PVT & EOS Tuning

2022

Hesham Mokhtar Ali

Senior Reservoir Engineer
in/heshammokhtarali/
1
 What is an Equation of State?
• Most petroleum engineers understand that engineering
calculations involve the properties of fluids.
• “Fluid” is a term used to describe gases and liquids.
• An equation of state (EOS) is nothing more than a fluid
model.
• Specifically,
– The EOS is a fluid model that takes a molar composition
(z) and predicts the phase and volumetric behavior of
the fluid (density, viscosity, FVF, Rs, etc.) over a wide
range of pressure (p) and temperature (T).
– An EOS is an equation that relates P, V, T and
composition (p-V-T-z) of a fluid system.

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 Equation Of State (EOS)
• EOS is an analytic expression relating P to V and T.
• Best method for handling large amounts of P-V-T data.
• Efficient and versatile means of expressing thermodynamic functions in terms of P-V-T data
• PV=ZRT is an equation of state
• Van der Waals EOS: a cubic in volume (or Z), three roots.

 RT  2 a ab
V  b 
3
V  V  0
 p  p p
• The two corrective terms to overcome the limiting assumptions of the ideal gas equation:

 The internal pressure or cohesion term to account for the cohesion forces, a/V2.

 The co-volume b, which represents the volume occupied by 1 mole at infinite pressure and results
from the repulsion forces which occur when the molecules move close together.

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 Redlich-Kwong’s (RK EOS)
• Redlich and Kwong (1949) observed that Vdw (a/V2) term does NOT contain the system
temperature to account for its impact on the intermolecular attractive force between the
molecules.
• They replaced the attraction pressure term with a generalized temperature-dependent term:
VdW EOS RK EOS

• RK equation in cubic form:

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 Soave-Redlich-Kwong (SRK) EOS
• Soave (1972) proposed a modification of RK EOS attraction pressure term.
• Soave replaced the explicit temperature term (a/T0.5) with a more generalized temperature-
dependent term [aα(T)] - dimensionless parameter:

RK EOS SRK EOS

• SRK EOS form: • α is a non-dimensionless temperature

dependent term which has a value of
1.0 at Tc
• α=f(ω) is the accentric factor

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 Peng-Robinson (PR EOS)
• Major failure of RK & SRK EOS is the unrealistically compressibility of Zc=0.333, and
consequent prediction of liquid densities

• To improve this modify the SRK EOS: RT a

p 
• Most widely used 2-parameter (a & b) EOS (V  b) (V  m1b)(V  m2b)
m1  1  2
m2  1  2

a  ac ( , T )
 1 2  1  m( )(1  Tr1/ 2 )

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 3-Parameter EOS – Volume Shift
• Peneloux et al. “volume shift” technique.
• Calculate properties as for 2-parameter EOS
• Shift volumes, and hence Z-factors
• Shift parameter of the heavier component are N
potentially variables for regression (mainly to V ( 3)  V ( 2 )   xi ci
match liquid densities) i 1

• Volume shifts has NO effect on the equal fugacities

conditions for thermal equilibrium, and hence the
ci  Vi EoS
( p st , Tst )  Vi Obs
( p st , Tst )
prediction of saturation pressures, K-values, etc.
• It only modifies molar volumes and hence Z-
factors, densities, etc.

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 Peng-Robinson (PR) EOS
• To improve the ability of EOS to predict liquid densities and other fluid properties, particularly in the
vicinity of the critical region.
• Peng & Robinson (PR) EOS:

• Where:
– a, b, and α have the same significance as they have in SRK model,
– Parameter c is a whole number optimized by analyzing the values of the terms Zc and b/Vc as
obtained from the equation
• Zc should be close to 0.28 and b/Vc should be approximately 0.26.
• An optimized value of c=2 gives Zc=0.307 and (b/Vc)=0.253.

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 Summary of Equations of State
EOS= Prepulsion - Pattraction

EOS Term 1 Term 2 Parameter Parameter

“a” “b”

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 Equations of State
• Make sure there is consistency between EOS currently selected in PVTsim and EOS used when the
fluid was generated.
• PVTsim supports the following EOS's, all of which may be used with or without Peneloux
volume correction.
– Soave-Redlich-Kwong (SRK) (Soave, 1972)
– Peng-Robinson (PR) (Peng and Robinson, 1976)
– Modified Peng-Robinson (PR78) (Peng and Robinson, 1978)

• Peneloux volume correction:

– All equations may be used with/without Peneloux volume correction (Peneloux et al., 1982).
– A constant or a temperature dependent Peneloux correction may be used.
– The temperature dependent volume correction is determined to comply with the ASTM 1250-80
correlation for volume correction factors for stable oils (Pedersen et al., 2002).
• For selected models like Asphaltene and, Flash and PVT simulations, PC-SAFT equation (Chapman et
al. 1988 and 1990) may be used.

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 The Mixing Rules
• To use EOS with mixtures, mixing rules are required to determine the terms (aα) and b for the
mixtures.

• The parameter kij is an empirically determined correction factor, Binary Interaction Coefficient (BIC).

• BIC is included to characterize any binary system formed by components i and j in the hydrocarbon
mixture.

• BICs are used to model the intermolecular interaction through empirical adjustment of the (aα)m term.

• Soave adopted the following mixing rules:

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 The Mixing Rules
• They are dependent on the difference in molecular size of components in a binary system and they are
characterized by the following properties:

– BICs between hydrocarbon components increases as the relative difference between their
molecular weights increases:

ki, j+1 > ki, j

– Hydrocarbon components with the same molecular weight have a BIC of zero:

ki, j = 0
– The BIC matrix is symmetric:

ki, j = kj,i

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 What is a Two-parameter EOS?
• A two-parameter cubic EOS is a PVT equation using 2 parameters “a” and “b ”, suggested by
van der Waals in 1873:
RT a
p  2
(V  b) V
– Parameter “a” is associated with the attractive force a/v2 between molecules in the fluid

– Parameter “b” is associated with the repulsive force RT/(v-b) between molecules in the fluid.

• Two-parameter EOS models:

– Redlich-Kwong (RK)

– Soave-Redlich-Kwong (SRK)

– Peng-Robinson (PR)

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 EOS Parameters
• The most common EOS models are Peng-Robinson (PR) and Soave-Redlich-Kwong (SRK) EOS.

• The PR and SRK is always given with 2 tables.

• The first table is comprised of component properties: critical pressure (pc), temperatures (Tc),
acentric factor (ω), molecular weight (M) and volume shift (s or c).

• The first EOS table:

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 EOS Parameters
• A third parameter c was introduced in 1981 (Peneloux et al.).

• This third parameter makes a simple volume shift of magnitude c (with molar volume units) for a given
phase and a given pressure and temperature

v = vEOS2 - c
• Often the third parameter is given in dimensionless form, s=c/b.

• With properly-determined values of s (c) for all components, accurate densities of both gas and liquid
phases can be expected (±1-3%) at all relevant (p,T) conditions.

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 Binary Interaction Parameters (BIP)
• The EOS second table defines the binary interaction parameters (kij),
• BICs are correction terms applied to each component pair (e.g. C1-C8) in a mixture, with kij=0
being no correction.
• The magnitude of BIP correction usually being ±0.05-0.2, and symmetry kij=kji.

• The correction term kij has most impact on the component equilibrium K-values (Ki and Kj, where K=y/x
for a given component), particularly at higher pressures.

• BIP table is a symmetric matrix.

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 Well Stream
Liquid
Gas Density,
Component MW Density, Mole %
g/cc
g/cc

Composition (Zi)
H2 Hydrogen 2.0160 0.0000 0.0000 0.0000
H2S Hydrogen sulphide 34.0800 0.8006 0.8006 0.000
CO2 Carbon dioxide 44.0100 0.8172 0.8172 0.235
N2 Nitrogen 28.0130 0.8086 0.8086 0.303
C1 Methane 16.0430 0.2997 0.2997 37.449
C2 Ethane 30.0700 0.3558 0.3558 7.989
Data of plus fraction C7+:
C3 Propane 44.0970 0.5065 0.5065 5.481
C7+, Mole % 33.56217 iC4 i-Butane 58.1230 0.5623 0.5623 1.522
nC4 n-Butane 58.1230 0.5834 0.5834 2.971
Molecular Wt (AMW), g/mol 184.2743 iC5 i-Pentane 72.1500 0.6238 0.6238 1.843
nC5 n-Pentane 72.1500 0.6305 0.6305 1.979
Density @ 60°F, g/cc 0.8183 C6 Hexanes 86.1800 0.6631 0.6634 4.771
Me-Cyclo-pentane 84.1600 0.7533 0.7533 0.915
Benzene 78.1100 0.8820 0.8820 0.056
Cyclo-hexane 84.1600 0.7827 0.7827 0.924
C7 Heptanes 100.2000 0.6875 0.6874 2.976

C7+ (C7+C36+)
A group of C8 Octanes 114.2300 0.7063 0.7061 2.949
heavier C9 Nonanes 128.2600 0.7212 0.7212 2.056
C10 Decanes 142.2850 0.7780 0.7780 2.234
components with
C11 Undecanes 147.0000 0.7890 0.7890 2.369
huge amounts of
isomers
Hexatriacontanes
C36+ plus 510.4938 0.9237 0.9237 0.074 17
 Well Stream Composition
Component Mol% MW Density (g/cm3)
N2 0.546 28.014
CO2 2.826 44.010
C1 55.565 16.043
C2 8.594 30.070
C3 5.745 44.097
iC4 1.009 58.124
nC4 2.435 58.124
iC5 0.895 72.151
nC5 1.240 72.151
C6 1.389 86.178 0.6640
C7+ 19.754 199.1 0.8468

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 EOS Characterization
• EOS Characterization workflow:

– Splitting of the plus fraction (C7+)

– Characterization of plus fraction pseudo-

components (assigning properties)

– Grouping or lumping to reduce the number

of pseudo-components

– Tuning (modifying) properties to match

laboratory data

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 Whitson Splitting
Splitting Grouping
• Original C7+ component split into several • Red fractions are regrouped into three (green)
new (red) fractions fractions.

Mole Fraction Mole Fraction

Original C7+ component

has high mole fraction

Original C7+ OriginalC7+

C7+ C7+
Molecular Weight Molecular Weight

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 Matching Data by EOS
• Most EOS characterizations are NOT truly predictive because errors in saturation pressure are commonly
10%, densities are 5%, and compositions may be off by several mole percent for key components.
• EOS may predict a Pd incorrectly when the measured saturation condition is a Pb, or vice versa.
• This lack of predictive capability by EOS can be because of:
– Insufficient compositional data for C7 fractions
– Inaccurate properties for C7 fractions
– Inadequate BIP
– Incorrect overall composition
• Therefore,
– The experimental data and fluid compositions should be checked for consistency.
– If PVT data are consistent and the fluid compositions are representative of the material analyzed in PVT
laboratory, modifying the parameters in the EOS to improve the fluid characterization will be
necessary. 21
 Improvement of EOS Characterization
• Modify the properties of heavy fractions making up C7 (Tc, pc, or direct multipliers on EOS
constants Ωa and Ωb) and BIP’s kij between C1 & C7 fractions.
– When an injection gas containing significant amounts of nonhydrocarbons, kij between non-
hydrocarbon & C7 fractions may also be modified.

• Make manual adjustments to EOS parameters through a trial-and-error approach:

– The trend is now to automate EOS modification procedure with non-linear regression, including
large amounts of measured PVT and compositional data.

• Coats & Smart recommend EOS modifications:

– Ωa & Ωb of C1
– Ωa & Ωb of the heaviest C7 fraction
– BIP (kij) between C1 & the heaviest C7 fraction
– (Non-hydrocarbon a & b & kij): for systems with significant amounts of nonhydrocarbon components

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 Tuning EOS Parameters
• The regression is a non-linear mathematical model that places global upper and lower limits on
each regression variable, ΩaC1 , ΩbC1, etc.
• The non-linear mathematical model determines the optimum values of these regression
variables that minimize the objective function:
Adjustment of the regression parameter

• Where:
– Wj = weighting factor on observation j
– Nexp=total number of experimental data points
– Ejexp = experimental (laboratory) value of observation j, such as pd, pb, or ρob
– Ejcal = EOS-calculated value of observation j, such as pd, pb, or ρob

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 Regression Parameters for Oil Mixtures
• PVT data to which Parameter Sat. Point CME Dif. Dep. SEP Viscosity Swelling CVD MMP

regression may be Sat. Point X X X X X X X

MMP X
performed. Bo X X
GOR (Rs) X X X
Rel. volume X X
Compressibility X
Y-Factor X
Oil density X X X X
Z factor Gas X X
Two-phase Z
X
factor
Gas Gravity X X
Bg X
Mole% removed X
Oil viscosity X X
Gas viscosity X X X

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 Regression Parameters for Gas Mixtures
• Gas condensate Parameter Sat. points CME CVD Separator Viscosity MMP
mixtures
Saturation Point X X X X X
MMP X
Z factor gas X X
Two phase
X
Z factor
Rel volume X
Liq vol% X X
Bo X
GOR X
Gas density X
Oil density X
Gas gravity X
Mole% removed X
Oil viscosity X
Gas viscosity X X

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 Regression for Plus Compositions
• In each iteration the parameters c1, d1 and e1 are recalculated to give the same Tc, Pc and m of a
component with a molecular weight of 94 and a density of 0.745 g/cm3 as is obtained with the standard
coefficients.

• This is done to ensure that Tc, Pc and m of the lower C7+ fractions are assigned properties, which are
physically meaningful.

• The user therefore has no control of the parameters c1, d1 and e1 in the regression input menu.

• The user may modify the default selection of regression parameters, but the number of regression
parameters must not exceed the number of experimental data points.

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 Regression Parameters
• Possible regression parameters.

Crit T (Critical temperature, Tc)

Crit P (Critical pressure, Pc)
Ac fac (Acentric factor, w)
Crit V (Molar critical volume, Vc)
Cpen (Peneloux or volume shift parameter, c)
Om A (EOS parameter, ωa)
Om B (EOS parameter, ωb)
kij (Binary interaction parameters in Classical mixing rule)
kij A (Binary interaction parameters kij A in T-dependent mixing rule)
kij B (Binary interaction parameters kij B in T-dependent mixing rule)
kij C (Binary interaction parameters kij C in T-dependent mixing rule)
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 Regression
Crit T
• Tc & Pc of C7+ components are the most effective
C1
regression parameters. C2
C3
• The specification means that:
iC4
– Tc of the two pseudo-components C7-C29 and C30-C58 nC4
iC5
are to be adjusted by the same % and by max. 10 %. nC5
– Tc of the pseudo-component C59-C80 is to be adjusted C6
C7-C29 X
independently and by max. 20 %. C30-C58 X
C59-C80 X
Max adj % 10 20

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 Correction Factors
• For a characterized fluid some correction factors are displayed.

• These are displayed under the Correction factors tab.

• A correction factor is 1.0 by default, but may change as a result of regression.

• Peneloux:

– Multiplication factor for the volume translation (Peneloux) parameters of the C7+ pseudo-
components.

• Viscosity Correction Factors:

– For LBC viscosity correlation

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 Lohrenz-Bray-Clark (LBC) Viscosity Correlation
• LBC viscosity correlation is widely used for compositional reservoir simulation.
• LBC viscosity correlation is a 4th order polynomial in density.
• Consequently, it is very sensitive to the density of the fluid.
• There is the option to regress on the critical volume or Z-factor used in calculating each component’s
contribution to the total viscosity.
• This critical volume or Z-factor is only used to calculate the viscosity, so remember that in a regression only
the viscosity observations themselves are used to tune these parameters.
• When experimental viscosity data are available, values of the coefficients a1– a5 and the critical
volume of C7+ are adjusted and used as tuning parameters until a match with the experimental data
is achieved.
• These adjustments are performed independent of the process of tuning EOS parameters to match other PVT
data.
• The key relationships of LBC viscosity model:

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Regression
Constant Constant
Saturation Separator Differential Swelling Equilibrium
Parameter Mass Volume Viscosity
Point Test Liberation Test Contact
Expansion Depletion
Weighting Pressure
GOR/Rs
High Medium
High
High High High
Medium
High
Low
Gravity (gas) Low Low
• Different Oil Density High Medium High High High
Weights may be Oil FVF (Bo) Medium Medium
assigned to the Gas FVF (Bg) Low
various Rel Vol Medium
experimental Liquid Vol% of
High High
Vd
data. Data with
Medium/Lo
a weight of zero Z-factor gas Medium Medium
w
is not regressed Z-factor two
Medium
to. phase
• Recommendatio Compressibility Low
ns for the Y Factor Low
%Prod Mole Low
relative weights
to assign to Oil viscosity High High High/Medium
different types of Gas viscosity Medium Medium Medium
experimental Swollen volume High
data. Oil Volume% Medium/High

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 Tuning EOS: Black Oil System
• After the splitting the sensitivity analysis was applied on the system “Regression techniques” to predict a
best PVT model with very low error between the measured and simulated value.

Before Tuning After Tuning

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 Tuning EOS: Gas Condensate System
• After the splitting the Before Tuning After Tuning

sensitivity analysis was

applied on the system
“Regression techniques”
to predict a best PVT
model with very low error
between the measured
and simulated value.

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 Hesham Mokhtar
Hesham Mokhtar

Hesham Mokhtar
Hesham Mokhtar
Hesham Mokhtar
Hesham Mokhtar