Chapter 4 EOS F

CHAPTER 4: Equation of State (EOS)
September 1316, 2016
Copyright 2016 ENERPROCO LLC. All rights Reserved.

Disclaimer
This presentation has been prepared for ENERPROCO LLC client.
The report is intended solely for the benefit of the client, and its contents and
conclusions are confidential and may not be disclosed to any other persons or
companies without ENERPROCOs prior written permission.
ENERPROCO retains all intellectual property interest associated with the

presentation.
The information upon which this presentation is based has either been supplied to
Copyright 2016 Enerproco LLC . All rights reserved.

us or comes from our own experience, knowledge and databases. The opinions
expressed in this report are those of ENERPROCO. They have been arrived at
following careful consideration and enquiry but we do not guarantee their
fairness, completeness or accuracy. The opinions, as if this date, are subject to
change. We do not accept any liability for your reliance upon them.
-1-
TBD
-2-
Equation of State (EOS)

Contents
Regression of EOS Parameters

Characterization of the Heavy Hydrocarbon Fraction
General Procedure for Fluid Characterization
EOS
General Rules of Thumb for Lumping
General Rules of Thumb for Regressing EOS Parameters
Example Regression of EOS Parameters

-3-
Equations of State (EPOS)
Arithmetic of EOS
EOS are mathematical relations between pressure, temperature and volume of a gas
or liquid. These equations are usually of a cubic form.
The ideal gas EOS (PV=nRT) was the first mathematical expression used to describe
the PVT behavior of gas.
The most commonly used EOSs in Petroleum Engineering is the Peng-Robinson EOS
(PR) and Soave-Redlich-Kwong (SRK).
EOS Calculations: Inputs and Outputs

Pressure Densities
Temperature
Composition
} { Fugacities
Equilibrium phase compositions

Critical pressure pci
Critical temperatur e Tci
Acentric factor i
Interactio n coefficien t dij
-4-
Equations of State (EOS)
Commonly-used EOS
Van-der-Waals (1873)
RT a
p= 2
v b v
where a and b are characteristics of the particular gas, R is the universal gas
constant, and is the molar volume.
Peng-Robinson
RT a
p=
v b v (v + b ) + b (v b )

The equation can be expressed as a cubic polynomial as follows:
Z 3 + ( B 1) Z 2 + ( A 3B 2 2 B ) Z ( AB B 2 B 3 ) = 0
with
vP a P bP
Z= A= B=
RT (RT ) 2 RT
-5-
Commonly-used EOS
p 2 p
= = 0
The Wa and Wb coefficients are derived from: v T v 2 T
2 2
R Tc b = 0.07780 RT c 1/2 = 1 + m(1 - T r ) m = 0.37464 + 1.54226 - 0.26992 2
1/2
a = 0.45724
Pc pc
a b
Soave-Redlich-Kwong
RT a
p=
v b v (v + b )

The equation can be expressed as a cubic polynomial as follows:
Z 3 Z 2 + ( A B B 2 ) Z AB = 0
2 2
m = 0.480 + 1.574 - 0.176 2
a = 0.42747 R T c b = 0.08664 RT c = (log pvr + 1)
pc pc
-6-
Mixing Rules
For a mixture, "a" and "b" become composition dependent, require mixing rules
nc
average molecular volumes,
b= yi b i ;
bi is proportional to the size
i=1
nc nc
quadratic mixing rule, " a" reflects the
a= yi y j a ij ;
strength of attraction between two molecules
i=1 j=1
(
a ij = a ii a jj )1 / 2 ( 1 dij )

dij interaction coefficient between species
i and j; dij = d ji
-7-
List of Properties to be Matched by Regressions
Saturation Pressure
Phase densities
Mole or volume fraction of a phase

EOS
Properties
K-value of all components
Phase viscosities

GOR, relative oil volume, swelling factors, liquid dropouts, etc.
-8-
General Regression of EOS Parameters
The parameters most commonly changed are Wa, Wb and the binary
interaction coefficients. By changing these parameters, the EOS can
be forced to match laboratory measured data.
Justification for altering theoretical EOS parameters

EOS
Parameters Methane Fraction. At reservoir conditions, methane is
usually well above its critical point, where there is no
theory or clear-cut guide to selection or alteration of W's.
Plus Fraction. The plus fraction, unlike all other

components, is a mixture of many components.

-9-
Details Regression of EOS Parameters
To modify all properties:
Pci, Tci, i, ai , bi
To modify saturation pressures and other properties:

Hydrocarbon interaction coefficient exponent and
individual interaction coefficients
EOS
Parameters To modify volumetrics only (densities, Z-factors, etc.):
Volume shift parameters
To modify viscosities only:

Viscosity correlation coefficients, component molar

volumes for viscosity calculations
- 10 -
Characterizing of the Heavy Hydrocarbon Fraction
Details Procedure for Fluid Characterization
Split the C7+ (or C6+) fraction into a suitable number of components.
1. Then use these C7+ components (usually 3 to 5 components) with the

standard components to develop a ten to fifteen component model for the
reservoir fluid.
Perform regression with fluid model.
Use HC binary interaction coefficient exponent, and Tc and Pc of the heaviest

C7+ components, and the volume shift factors for all C7+ components.
2.
If there is a lot of CO2 present in the mixture also include the binary

interaction coefficients between CO2 and the C7+ components as regression
parameters.
Include all available experimental PVT data in the regression calculation.
3. These include saturation pressure, constant composition expansion,

differential liberation, swelling tests, separator tests, and phase equilibrium
data.
- 11 -
Details Procedure for Fluid Characterization
Perform regression. If a good match is achieved then stop; otherwise try some of
the following changes:
Change the weight some of the experimental data, usually saturation pressure has
4. a high weight
Add Tc and Pc of more C7+ components to the regression variables
Change the default values of maximum and minimum values of the regression
variables that are at their limits
If the above steps do not improve the match go back to Step 1 and redo the
5. splitting of the C7+ and repeat steps 2 to 4
If the number of components is too large for the desired simulation runs, lump the
components into fewer components. Then perform regression on the lumped

6. component system using as few parameters as possible. Tc of the heaviest
component is often a good choice.
Match any available viscosity data in a separate regression in which only the
7. viscosity model parameters are adjusted.
Test the model over the anticipated range of P, T and composition! Is spurious
8. multiphase behaviour predicted? Do calculated K-values follow physically realistic
trends? Etc
- 12 -
Example
Example:
a) Reported composition
Component Mole %
CO2 3.03
N2 0.33
C1 41.33
C2 8.89
C3 5.95
iC4 1.34
nC4 2.78

iC5 1.22
nC5 1.44
C6+ 33.69
API gravity of C6+ @ 15oC = 35.3
Specific gravity of C6+ = 0.8478
Molecular weight of C6+ = 202
- 13 -
Example
Example:
b) Modelled fluid composition
Component
Number Component Mole %
1 CO2 3.03
2 C1 + N2 41.66

3 C2 - C3 14.84
4 C4 - C5 6.78
5 C6 - C12 16.64
6 C13 - C20 11.65
7 +
C21 5.40
- 14 -
Example
Example:
Modelled fluid composition CO2 Pressure-Composition Diagram

- 15 -
Example
Example:
Modelled fluid composition original and regressed properties
Component Pc (atm) Tc (K)

Number Component Initial Final Initial Final
1 CO2 72.80 72.80 304.2 304.2

2 C1, N2 45.31 45.31 190.1 176.0*
3 C2-C3 45.64 45.64 332.9 383.0*
4 C4-C5 35.54 35.54 438.2 438.2

5 C6-C12 26.69 26.69 621.0 621.0
6 C13-C20 19.84 19.84 747.3 747.3
+
7 C 21 14.65 14.65 888.2 941.0*
Initial dCO2 I = 0.1I = 2,3,...,7
Final dCO2 i = 0.1i = 2,3,...,7,i 6

dCO2 6 = 0.051 *
*Parameters used during regression

- 16 -
1. Group components with similar critical properties or with

similar K-values at reservoir conditions
2. Group all components with smaller compositions (<1%)
3. Lump non-hydrocarbon gases in with hydrocarbon gases that

have similar properties (N2 with C1, CO2 with C2), unless one of
General Rules of
these non-hydrocarbon gases will be injected
Thumb for
Lumping
4. Do not group light and heavy components

5. The lumped components should have similar proportions
whenever possible
6. Most hydrocarbon system can be adequately modelled with

four to eight components
- 17 -
A Common Lumping Scheme
The following 6-component lumping scheme usually gives good results:

C1 + N2
C2 + C3 + CO2
i-C4 + n-C4 + i-C5 + n-C5 + C6
C7 + C8 + C9
Split C10+ into two hypothetical components

- 18 -
1. Calculated fluid properties are very sensitive to properties of

the heavy or plus fractions and Methane, so a s and b S
of these components are good targets for optimization.
General Rules of 2. Target the heavy ends first, then include Methane if necessary.
Thumb for
Regressing EOS 3. If densities and saturation pressure cant be matched
Parameter simultaneously, match densities first then fine tune saturation
pressure.
4. Densities can be adjusted by adjusting the density of the plus

fraction.
- 19 -
Exercise 3: Raleigh Oil (Required File: Raleigh black oil-data.xls)
Objective: Plus fraction splitting, matching experimental constant composition expansion,
separator test and differential liberation tests.
1. Initialize WinProp through CMG launcher.
2. Insert a title: plus fraction characterization and select PR (1978), Psia & deg F,
feed as moles in the specify titles, EOS and unit system form.
3. In the component selection/Properties form add the following library components
and compositions as given in the file: Raleigh black oil-data.xls.

Figure 20: black oil composition for Raleigh oil
- 20 -
4. To split the C7+ fraction into
pseudocomponents; double
click on Plus fraction
Splitting" form. on "General"
Tab; Specify Gamma
distribution function, 4
pseudocomponents, The first
single carbon number in plus
fraction as7 and leave others as
default Go to "Sample 1" Tab.

Figure 21: Plus fraction splitting for Raleigh Oil.
5. Input the MW+ as 190, SG+ as 0.8150 and Z+ (mole fraction of C7+ fraction) as 0.2891.
Make sure alpha is equal to 1.
6. Save the dataset as raleigh oil.dat and run it. After running the data set, use the Update
component properties in the File menu. and save the data set as raleigh oil_plus
fraction splitting.dat. You will now notice that 4 hypothetical pseudo components have
been added in the components form.
- 21 -
7. In order to match the CCE, Differential liberation and separator test, use the data
given in the file Raleigh black oil-data1.xls. then open "Saturation Pressure",
"constant composition expansion", "separator" "differential liberation" forms in
sequence. Input the experimental data given in the file Raleigh black oil-data1.xls.(
you can also input all above forms, from another WinProp dataset).
8. On the Component Selection/properties form, set the volume shifts to the

correlation values. Save your model as raleigh oil_experimental data.dat and run it
once to validate your model and check for errors in the input data.
9. Click on Regression /start on top menu and open Open "Regression Parameters" form

before "Saturation Pressure" form( before any regression calculation) and insert "
End Regression " form at end(after all forms that are supposed to be included in
regression process, i.e. CCE, Saturation Pressure, Differential Liberation and Separator
). This defines the Regression Block.
10. Select the heaviest pseudocomponents Pc and Tc, volume shifts of all C7+
pseudocomponents and C1, and the hydrocarbon interaction coefficient exponent as
regression variables. Set the convergence tolerance to 1.0E-06 in "Regression
Controls" tab and then save and run the data set.
- 22 -

Figure 22: Regression control for experimental data matching.
11. Adjust the weight of some key experimental data points. Try setting the weight for
separator API gravity to 5.0, saturation pressure to 10.0, and differential liberation API
gravity at standard conditions to 0.0. Re-run the regression.
12. In some cases, you may have to change the lower and upper bounds of the regression
parameters depending on whether these bounds are reached during the regression. In
this case the following bounds were used:
- 23 -
13. Analyze the *.out file and

refer to the summary of
Regression Results for
comparison of the
experimental versus
calculated values.
14. After completing the match to

the PVT data, update the
component properties and

again save the file under a
new name as raleigh
oil_experimental data_vis.dat
Figure 23: Variable bounds used during the regression
in preparation for viscosity
matching.
15. For viscosity matching, temporarily exclude the saturation pressure, constant
composition expansion and separator calculations from the data set by right-clicking
on each option and selecting Exclude from the pop-up menu.
- 24 -
16. In the "Differential Liberation" form, set the weight for the viscosity data to 1.0, and all
other weights to 0.0.
17. On the viscosity parameters tab of the "Regression Parameters" form, remove all
previously selected parameters, and then select Vc, vis(l/mol) for C1 and the C7+
pseudo components as regression variables. Run the data set.
18. After completing the match to the viscosity data, update the component properties and
save the file under a new name raleigh oil_Blackoil PVT.dat in preparation for
generating the IMEX PVT table.

19. Remove the regression forms and include any options that had previously been
excluded. Add a Black Oil PVT Data option at the end of the data set.
20. On the Black Oil PVT Data form, enter the saturation pressure data, desired pressure
levels and the separator data. Enter mole fractions of 0.1, 0.2 and 0.3 for the swelling
data.
- 25 -

Figure 24: Black oil PVT export for IMEX. Figure 25: Pressure levels for back oil PVT
- 26 -

Figure 26: Water properties for black oil PVT
21. Leave the Oil Properties controls at the defaults, and then select Use solution gas
composition for the swelling fluid specification on the gas properties tab. Run the
data set.
- 27 -
Equations for Compositional Simulation
Equations
Mass balance equation :

( y i g u g )+ ( x i o u o )= - [ ( S o o x i + S g g y i )]
t
Darcy's equations for each flowing phase are identical to the Black Oil equations:
kk rg Pg

ug =
g x
Where: Pcog = Pg Po
Pcow = Po Pw
So + Sg = 1
- 28 -
Equations
The phase behavior is depend on pressures and composition, so that the functional
dependencies may be written
o , g , o , g = f(p, T, x i , y i , z i )
o ( Po , x1 , x2 ,...)
g ( Pg , y1 , y2 ,...)
o ( Po , x1 , x2 ,...)
g ( Pg , y1 , y2 ,...)

The equilibrium K-values may be used to determine component ratios:
yi
= K i ( P, T , xi , yi )
xi
- 29 -
Equations
Constraint equation for mole fractions in equilibrium:
n =
i
= x
i = y
i
i
i
i 1.0
L +V =
1
=
ni Lxi + Vyi
o So

L=
o So + g S g
g Sg
V=
o So + g S g
- 30 -
TBD

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- 31 -

Chapter 4 EOS F

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Chapter 4 EOS F

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CHAPTER 4: Equation of State (EOS)

September 1316, 2016

Copyright 2016 ENERPROCO LLC. All rights Reserved.

This presentation has been prepared for ENERPROCO LLC client.

ENERPROCO retains all intellectual property interest associated with the

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Regression of EOS Parameters

Copyright 2016 Enerproco LLC . All rights reserved.

EOS Calculations: Inputs and Outputs

Copyright 2016 Enerproco LLC . All rights reserved.

Interactio n coefficien t dij

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Mole or volume fraction of a phase

Copyright 2016 Enerproco LLC . All rights reserved.

Justification for altering theoretical EOS parameters

Plus Fraction. The plus fraction, unlike all other

Copyright 2016 Enerproco LLC . All rights reserved.

To modify saturation pressures and other properties:

To modify viscosities only:

Copyright 2016 Enerproco LLC . All rights reserved.

1. Then use these C7+ components (usually 3 to 5 components) with the

Perform regression with fluid model.

Use HC binary interaction coefficient exponent, and Tc and Pc of the heaviest

Copyright 2016 Enerproco LLC . All rights reserved.

Include all available experimental PVT data in the regression calculation.

3. These include saturation pressure, constant composition expansion,

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Component Pc (atm) Tc (K)

1 CO2 72.80 72.80 304.2 304.2

Copyright 2016 Enerproco LLC . All rights reserved.

Final dCO2 i = 0.1i = 2,3,...,7,i 6

*Parameters used during regression

1. Group components with similar critical properties or with

2. Group all components with smaller compositions (<1%)

3. Lump non-hydrocarbon gases in with hydrocarbon gases that

Copyright 2016 Enerproco LLC . All rights reserved.

6. Most hydrocarbon system can be adequately modelled with

The following 6-component lumping scheme usually gives good results:

Copyright 2016 Enerproco LLC . All rights reserved.

1. Calculated fluid properties are very sensitive to properties of

4. Densities can be adjusted by adjusting the density of the plus

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

8. On the Component Selection/properties form, set the volume shifts to the

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

13. Analyze the *.out file and

14. After completing the match to

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Mass balance equation :

Copyright 2016 Enerproco LLC . All rights reserved.

Copyright 2016 Enerproco LLC . All rights reserved.

Constraint equation for mole fractions in equilibrium: