· =
c
c
P
T R
b
·
· = 08664 , 0
Preceding Correlations
Soave – Redlich – Kwong (SRK) (1972) :
SRK replaced the term dependent on the temperature of the equation of
RK by an expression ∝ (T, ω) function of the temperature and of the
acentric factor:
) (
) (
b v v
T a
b v
T R
P
+ ·
÷
÷
·
=
c
c
c
P
T R
a
2 2
42747 , 0
·
· =
c
c
P
T R
b
·
· = 08664 , 0
) ( ) ( T a a T a
c c
o o ~ ~
( )
2
5 , 0
1 1


.

\



.

\



.

\

÷ + ~
c
T
T
k T o
2
176 , 0 574 , 1 480 , 0 w w k · ÷ · + ~
ω = is the acentric factor
of each pure substance ,
this parameter measures
the sphericity of the
molecules
k = is a constant
characteristic of each
substance
α(T) = dimensionless
parameter dependently
of T.
Equation Studied
Peng and Robinson (PR) (1976):
PR improved the prediction of µ
L
particularly closed to the critical
region, treating the dimensionless factor for the attraction
parameter as a function of acentric factor and reduced
temperature:
( ) b v b b v v
a
b v
T R
P
÷ + + ·
÷
÷
·
=
) (
o
c
c
P
T R
a
2 2
45724 , 0
·
· =
( )
2
5 , 0
1 1


.

\



.

\



.

\

÷ + ~
c
T
T
k T o
2
2699 , 0 574 , 1 3746 , 0 w w k · ÷ · + ~
c
c
P
RT
b 07780 , 0 =
Deriving the Equation
PR departed from the equation of state of SRK improving liquid
density values and accuracy for vapor pressures and equilibrium
ratios.
Base equation of SRK:
PR proposed the need for an improvement in the ability of the
equation of the state to predict liquid densities, particularly close
to the critical region, as illustrated the following equation
Deriving the Equation
As VdW showed to determine the values of the two constants a and b
PR solved these derivatives regardless of the type of substance and set an
universal gas compressibility factor Z= 0.307 , and the parameters a and b
can be calculated in a traditional way using in the following equations:
Deriving the Equation
Important: At temperatures others than critical the values of a and b,
can be calculated using:
Where ∝ (Tr, ω) will
be equal to 1 at
critical temperature
Deriving the Equation
PR used the fugacity of each of the phases to determine the balance
conditions of each phase, through the equation:
The fugacity in each phase was introduced to develop a thermodynamic
equilibrium. The fugacity is a measure of the potential for transfer of the
components between phases ,where the phase with the lower component
fugacity accepts the component from the phase with a higher component
fugacity. Therefore, the condition of the thermodynamic equilibrium can be
expressed mathematically using the Newton’s method by:
Deriving the Equation
With a convergence criterion of ƒ
L
 ƒ
V
≤ 10
4
kPa about two to four
iterations were required to obtain the value of o at each temperature.
For all substances examined by PR the relationship between o and Tc can
be described by the following equation:
Where k is a constant characteristic of each substance:
and ω is the acentric factor of each pure substance
) 1 ( 1
2 1 2 1
r
T k ÷ + = o
2
26992 . 0 54226 . 1 37464 . 0 e e÷ + = k
Deriving the Equation
Rearranging the PR Equation of State
It can be expressed as a cubic equation, in a more practical form in terms
of the compressibility factor and replacing the molar volume with ZRT/P,
as following:
Where:
For pure components:
Deriving the Equation
And for mixtures:
This Form of the equations produces one or three real roots depending
upon the number of phases in the system. In the two phases region the
largest root is for the compressibility factor of de vapor, while the smallest
positive root corresponds to the liquid.
Considerations Used
The PR parameters are expressed in function of the critical properties and acentric
factor (e).
The equation shows accuracy values for Z and µ
L
at critical conditions.
The mixing rules did not have to use more than one binary interaction parameter,
which must be independent of P, T and composition. The mixture parameters used are
defined for the following mixing rules:
Where o
ij
is an empirically determined binary interaction coefficient characterizing the binary formed by
component i and j.
The equations had to be applicable to calculate all the properties of the fluids for
natural gas processes .
¿¿
¿¿ ¿
÷ =
÷ =
= =
i j
ij T T j i T
T T T
i j
T j i T
j
j j
j i
j i ij
ij
a a y y a
a a ij a
a y y a b y b
) 1 ( ) (
) )( 1 (
2 / 1
2 / 1
o
o
Modifications
Nikos et al. in 1986 proposed a generalized correlation for
generating the binary interaction coefficient, .The authors correlated
these coefficients with system pressure, temperature, and the
acentric factor
Where i refers to the principal component, N
2
, CO
2
, or CH
4
, and j
refers to the other hydrocarbon component of the binary.
The acentricfactordependent coefficients K0 K1 and K2, are
determined for each set of binaries.
Modifications
PRVT, StryjekVera (1986) proposed an improvement in the
reproduction of vapor pressures of a pure component by the PR EOS, by
replacing the K term in the equation
with the following expression:
0.7 < Tr < 1
Tr <0.7
Modifications
COMPONENT K
1
Nitrogen
Carbon dioxide
Water
Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
0.01996
0.04285
–0.06635
–0.00159
0.02669
0.03136
0.03443
0.03946
0.05104
0.04648
0.04464
0.04104
0.04510
0.02919
0.05426
0.04157
0.02686
0.01892
0.02665
0.04048
0.08291
For components with a reduced
temperature greater than 0.7,
the optimum values of K1 for
compounds of industrial interest
are tabulated below:
Modifications
Ahmed (1991) To use the PengRobinson equation of state to predict
the phase and volumetric behavior of mixtures, one must be able to
provide the critical pressure, the critical temperature, and the acentric
factor for each component in the mixture. But the procedure is
inadequate for calculating the parameters a, b, and α of the equation for
the C7+ fraction.
parameter D as defined by the ratio of the molecular weight to the specific
gravity of the heptanesplus fraction:
Modifications
For parameters a and b of C7+, the following generalized correlation
is proposed
Solutions of the Equation
Cubic Equation Generalized:
Schmidt and Wenzel (1980) demonstrated that all the cubic equations of
state can be expressed as:
Liquid
Vapor
Other
2 2
wb ubv v
a
b v
T R
P
+ +
÷
÷
·
=
EOS u w
VdW
0 0
RK 1 0
SRK 1 0
PR 2 1
Heyen 1w f(w,b
)
Kubic f(w) u
2
/4
PatelTeja
1w f(w)
Schmidt
Wenzel
1w f(w)
YuLu f(w) u3
Solutions of the Equation
Algorithm of the Equation
Input Values
Composition (X
i
,Y
i
)
Temperature and Pressure of operations(T,P)
Acentric factor(ω)
Critical Pressure and Critical Temperature (T
c
,P
c
)
Constant of gas (R)
Calculate the parameters , b and α for each component in the system.
Calculate the mixture parameters and b
m
for the gas and liquid phase.
Solutions of the Equation
Calculate the coefficients A and B for the gas and liquid phase.
Solve cubic equation for the compressibility factor of the gas and liquid
phase.
Obtain the root of cubic equation with the coefficients A and B
Obtained Z you can calculate Volume or density.
Application in the Oil
Industry
The PengRobinson EOS has become the most popular equation of
state for natural gas systems in the petroleum industry.
A slightly better performance around critical conditions makes the
PR EOS somewhat better suited to gas/condensate systems.
PR obtains better liquid densities than SRK.
Thank You!