Manual Winprop PDF

User's Guide
WinProp
Phase Property Program
Version 2010
By Computer Modelling Group Ltd.

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Preface
WinProp is CMG's equation of state (EOS) multiphase equilibrium and properties
determination program. WinProp features techniques for characterizing the heavy
end of a petroleum fluid, lumping of components, matching laboratory PVT data
through regression, simulation of first and multiple contact miscibility, phase
diagrams generation, asphaltene and wax precipitation modelling, compositional
grading calculations as well as process flow simulation.
This User's Guide presents a comprehensive description of the steps involved in
obtaining a PVT data suitable for inclusion in data files for CMG's GEM, STARS or
IMEX simulators. This User's Guide is aimed at reservoir engineers who want to use
WinProp to predict phase behavior of reservoir fluids as well as characterize these
fluids for reservoir simulation. It requires some knowledge of phase behavior as it
pertains to the different fluid types found in reservoirs.
Every attempt has been made in the preparation of this User's Guide to provide the
user with all the necessary details. If questions arise, please contact:

#150, 3553 – 31 Street N.W.
Calgary, Canada
T2L 2K7
Telephone: (403) 531-1300 Fax: (403) 289-8502 E-mail: cmgl@cmgl.ca
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Contents
New Features 1
New Features in WinProp 2010.10...............................................................................1
New Features in WinProp 98.00.................................................................................12
New Features in WinProp 97.00.................................................................................14
Introduction 17
What is WinProp?.......................................................................................................17
Use of this Manual......................................................................................................18
Installation ..................................................................................................................18
Confidentiality ............................................................................................................18
Template Data Files ....................................................................................................19
Tutorial Section 21
Overview.....................................................................................................................21
Getting On-Line Help .................................................................................................21
Creating, Opening and Saving Data Files...................................................................21
Running, Viewing Output and Creating Plots ............................................................22
Copying Between Different Data Files.......................................................................23
Setting Up a Regression Run ......................................................................................23
User's Guide WinProp Contents • i

Using the Update Component Properties Feature of WinProp................................... 23
View the Keyword Data File Created by WinProp .................................................... 24
Selecting a User-Defined Editor................................................................................. 24
Editing the Data Set.................................................................................................... 24
Table Import Wizard .................................................................................................. 25
Overview ....................................................................................................... 25
Using the Table Import Wizard..................................................................... 26
Data Set Structure 31

Overview .................................................................................................................... 31
Editing Data Set.......................................................................................................... 32
Titles/EOS/Units Selection 33
Overview .................................................................................................................... 33
Data Input ................................................................................................................... 33
Comments...................................................................................................... 33
Title 1, Title 2, Title 3 ................................................................................... 33
Equation of State ........................................................................................... 34
Units .............................................................................................................. 34
Feed ............................................................................................................... 34
Components 35
Component Selection and Definition ......................................................................... 35
Library Components...................................................................................... 35
User Component with Known Properties...................................................... 36
User Component with Known SG, Tb and MW ............................................ 37
Component Properties ................................................................................................ 38
Notes on Component Properties.................................................................... 39
Interaction Coefficients .............................................................................................. 43
Hydrocarbon-Hydrocarbon Interaction Coefficients..................................... 44
Other Interaction Coefficients ....................................................................... 46
Viscosity Parameters .................................................................................................. 46
Jossi-Stiel-Thodos Correlation ...................................................................... 46
Pedersen Correlation ..................................................................................... 47
Aqueous Phase ........................................................................................................... 48
Aqueous Phase Salinity ................................................................................. 48
Henry’s Law Constant Correlation................................................................ 49
Activation of Second Set of Component Properties................................................... 49
GEM Fluid Model Generation and Component Properties Printing .......................... 50
Importing Components with the Table Import Wizard .............................................. 51
ii • Contents User's Guide WinProp

Common Data Required for All Options 53
Overview.....................................................................................................................53
Composition Specification..........................................................................................53
Initial K-Values...........................................................................................................55
Output Level ...............................................................................................................55
Stability Test Level.....................................................................................................55
Two-Phase Saturation and Phase Boundary Calculations 57

Overview.....................................................................................................................57
Saturation Pressure .....................................................................................................57
Saturation Temperature...............................................................................................58
Phase Boundary and Quality Line Calculations .........................................................58
Envelope Specification ..................................................................................59
Envelope Construction Controls ....................................................................61
Cricondenbar/Cricondentherm Calculation ................................................................62
Critical Point Calculation............................................................................................62
Flash Calculations 63
Overview.....................................................................................................................63
Common Input for Two-Phase Flash, Multiphase Flash and Asphaltene/Wax
Modelling Calculations...............................................................................................63
Two-Phase Flash Calculations....................................................................................64
Multiphase Flash Calculations....................................................................................64
Asphaltene/Wax Modelling ........................................................................................65
Theoretical Background.................................................................................65
Input Data - Asphaltene/Wax Modelling.......................................................67
Single-Phase Calculation ............................................................................................70
Isenthalpic Flash Calculations ....................................................................................70
Theoretical Background.................................................................................70
Input Data - Isenthalpic Flash ........................................................................72
Three-Phase Boundary Calculation 73

Background.................................................................................................................73
Input Data ...................................................................................................................73
Envelope Specification Tab ...........................................................................73
Envelope Construction Controls Tab.............................................................75
Initial K-Values Tab ......................................................................................76
User's Guide WinProp Contents • iii

Component Splitting and Lumping 77
Overview .................................................................................................................... 77
Characterization of Multiple Related Samples........................................................... 78
Splitting the "Plus" Fraction....................................................................................... 78
Importing Extended Analysis Data with the Table Import Wizard............................ 82
Numerical Cleaning of Mud-Contaminated Samples................................................. 83
Lumping of Components............................................................................................ 84
Transferring Results to Other Data Sets ..................................................................... 85
Laboratory Calculations 87
Overview .................................................................................................................... 87
Recombination of Separator Oil and Gas................................................................... 87
Compressibility Calculation ....................................................................................... 90
Constant Composition Expansion .............................................................................. 90
Differential Liberation................................................................................................ 92
Constant Volume Depletion ....................................................................................... 94
Separator Test............................................................................................................. 97
Swelling Test............................................................................................................ 101
Importing Laboratory Experiment Data with the Table Import Wizard................... 103
Multiple Contact Miscibility Calculations 105

Overview .................................................................................................................. 105
Data Input ................................................................................................................. 106
Regression 111
Overview .................................................................................................................. 111
Organization of the Input Data ................................................................................. 111
Parameter Selection.................................................................................................. 112
Automatic Regression Parameter Selection ............................................................. 114
Grouping Regression Variables................................................................................ 114
Regression Variable Bounds .................................................................................... 115
Regression Control Parameters ................................................................................ 116
Transferring Results to Other Data Sets ................................................................... 116
Compositional Grading 119

Overview .................................................................................................................. 119
Data Input ................................................................................................................. 120
iv • Contents User's Guide WinProp

STARS PVT Data Generation 123
Overview...................................................................................................................123
Use of the STARS PVT Generation Option .............................................................123
Input Data (STARS) .................................................................................................124
Basic STARS PVT Data ..............................................................................124
Gas-Liquid K-Value Tables.........................................................................126
Gas-Liquid and Liquid-Liquid K-Value Tables ..........................................127
Gas-Liquid and Solid-Liquid K-Value Tables.............................................128
Feed and K-Value Plotting Controls............................................................129
Process Flow 131

Overview...................................................................................................................131
Data Input - Process Flow.........................................................................................132
Black-Oil PVT Data Generation 135

Overview...................................................................................................................135
Laboratory Procedure ...............................................................................................144
Input Data .................................................................................................................144
References 149
List ............................................................................................................................149
Appendix A 153
Case Studies..............................................................................................................153
Case Study Number 1: Gas Condensate Modelling....................................153
Case Study Number 2: Solubility of CO2 in Brine .....................................163
Case Study Number 3: Asphaltene Precipitation Modelling ......................174
Appendix B 183
Equations ..................................................................................................................183
Cubic Equation of State ...............................................................................183
Phase Stability Test......................................................................................188
Two-Phase Flash Calculation ......................................................................190
Saturation Calculation..................................................................................191
Cricondenbar/Cricondentherm Equations....................................................193
Phase Diagram Construction .......................................................................193
Three Phase Flash Calculation with Equation of State ................................197
Three Phase with Isenthalpic Flash Calculation ..........................................198
Flash Calculation Involving Water ..............................................................200
User's Guide WinProp Contents • v

Critical Point Calculations........................................................................... 203
Viscosity Correlation................................................................................... 204
Solution of Non-Linear Equations .............................................................. 206
Plus Fraction Characterization .................................................................... 207
Interfacial Tension Calculations.................................................................. 211
Regression ................................................................................................................ 211
Introduction ................................................................................................. 211
The Regression Method............................................................................... 212
Application of the Regression ..................................................................... 213
Properties of Components ........................................................................................ 216
User Components ........................................................................................ 218
Interaction Coefficient................................................................................. 220
Nomenclature ........................................................................................................... 222
References for Appendix B ...................................................................................... 224
vi • Contents User's Guide WinProp

New Features
New Features in WinProp 2010.10

New Approach for the Multiple Contact Miscibility Calculation
A Tie Line calculation method has been added to WinProp in the Multiple Contact Miscibility
Calculation section to calculate the minimum miscibility pressure (MMP) or minimum
miscibility enrichment (MME). This method takes the combined condensing and vaporizing
displacement mechanisms into consideration, as well as the existing pure vaporizing or pure
condensing mechanisms. With the pressure or enrichment increasing, all key tie lines, including
the initial tie line, injection tie line and the crossover tie lines, can be found simultaneously
based on the method of characteristics theory. The MMP or MME can be determined once any
of these key tie lines’ length becomes zero. Please see the Multiple Contact Miscibility
Calculation section of the User’s Guide for more details. Use of the feature is illustrated in the
mcm-combined-U2002rich-MMP.dat template data set.
Liquid Viscosity-Temperature Table for Multiple Pressures
The STARS PVT generation option can now calculate and output multiple liquid viscosity-
temperature tables over a defined pressure range. This is compatible with a new STARS option
to allow pressure dependence of liquid viscosities available in STARS 2010.10.

Numerical Cleaning of Mud-Contaminated Samples
A new feature has been added to WinProp in the Component Splitting and Lumping section.
WinProp now can determine the original composition of the reservoir fluids from mud-
contaminated samples. WinProp uses the skimming method, subtraction method or a
combination of both methods to numerically clean the mud-contaminated samples. If the level
of mud contamination is available and the mud composition is also provided, a direct
subtraction method will be used to numerically clean the contaminated sample. If the level of
mud contamination is not available but the mud composition is provided, a combination of the
skimming method and subtraction method will be used to estimate the level of contamination
first, and then numerically clean the contaminated sample. If there is no information about the
level of contamination and mud composition, WinProp can use skimming method to
numerically clean the contaminated sample based on the first and last SCN in the mud. Please
see the Component Splitting and Lumping section of the User’s Guide for more details. Use of
the feature is illustrated in the mudclean_split.dat template data set.
User's Guide WinProp New Features • 1

STARS PVT Generation
A number of enhancements have been made to improve the liquid density parameters. The feed
composition is flashed at reference pressure and temperature so that a stable liquid composition
is used for all calculations. Once this is done, Compressibility, first and second thermal
expansion coefficients are determined from a perturbation calculation. Finally the cross
coefficient (P and T) is determined by optimization to best fit surface conditions and a user-
specified range of reservoir condition densities. These changes result in a decreased sensitivity
to the choice of reference conditions, more accurate compressibility parameters, and a better
match between the EOS and STARS fluid model densities, which are now shown in a table in
the .out file.
The reference phase for components can now be specified as AQUEOUS, the previous default
was that all components are OLEIC. This means that K-values for gas-water systems can be
generated.
In addition, the solid K-value table generation has been improved, as well as the map of
WinProp EOS vs. STARS k-value flash results.
Aqueous Phase Property Models
Accurate models for the Henry’s constants of CO2, N2, H2S and CH4 have been implemented,
taking into account pressure, temperature and salinity (salting-out coefficient). These models
are activated by selecting the option button for “Harvey’s Method (1996)” on the “Aqueous
phase” tab of the Component properties dialog. These correlations are also implemented in
GEM 2008.10. The existing aqueous phase solubility models are still available in WinProp.
The Kestin correlation is now used for aqueous phase viscosity when the OGW flash is
specified in WinProp.
Calculation of Temperature-Dependent Asphaltene Parameters
It is now possible to enter multiple asphaltene onset pressures at different temperatures in the
asphaltene flash dialog. These values are used to calculate the temperature-dependent
parameters of the asphaltene precipitation model.

IMEX Volatile Oil PVT Table Generation
Black oil PVT tables can be generated for the new IMEX volatile oil option. Undersaturated gas
compressibility and viscosity may be represented using only the dry gas and saturated gas
endpoints, or with a complete table of values between these endpoints. The “endpoints” form
uses the new PVTVO table. To allow modelling of nonlinear effects in the gas compressibility
and viscosity, undersaturated gas property tables are used in conjunction with the PVTCOND
table, as for the Gas-Water with Condensate model in IMEX.
2 • New Features User's Guide WinProp

Other Enhancements for IMEX PVT Table Generation
For all IMEX PVT tables, the user can now choose to generate gas formation volume factors,
gas expansion factors, or gas Z-factors. This applies to the saturated tables (PVT, PVTG,
PVTCOND and PVTVO) as well as the undersaturated gas tables, which can now take the
form BGUST, EGUST or ZGUST.
For IMEX PVTCOND and PVTVO tables, calculation of the condensate/gas ratio at low
pressures has been modified for improved performance in the simulator.
Scaling Differential Liberation Oil FVF and GOR to Bubble Point Oil Volume
For the differential liberation experiment, oil formation volume factor and solution gas/oil ratio
can be scaled to the bubble point oil volume rather than the residual oil volume. This provides
oil shrinkage and cumulative gas released per volume of bubble point oil, and eliminates the
need for the EOS to accurately represent the residual oil volume. The scaled values can be used
in regression. Summary plots show both the original data and the scaled values.
STARS PVT Generation
For STARS PVT generation, new methods have been implemented to generate the component
liquid viscosity table. Apparent liquid viscosities of light components can be generated by
perturbing the dead oil at each temperature, which will give accurate liquid viscosities of
solvent components which may vaporize at higher temperatures ("match dead oil" method).
Smooth curves for all component viscosities may be generated by scaling the liquid viscosities
at low temperatures, then extrapolating to higher temperatures ("scale viscosities" method).
More accurate determination of phase viscosity and density, and reduced sensitivity to choice
of reference condition, have been achieved by using stable liquid properties in STARS
component property calculations.
Saturation Pressure/Regression Enhancement
Saturation Pressure calculation results are checked for stability. This prevents the regression
algorithm from converging to an unstable two-phase saturation condition, within a three-phase
region.

Enhancements of existing features and code clean up.

A number of WinProp’s calculation options have been enhanced, including the following:
Irreversible Asphaltene Calculation
The asphaltene flash has been enhanced to allow specification of an equilibrium constant for
conversion of reversible to irreversible asphaltene. The irreversible asphaltene can be
interpreted as flocculated solid particles. This technique has been designed to allow the
simulation of laboratory forward and reverse contact experiments with series of asphaltene
flash calculations.

Oil-Gas-Water (OGW) Flash Calculations
The OGW flash has been improved to give greater stability and better convergence characteristics
for difficult problems, for example light and intermediate hydrocarbons with steam.
STARS Aqueous-Liquid and Aqueous-Vapor K-Value Generation
In addition to the improvements of the OGW flash listed above, the generation of STARS K-
values including aqueous phases has been enhanced with improved extrapolation algorithms.

A number of WinProp’s calculation options have been enhanced, including the following:
Compositional Gradient Calculation
For the non-isothermal model, temperatures are now output to the summary table, error
trapping has been improved, and the input of the temperature gradient has been modified so
that positive gradient values now indicate increasing temperature with depth.
Viewing Simulator PVT Models
Menu items have been added to allow easy viewing of the files generated for GEM, IMEX or
STARS component models, analogous to the WinProp output file viewing procedure.
Temperature-Dependent Volume Shifts
The Rackett’s Z-Factor is now re-calculated during lumping or regression calculations, so
that the temperature-dependent volume shift technique will maintain consistency with
pseudocomponent specific gravities.
STARS PVT Model Generation
Liquid-phase component viscosities for light components are now back-calculated from live oil
and dead oil viscosities, rather than computing them directly from the WinProp viscosity model.

Gamma Distribution Characterization Enhancements
The following enhancements have been implemented for the gamma distribution
characterization: (1) Specification of the bounds on the molecular weights has been improved
when using the “variable molecular weight interval” method for fitting the distribution
parameters to extended analysis data. (2) When specific gravity data is available with the
extended analysis, coefficients in the specific gravity-molecular weight correlation are
adjusted to best fit the data. (3) Use of the gamma distribution to extrapolate extended
analysis data to higher carbon numbers has been improved to provide better consistency with
input physical property data.

Separator Calculation for Gas Condensates
Calculation of dry gas and wet gas formation volume factors has been implemented when the
separator calculation is used with gas condensate fluids. The dry gas FVF is defined as the
volume of gas at the dew point pressure divided by the volume of gas from all separator
stages evaluated at standard conditions. The wet gas FVF is defined as the volume of gas at
the dew point pressure divided by a hypothetical surface wellstream volume, calculated under
the assumption the entire wellstream is in the gas phase with a Z-factor of one. The
condensate/gas ratio is also reported.
In addition, the average separator gas gravity from all separation stages is now being output
for oil and condensate fluids.

IMEX GASWATER_WITH_CONDENSATE PVT Table Generation
The black oil PVT option has been expanded to allow generation of PVT tables for the IMEX
GASWATER_WITH_CONDENSATE fluid model. This model allows description of
condensate liquid dissolved in the gas phase or present as a free liquid in the reservoir and at
surface conditions. This option may be used for dewpoint fluids (gas condensates) only. The
tables are generated by simulating a constant volume depletion experiment. For each pressure
level in the constant volume depletion, a row in the *PVTCOND table for the saturated
properties is written. Individual *BGUST and VGUST tables are written for the gas formation
volume factors and gas viscosities corresponding to each saturation pressure in the *PVTCOND
table. Use of the feature is illustrated in the imex_condensate.dat template data set.
Regression on Secondary Stream Mole Fraction
The ability to select the mole fraction of the secondary stream, used to define the feed
composition for a calculation option, has been added to the regression calculation. The feed
composition can be defined as a mole fraction weighted mixture of the primary and
secondary compositions. This mole fraction can be adjusted during regression to match any
of WinProp’s allowable experimental data types. One application of this feature is to
determine the mole fraction of a separator gas stream necessary to recombine with a separator
oil stream to achieve a specified GOR. Use of this feature is illustrated in the template data
set regress_stream-frac.dat.
Automatic Selection of Regression Parameters
For users with limited experience in tuning equation of state parameters to match experimental
data, a facility is provided to automatically select regression parameters based on the types of
experimental data entered in the calculation options within the regression block. WinProp will
select a combination of critical properties of the heavy end pseudocomponents, volume shift
parameters, hydrocarbon binary interaction parameter exponents and viscosity parameters to be
adjusted during regression, depending on the experimental data entered. The automatic parameter
selector will not remove any parameters already selected by the user. Also, once the automatic
parameter selection process is complete, you may add or remove regression parameters manually.

Minimum Miscibility Enrichment Level
A minimum miscibility enrichment level option has been added to the multi-contact miscibility
calculation. This feature allows calculation of the minimum fraction of rich gas required to be
added to a lean gas stream to achieve multi-contact miscibility with an oil at a specified
pressure. A minimum rich gas fraction and a number of gas fraction steps are specified.
WinProp performs multiple-contact calculations for each step in the rich gas fraction, and
interpolates to determine the minimum enrichment level for multi-contact miscibility. Results
of the calculations for each solvent gas mixture tested are displayed on ternary diagrams.
This feature is an addition to the existing multi-contact calculation for determination of the
minimum miscibility pressure for a given oil and solvent.
K-Value Plotting
The phase property plotting feature has been enhanced to allow generation of K-value plots
for the 2-phase flash, multiphase flash, and the STARS K-value calculation options. Gas-
Liquid, Liquid-Liquid and Aqueous-Liquid K-value plots may be generated. The results are
shown as the log of the K-value for each component, plotted against pressure, temperature or
composition, depending on which independent variable has been specified for the flash.
STARS Fluid Model Generation Enhancements
The options for treatment of surface streams for STARS production reporting can now be
specified in WinProp. This includes specifying the surface pressure and temperature, the flash
options *SEGREGATED or *KVALUE and also the new option for specifying K-values
which are used only for the surface flash. The ability to specify these K-values separately
from the K-value tables allows the pressure and temperature range for the tables to be
concentrated on the expected reservoir conditions, but still calculate accurate surface phase
splits. Both Gas-Liquid and Liquid-Liquid K-values at the surface can be specified.
The extrapolation algorithm for determining component K-values outside of the range of
convergence of the flash calculations has also been improved.

Thermal Compositional Gradient Model
Beginning with the 97.00 release, WinProp has had the capability to perform isothermal
gravity/chemical equilibrium calculations for the determination of compositional grading due
to gravity. The 2001.10 release includes the option to incorporate thermal effects on the
gradient calculation. The model equations are developed based on the zero mass flux
condition. Calculations may be performed without thermal diffusion (passive thermal
gradient case) or with thermal diffusion coefficients determined from correlations or entered
as constant values for each component.

STARS PVT Data Generation Enhancements
A number of features for creating STARS component property and K-value data have been
added to WinProp. For component properties the following features have been implemented:
optional use of WinProp’s viscosity model for component viscosities as opposed to the
corresponding states model, optional output of viscosity versus temperature table instead of
correlation coefficients, and the generation of viscosity and density nonlinear mixing
functions. For K-value data, the features added include: generation of liquid-liquid and gas-
liquid K-value tables simultaneously, generation of composition dependent K-value tables,
use of STARS defaults for water K-values, indication of which K-values have been
extrapolated in the tables, and output of a map comparing the WinProp calculated phase split
to that determined from the K-value tables.
Please see the STARS PVT Data Generation section of the User’s Guide for more details.
WinProp-ModelBuilder Integration
Several features have been introduced to enhance the data flow between WinProp and
ModelBuilder. The concept of PVT “Meta-Data” has been introduced; this refers to the
equation of state model and mixture composition used to generate the PVT data for IMEX or
STARS (for GEM, the equation of state model used is the same as in WinProp, so Meta-Data
is not required). In this release of WinProp, the PVT Meta-Data will be written out to the file
with the IMEX fluid model. When this file is imported into ModelBuilder, the Meta-Data will
be read in and stored in the simulator data set. If it is desired at a later date to analyze or
modify the PVT data in some way, WinProp can be launched from within ModelBuilder and
the Meta-Data EOS description will be restored to WinProp.
The GEM EOS model can also be sent to WinProp by launching from within ModelBuilder.
In this case, compositions determined from the initial conditions section will be transferred to
WinProp as well.
Additional PVT Tables
An alternate format for black oil PVT tables has been added to the existing options for
creating various IMEX or extended black oil PVT tables. The alternate format includes
writing of the PVT table in order from highest to lowest pressure, and writing out a table of
multiplying factors for the undersaturated oil compressibilities and viscosities. Enhancements
to the extrapolation methods for generating PVT properties above the original saturation
pressure of the oil have also been implemented.
Laboratory Experiment Enhancements
The maximum number of separators which may be specified with the constant volume depletion
experiment and also for the black oil PVT data generation option has been increased to 8.
Liquid dropout for the constant composition and constant volume depletion experiments can
now be specified as a percentage of the cell volume at the saturation pressure, or as a
percentage of the cell volume at the current pressure step.

Interface Enhancements
The differential liberation and constant volume depletion experiment data entry forms have
been redesigned to allow entry of pressure step data in row format, for improved compatibility
with experimental PVT reports. Data for material balance and consistency check calculations is
now entered on a separate table which is linked to the main table with the pressure information.
Pasting of data to any grid which allows a variable number of rows has been modified to
automatically increase the number of rows in the table if required to hold all of the data being
input.

Automatic Generation of Quality Lines on Phase Diagrams
A feature has been added to the 2-phase envelope calculation option to allow the user to select
lines of constant mole or volume fraction to be calculated and displayed on the plot of the phase
envelope.
In addition the algorithm has been improved so that the initial guess for the starting point is
generated internally. The user no longer needs to initialize phase envelope calculations with a
flash or saturation pressure calculation or provide a good guess for the starting point directly.
It should now be possible to generate a 2 phase pressure temperature envelope with default
selections reliably.
Additional PVT Tables
For CMGL’s IMEX simulator, WinProp can now generate Gas-Water PVT tables.
“Extended” Black Oil type PVT tables can be generated including the Rv data describing oil
solubility in the vapor phase. These data are generated by simulating a constant volume
depletion or a differential liberation laboratory experiment. Oil properties are obtained by
material balance calculations or directly through EOS separator calculations. A number of
methods are available for extrapolating individual curves beyond the original saturation
pressure. These tables are output in a generic format. The user can then customize this data
for use with specific extended black oil reservoir simulation programs.
Additional Experimental Data
The constant composition expansion experiment option has been enhanced to allow regression
on the following experimental data: viscosity, density, compressibility factor and single phase
oil compressibility. These data are included in the regression only when the corresponding
property can be calculated by the program. For example single phase oil compressibility data
will not be used in regression for a dew point fluid.
Asphaltene Precipitation Modelling Case Study
A new case study is included in the User’s Guide and on-line help which describes the
development of a model for prediction of asphaltene precipitation from a black oil under
pressure depletion. The case study illustrates characterization of the oil, regression to match
fluid phase behavior data, specification of the asphaltene model parameters, and calibration
of the model with experimental precipitation data.
All of the case studies are now included in Appendix A.

A feature has been added to allow calculation options to be temporarily excluded from the
data set, rather than deleting them entirely. Options are excluded/included from the main
control form by right-clicking on the desired row and making a selection from the pop-up
menu. One application of this feature is to temporarily reduce the number of calculation
options within a regression block to try and obtain a match to some key data. After an initial
regression run, the component properties can be updated and calculation options that were
excluded can be included again for further regression runs.
Data entry and navigation on the grids has been improved by enabling use of the left and right
arrow keys, in addition to the up, down and enter keys.

Enhancements to Aqueous Phase Solubility Calculations
WinProp supports calculation of solubility of light gas and hydrocarbon components in the
aqueous phase using Henry’s law. This feature is enabled by selecting flash type OGW (Oil-
Gas-Water) on the OGW/EOS Multiphase Flash form. Henry’s law constants can be
entered by the user or calculated internally using correlations fit to experimental solubility
data. Two new features have been added for modelling aqueous phase solubility.
First, modification of the internally calculated Henry’s constants to account for salinity of the
aqueous phase has been implemented. By default, the internal Henry’s constants are for pure
water. To predict solubility of components in brine, all that is required is brine salinity, in
terms of equivalent NaCl concentration. This is entered on tab Aqueous phase of the
Components Selection/Properties form.
The second feature implemented is regression on the aqueous solubility parameters to match
experimental solubility data. Component reference Henry’s constants, i.e. Henry’s constant at
a specified reference pressure, and molar volume at infinite dilution can be adjusted to match
experimental data. Please see the “Components” section for further description of Henry’s
constants.
Case Study number two, in the “Tutorial” section, illustrates the use of both of these new
features.
Pedersen Viscosity Correlation
WinProp now allows use of the Pedersen corresponding states viscosity correlation in
addition to the Jossi-Stiel-Thodos (JST) correlation. The Pedersen correlation is expected to
give better liquid viscosity predictions for light and medium gravity oils than the JST model.
The Pedersen correlation is not dependent on having accurate density predictions as the JST
technique is. Parameters in either correlation may be adjusted during regression to match
experimental viscosity data. Please see the “Components” section for more information on
viscosity models.

Generation of PVT Properties for CMG’s IMEX Simulator
WinProp can now generate the PVT data corresponding to the light oil and the pseudo-
miscible models of CMG’s IMEX simulator. Earlier releases targeted the black oil model
only. In addition, the aqueous phase properties can now be estimated from built in
correlations as an alternative to entering the values directly. The PVT fluid model data with
the associated IMEX keywords is written to an output file with the extension (.imx). This file
can be referenced as an include file in an IMEX data file. Please refer to the “IMEX PVT
data generation” chapter of this manual for a complete discussion.
Consistency Checks and Material Balance Calculations
A number of tools are available in WinProp for evaluating the quality of PVT data provided
to the reservoir engineer from laboratory or field measurements. The data is typically used to
tune the EOS model. It is imperative therefore that the PVT data is analyzed critically prior to
any detailed regression calculations. The tools available include Hoffman plots and material
balance calculations.
Material balance calculations for the constant volume depletion (CVD), differential liberation
(DL) and separator options are performed if the required data is entered. For these experiments,
the required data are generally reported in a typical PVT report from a laboratory.
A Hoffman plot is generated for the recombination option based on the entered oil and gas
compositions. Hoffman plots are also created with the CVD, DL and separator options if
sufficient data is entered to calculate the oil phase compositions from a component material
balance. Refer to the chapter on “Laboratory Calculations” for more detail as well as
template cases matbal-bo.dat and matbal-gc.dat.
Changes to the Multiple Contact Miscibility (MCM) Option
A number of enhancements have been made to the MCM option with the objectives of 1)
alleviating difficulties in interpreting the program results and 2) determining and reporting
multiple and first contact miscibility pressures directly. With respect to point one, the criteria
used for stopping the forward and backward contact flash calculations are reported in the
output file. The most likely reasons are either miscibility is achieved or there is no change in
the oil and gas compositions from the previous contact. With respect to point two, the user
can now enter a range of pressures for the calculation. If multiple and/or first contact miscible
pressure(s) are found in this pressure interval then these values are reported at the end of the
output listing. Ternary diagrams are also automatically created at designated intervals.
Specification of Mole Fraction Steps for Flash Calculations
The ability to specify steps in the primary mole fraction making up the feed to a flash
calculation has been implemented for two-phase, multiphase and asphaltene/wax flash
calculations. This allows the specification of flashes for a number of mixtures of the primary
and secondary compositions on a single flash form. This feature is similar to the existing
capability for specifying pressure and temperature steps. These steps can be defined with the
feed specification on the first tab of each flash calculation.

Plotting Capability Added to Two-Phase and Multiphase Flash
When a series of flash calculations have been specified by setting temperature, pressure or
mole fraction steps, plots of the phase properties can be generated. Up to three phase
properties, such as molecular weight, compressibility factor or phase mole fraction, can be
selected for each flash calculation. One plot is generated for each property and each phase.
When plotting is activated, steps can be specified in one or two of the variables: pressure,
temperature and mole fraction. If steps are specified for only one variable, the plots are
generated with that variable as the independent variable, and the phase property as the
dependent variable. Up to 100 steps in the independent variable are allowed. When steps are
specified for two variables, one variable is treated as a parameter variable, and curves of the
phase property are displayed for each value of the parameter variable. Up to 8 steps in the
parameter variable are allowed.
The phase properties to be plotted are selected on tab Plot Control of the flash calculation
forms.
Plotting Capability Added to Asphaltene/Wax Flash
The asphaltene/wax flash has a plotting feature similar to the one described above for the
two-phase and multiphase flashes. This allows generation of plots such as weight %
precipitate as a function of solvent concentration or pressure.
A special plotting feature implemented for the asphaltene/wax flash is the generation of a
pseudo-ternary diagram to display the results of flash calculations in terms of the predicted
phase split, i.e. liquid-vapor, solid-liquid etc. The results are shown for a number of dilution
lines defined by the user.
Plot specification is done on tab Plot Control of the asphaltene/wax flash calculation.
Three-Phase Envelope Automatic Plot Generation
Automatic plot generation has been implemented for the three-phase boundary calculation.
Excel plots can now be created for three-phase P-T, P-X and T-X diagrams. These plots can
be created by selecting File|Create Excel plots after running a data set with a three-phase
envelope calculation option.
Ternary Diagram Two-Phase Envelope Generation
The capability to create ternary or pseudo-ternary two-phase boundaries has been added to the
two-phase envelope calculation option. This calculation locates points in composition space
defining the two-phase vapor-liquid phase boundary on a triangular diagram. This can be
considered a static or single-contact calculation, as opposed to the multiple contact calculation
option which performs a dynamic simulation of multiple contact miscibility processes.
This feature is enabled by selecting Pseudo-Ternary Phase Envelope on the Two-phase
envelope calculation option form.
Table Import Wizard
A Table Import Wizard has been implemented in WinProp to assist the user in importing data into
WinProp from existing Excel or ASCII format files. The wizard guides the user through the steps
of selecting data to be imported, defining units and performing unit conversions, and inserting the
imported data into the correct locations in WinProp’s data structure. Table import is available for
the following forms: Component Selection/Properties, Plus Fraction Splitting, Constant
Composition Expansion, Differential Liberation, Constant Volume Depletion and Swelling
Test. An example illustrating the use of the Table Import Wizard is given in the “Tutorial”
section of the manual. Information regarding the specific implementation for the forms listed
above may be found in the “Components”, “Component Splitting and Lumping”, and
“Laboratory Calculations” sections.
Two toolbars are provided for easier access to items previously available through the menus
alone. The main toolbar contains buttons corresponding to items in the File and Edit menus.
This toolbar targets frequently performed tasks such as opening and saving files, generating
the results, viewing the output file and creating plots. This toolbar is not customizable and is
permanently displayed. A second toolbar contains buttons corresponding to often used
calculation options. These buttons are grouped to mirror the organization of the menus. This
toolbar is customizable. The user can remove any of the buttons selected by default and add
buttons corresponding to options not originally chosen. Once the toolbar is customized the
settings are saved for subsequent sessions. The options toolbar can also be removed from the
interface and reinstituted at a later time.
The menu system is revised with the objective of creating more intuitive classes. Similarly,
the names of the forms corresponding to the calculation options are modified to be more
descriptive. Forms for the constant volume depletion, separator test and differential liberation
are redesigned in light of the additional data that can now be entered for material balance
calculations. Other enhancements include the addition of progress bars in specific situations.
A progress bar is shown when loading or saving the component form for example.

Additional Methods for Heavy Fraction Characterization
The three-parameter gamma distribution is now available in WinProp to describe the
molecular weight versus mole fraction relationship for the heavy fraction of a petroleum
fluid. The Gaussian quadrature method is used in evaluating the integral of this distribution
function. The molecular weight of the pseudo components selected corresponds to the
quadrature points. Good VLE results are obtained with this method with a small number of
pseudo components. In addition the Gamma distribution and Gaussian quadrature can be used
to generate a single set of pseudo components for multiple related samples with different plus
fraction molecular weight and specific gravity. Related mixtures have the same compounds
but in varying proportions, for example saturated oil and its equilibrium gas or fluids from
different depths in a reservoir with a compositional gradient. Parameters of the Gaussian
distribution function are obtained by nonlinear regression if extended analysis data is entered
or from generalized correlations if only plus fraction specific gravity and molecular weight
are available. Where multiple samples are involved each sample can have extended analysis
data entered if available. Please refer to the “Component Splitting and Lumping chapter of
this manual for a more extensive discussion.

Generation of PVT Properties for IMEX Black Oil Model
WinProp can now generate the PVT data corresponding to the “black oil” model of CMG’s
IMEX simulator. This data is written out to an output file with the extension blk. This file can
then be referenced as an include file in an IMEX data file. The properties of the oil phase
(formation volume factor, gas oil ratio) are generated by flashing the equilibrium liquid at each
stage of the “differential liberation” directly through the user specified separator train. The
range of the PVT table can be extended to include pressures above the original oil bubble point
pressure by generating the swelling curve. This way the table can handle variable bubble point
scenarios arising for example from gas injection or solution gas migration followed by re-
pressurization. This option can be found under Options | "Black oil model PVT data." Please
refer to the “Black oil PVT data generation chapter of this manual for a complete discussion.
Process Flow and Isenthalpic Flash Options
Data entry forms for the Process flow and Isenthalpic flash options have been added to
WinProp. The process flow option can be added to the data file by selecting Calculations |
Process flow from the menu and isenthalpic flash by selecting Calculations | Isenthalpic
flash. For the process flow sample template are process1.dat, process2.dat and process3.dat.
For isenthalpic flash the sample templates are isenth1.dat, isenth2.dat and isenth3.dat. Please
refer to the chapter titled “Process flow” for detailed discussion of the process flow option
and the “Flash calculations chapter for more details on the isenthalpic flash option.
Support for Multiple Hydrocarbon-Hydrocarbon Binary Interaction Exponents
Hydrocarbon components are identified by a value of 1 on the HC column of the component
table on the Component form. Binary interaction coefficients between two hydrocarbon
components are calculated from a correlation, which involves the critical volume of each
component and an exponent parameter. In contrast to previous versions of WinProp where all
HC-HC binaries were calculated based on a single exponent parameter, the user can now
group pairs of binary and specify a different exponent parameter value for each group. These
individual group exponents can be also selected as regression parameter(s). Please see the
chapter entitles “Components and “Regression for more details.
Handling of the “Regression Block” in a Data File
In WinProp the regression block refers to the calculation options that are between the
“Regression” and “Start regression” forms. For a case to run successfully all options in this
block must have at least one piece of experimental data entered and all options outside the
regression block are required not to have any experimental data entered. WinProp will now
attempt to ensure that these requirements are met when the user attempts to run a given case
while preserving the data that has been entered. For example if there an option within the
regression block then this option will be moved out of the regression block. If there is an
option with experimental data outside the regression block then the experimental data will be
written out to the data file with the accompanying keyword(s) commented out.
This will also allow the user to retain the experimental data that were entered for regression
when regression is removed from the data file, that is “Regression” and “End regression”
forms are removed. The entered experimental data will be shown where appropriate with the
program predictions on plots even if there is no regression involved in the run.

The list of the five most recently files accessed by WinProp is now available on the File
menu. This is a faster way of selecting a case than through the file open dialog box.
Interface enhancements include the ability to redirect the screen diary to an output file. To
redirect select “Redirect to file DBPROP.XXX” under File | Screen menu. The user can now
select an editor other than Notepad by invoking the Editor | “User editor select” option
under the File menu. This will open a file dialog box. Using the file dialog select the
executable file corresponding to the desired editor.
WinProp allows up to open up to 8 different cases (data files) to be open simultaneously,
primarily to allow various calculation option forms to be copied between different data files.
This saves the user from having to type in data values multiple times. The MDI capability
also facilitates comparing the data entered for a given form across data files. A number of
checks have been implemented to avoid violating the internal design limitations of this
option. For example forms can be opened only when a single case is loaded and a case cannot
be closed until all the open forms are closed.
In previous versions of WinProp the data in a table (grid) could be changed via a text box
positioned outside the table. With WinProp 98.00 a floating text box positioned exactly on the
desired cell is used for table (grid) edits. To erase the current value or text in a cell and enter a new
value or text, position the cursor on that cell and start typing. To edit the contents of a cell,
position the cursor on that cell and double click with the left mouse button. The cell contents are
updated when the carriage return (Enter) key is pressed or if the cursor is moved to another cell.
Please note that changing the focus to a new control will not update the grid (table) contents.

Compositional Grading Calculations
Significant compositional variation with depth can occur in deep reservoirs with near critical
fluids or for fluids where there is a large variation in molecular weight between the light and
heavy constituents. This effect is important in estimating materials in place as well as field
development and operation strategy. WinProp now has the capability of simulating this
phenomena based on the isothermal gravity/chemical equilibrium (GCE) formulation. This
option can be found under Calculation Options|Compositional Gradient. A complete
discussion can be found in the chapter titled Compositional Grading.
Generation of PVT Properties for STARS
STARS is CMG's steam and additive thermal simulator. WinProp can generate the complete
PVT data required by STARS. This includes component partial densities, compressibility and
thermal expansion factors as well as liquid component viscosity coefficients. WinProp can
also generate tabular K-value data between any two phases that STARS supports. STARS
used K-values to determine the number of phases in equilibrium and the composition of each
phase. The PVT data is printed in a format suitable for direct inclusion in a STARS data file.
The output of this option is directed to a file with a suffix .tbl. This option can be found under
Options|Print STARS PVT Table. Please refer to the STARS PVT Data Generation
chapter of this manual for a more extensive discussion.

Regression Enhancements
It is now possible to specify more than one component for a given property such as the
critical pressure as a single variable in regression. The members of the group will in general
have individual initial values and bounds. In regression the same increment is applied to all
members of the group. This feature can be useful if it is desired to maintain a certain trend or
symmetry for a given property or in avoiding regressing on a property belonging to a
component with a small mole fraction. For information on how to define group variables
refer to the Regression chapter of this manual.
Summary plots showing before regression, after regression and experimental data are now
generated automatically when Excel plots are created from a regression run. Individual plots
showing calculated results are still available, with new titles indicating before or after
regression calculations.
Conversion from CMGPROP to WinProp Format
A conversion utility is provided within WinProp to translate files created for CMGPROP on
UNIX or PC platforms. This utility can be invoked by selecting Options|Convert from
Cmgprop to WinProp. The user is advised to open each form and verify the results of the
conversion carefully. Please use the Save As option under the File menu to save the
WinProp compatible data file to avoid overwriting the original CMGPROP data file. The
original file will be an important aid in case difficulties are encountered in conversion and in
verifying the conversion. There are a number of situations that can pose difficulties for the
converter including the use of wildcards in specifying array values and presence of comment
marker on a line where array values are stipulated. Please edit the CMGPROP data file
eliminating these situations prior to using the conversion utility.
MDI Capability
The Multiple Document Interface (MDI) Feature is now implemented in WinProp. This
allows the user to open up to eight files at once. This has significant advantages for example
when the user desires to compare output files for two or more cases or in the ease with which data
corresponding to various calculation options may be copied between different data files. Refer to
the section copying between different data files under the Tutorial chapter of this manual.
Update Component Properties Feature
Upon completing a splitting, lumping or regression calculation where the number of
components are changed or the component properties modified, WinProp writes out the
revised component information in an output file with the suffix .rls. With the previous version
of WinProp the user would run a file, for example test1.dat with a splitting calculation, use
File|Open to open test1.rls, use File|Save As to rename to test2.dat for example and then
continue working with this file by appending calculation options to it. This procedure is now
automated with the introduction of the update component properties selection under the
Options menu. The user still runs the splitting calculation with test1.dat. Once the calculation
is carried out, update component properties is invoked. This updates the information on the
Composition and Component forms. The user then removes the splitting calculation from the
data file and appends the desired calculation options. Optionally the user may wish to save this
file with a different file name say test2.dat to retain a complete work record of the session.

Addition of Bounds Tab on the Regression Form
An additional tab showing the initial value and the lower and upper bound selected by WinProp
for each regression variable specified has been added to the Regression form. The user may
subsequently edit the bounds. The capability to restore values back to their default selections is
provided as well. This provides the user greater flexibility in arriving at an EOS description based
on the specific characteristics of the fluid being considered and the PVT data available.
Volume Shift Specification
Additional flexibility is introduced in selecting values for the volume shift parameter for each
component. Previously the default was a value of zero for all components. The new default is a
value generated from the correlation for library components and a value of zero for user defined
components. The user may apply the correlation values to all components by selecting Reset to
Correlation Values from the Volume Shift menu on the component form. Alternatively the user
may revert to the older default by selecting Reset to Zeros. The user can still specify a value for
any component which is different from either correlation or zero by editing the cell directly.
Support of Two Sets of EOS Parameters
WinProp now supports the concept of two different EOS models. When two sets are enabled
the first set is used for calculations at reservoir conditions and the second set for surface or
separator conditions. With this provision it is possible to match PVT experimental data at
surface conditions (typically separator API and GOR data) independently from data at reservoir
conditions. This makes it possible to obtain much more accurate predictions over the wide
range of conditions encountered as the fluid is produced and processed on the surface with a
realistic number of components for compositional simulation. Please refer to the Component
and Regression chapters for details.
Extended Separator Option
The conventional separator operation involves the liquid phase output from a given separator
becoming the feed for the next separator in sequence downstream and the vapor phase joining
the gas product stream. This arrangement is not always optimal particularly for rich gas
condensates. For modeling alternative separation strategies the separator option is enhanced to
allow additional product streams such as LPG and in providing flexibility in the selection of the
destination of the liquid and vapor stream from each separator. Please review the section on
separator calculation in chapter Laboratory Calculations for more information of this feature.
Multicomponent Solid Precipitation Model
The solid precipitation model is now suitable for modeling both wax and asphaltene
precipitation scenarios. The thermodynamic model has been enhanced as follows: the
precipitate is now modeled as a multicomponent solid in contrast to the earlier single
component pure solid phase assumption, non-isothermal conditions are treated, and up to
three fluid phases in equilibrium with the solid are allowed.

Introduction
What is WinProp?
Welcome to WinProp, the Windows version of CMGPROP.
WinProp is CMG's equation of state multiphase equilibrium property package featuring fluid
characterization, lumping of components, matching of laboratory data through regression,
simulation of multiple contact processes, phase diagram construction, solids precipitation,
and more. Laboratory experiments considered in WinProp include recombination of
separator oil and gas, compressibility measurements, constant composition expansion,
differential liberation, separator test, constant volume depletion and swelling test.
You can use WinProp to analyze the phase behavior of reservoir gas and oil systems, and to
generate component properties for CMG's compositional simulator GEM, black oil simulator
IMEX and steam and additives thermal simulator STARS.
WinProp contains a graphical interface that allows you to prepare data, run the phase property
calculation engine, view the output with an editor, and create plots with Excel™.
WinProp creates keyword data files to drive the phase behavior calculation engine. Besides
the regular keywords that were required by the CMGPROP program, these data files contain
special control character strings for the graphical interface. A conversion utility is provided
within WinProp for users who have been using CMGPROP on a UNIX platform or on the PC
to facilitate the migration to WinProp.
User's Guide WinProp Introduction • 17

Use of this Manual
This User's Guide describes the different forms and options for entering data into WinProp.
It is also available as on-line help. This User's Guide is aimed at reservoir engineers with
some background knowledge on the phase behavior and characterization of reservoir fluids.
Good references on these topics can be found in Ahmed [1], Pedersen, Fredenslund, and
Thomassen [30] and McCain [17] (see the “References” section). For more details on phase
equilibrium thermodynamics, please see Sandler [35] or Walas [37].
Every attempt has been made in the preparation of this User's Guide to provide you with all
of the information necessary to run the program and understand the calculations being
performed. If questions arise, please contact:
#150, 3553 – 31 Street N.W.
Calgary, Canada T2L 2K7
Telephone: (403) 531-1300
Fax: (403) 289-8502
Email: support@cmgl.ca Website: www.cmgl.ca
Installation
All CMG software must be installed from the CD-ROM by running the Setup program.
Please refer to the detailed installation instructions that are packaged with the software for
additional information.
Confidentiality
All components of CMG's technology including software and related documentation are
protected by copyright, trademark and secrecy. CMG technology can be used only as
permitted by your license from CMG. By the license, you have agreed to keep all CMG
technology confidential and not disclose it to any third party. All rights reserved. No part of
this publication may be reproduced or transmitted in any form or by any means, electronic,
mechanical, or otherwise, including photocopying, recording, or by any information
storage/retrieval system, to any party other than the licensee, without the written permission
of Computer Modelling Group Ltd.
18 • Introduction User's Guide WinProp

Template Data Files
A number of example data files are located in the "TPL" directory located under the WinProp
directory. A brief description of each of the available template data files is shown below:
Data file name Description
AqueousCO2-08-Harvey.dat Aqueous phase properties calculation using Harvey’s method
case_study-1.dat Data for case study number 1 (See Appendix A)
case_study-2.dat Data for case study number 2 (See Appendix A)
case_study-3-asph.dat Data for case study number 3 (See Appendix A)
case_study-3-regress.dat Data for case study number 3 (See Appendix A)
case_study-3-split.dat Data for case study number 3 (See Appendix A)
cce.dat Constant composition expansion calculation
compgrad-blackoil.dat Compositional gradient calculation - black oil
compgrad-voloil.dat Compositional gradient calculation - volatile oil
compress.dat Single-phase liquid compressibility calculation
cricon.dat Cricondenbar and cricondentherm calculation
critical.dat Critical point calculation
cvd.dat Constant volume depletion simulation
diflib.dat Differential liberation experiment simulation
envel_2ph-pt.dat Two-phase pressure-temperature envelope construction
envel_2ph-px.dat Two-phase pressure-composition envelope construction
envel_2ph-tern.dat Two-phase pseudo-ternary diagram construction
envel_3ph-pt.dat Three-phase pressure-temperature envelope construction
envel_3ph-px.dat Three-phase pressure-composition envelope construction
extended_blackoil.dat Extended black oil PVT tables with oil vaporization
flash-2ph.dat Two-phase EOS flash calculation
flash-3ph.dat Three-phase EOS flash calculation
flash-isenth1.dat Isenthalpic flash - 2 component system
flash-isenth2.dat Isenthalpic flash - 6 component system
flash-isenth3.dat Isenthalpic flash - single component system
flash-ogw.dat Three-phase oil-gas-water Henry's law flash calculation
format2_blackoil.dat Alternate format black oil PVT tables
imex_condensate.dat IMEX gas-water with condensate PVT model data generation
imex_voloil.dat IMEX volatile oil PVT model data generation
imex-blackoil.dat IMEX PVT model data generation
labpvt-bo1.dat Lab PVT experiment simulations – black oil no. 1
labpvt-gc1.dat Lab PVT experiment simulations – gas condensate no. 1
lumping.dat Lumping "plus fraction" components
matbal-bo.dat Material balance checks for black oil PVT experiments
matbal-gc.dat Material balance checks for condensate PVT experiments
User's Guide WinProp Introduction • 19
mcm-condensing.dat Condensing gas drive multicontact miscibility calculation
mcm-vaporizing-co2.dat Vaporizing CO2 drive multicontact miscibility calculation
mcm-combined-H95-8lean.dat Condensing and vaporizing combined drive MMP calculation
mcm-combined-U2002rich.dat Condensing and vaporizing combined drive MMP calculation
mcm-Z12-5-MME.dat Condensing and vaporizing combined drive MME calculation
process-cvd.dat Process flow – simulation of constant volume depletion test
process-mcm.dat Process flow – simulation of multiple contact experiment
process-plant.dat Process flow – simulation of a gas plant
recombine.dat Recombination of separator oil and gas streams
regress-blackoil1.dat Black oil no. 1 regression
regress-blackoil2.dat Black oil no. 2 regression
regress-compress.dat Liquid compressibility regression
regress-condensate1.dat Gas condensate no. 1 regression
regress-condensate2.dat Gas condensate no. 2 regression
regress-critical.dat Critical point regression
regress-flash_2ph.dat Two-phase flash regression
regress-flash_3ph.dat Three-phase EOS flash regression
regress-flash_ogw.dat Three-phase Henry's law flash regression
regress-lightoil.dat Light oil regression
regress-multicontact.dat Multiple contact data regression
regress-sat_pres.dat Saturation pressure regression
regress-separator.dat Separator data matching with 2nd EOS set parameters
regress-singlephase.dat Single phase properties regression
regress-viscosity.dat Regression for viscosity matching
sat-pressure.dat Saturation pressure calculation
sat-temperature.dat Saturation temperature calculation
separator.dat Separator calculation
singlephase.dat Single-phase fluid properties calculation
solid-asph_plots.dat Plot construction for single component asphaltene model
solid-asph1.dat Single component solid asphaltene precipitation
solid-asph2.dat Heavy oil with 2 component solid precipitation
solid-phenanthrene.dat Pure component solid (phenanthrene) precipitation
solid-wax.dat Multicomponent wax precipitation
split-mw_analysis.dat Characterization - MW versus mole fraction data
split-mwsg_analysis.dat Characterization - MW, SG versus mole fraction data
split-mwsg_plus.dat Characterization – plus fraction MW and SG only
split-mwsgtb_analysis.dat Characterization - MW, SG ,TB versus mole fraction data
stars-comp_props.dat Component PVT properties generation for STARS
stars-vl_kvalues.dat Vapor -Liquid K-values generation for STARS
stars-vlaq_kvalues.dat Vapor -Liquid-aqueous K-values generation for STARS
stars-vls_kvalues.dat Vapor -Liquid-solid K-values generation for STARS
swelling.dat Swelling experiment simulation
20 • Introduction User's Guide WinProp

Tutorial Section
Overview
This chapter includes information on the mechanics of creating, editing, saving and running
data sets in WinProp, as well as viewing the output files and creating plots.
Example case studies with step-by-step instructions for performing some PVT modelling
tasks are described in Appendix A.
Detailed instructions for using all of the calculation options available in WinProp are given in
the remaining chapters.
Getting On-Line Help

Selection of Help on the menu provides you with the following options:
Contents The table of contents for the help file is displayed

Search for Help on... You can search for help on a particular topic
Help on current form The help on the current form is displayed
The help on current form can be also invoked by pressing the function key F1
Creating, Opening and Saving Data Files

You can create a new data file by selecting File|New from the menu. WinProp puts three
undefined forms in the data set: Titles/EOS/Units, Component Specification/Properties,
and Composition. An existing data file can be opened by selecting File|Open.... A file
browser will appear to assist you in the file selection.
You save a data file by selecting File|Save. A data file can be saved under a different file
name by selecting File|Save As....
By convention all data set names have the (.DAT) suffix. The following files are created
when running WinProp:
User's Guide WinProp Tutorial Section • 21

File suffix Description
.out ASCII file containing calculation results.
.gem Output of component properties in a format suitable for the
compositional simulator GEM.
.gmz Output of composition versus depth data in format suitable for inclusion
within the GEM simulator data file.
.str Output of PVT data in format suitable for inclusion within STARS
simulator data file.
.imx Output of the “black oil”, “light oil” or “pseudo-miscible” model PVT
data in format suitable for inclusion within the IMEX simulator data file
or extended black oil tables in a “generic” format.
.rls Output of component properties from the regression or lumping and
splitting procedure.
.srf Output for plotting.
.xls Excel™ file containing data and plots that are created from an .srf file.
The results are written to files with the (.out) suffix. When you invoke the regression or
lumping or splitting procedures, WinProp also creates a file with the suffix (.rls.) This file can
be opened to create a new data set (see Chapters on “Component splitting and lumping”
and “Regression”). If you select the component printing option for CMG’s compositional
simulator GEM on the form CMG GEM EOS Model, the component properties are printed
to a file with the suffix (.gem) in a format suitable for GEM. If the CMG STARS PVT Data
option is selected then an output file with the suffix (.str) is created. If the “Write GEM
*ZDEPTH …” checkbox on the Compositional Gradient form is checked off then the
composition versus depth information is written out to a file with the suffix (.gmz.). If the
calculation option to generate PVT data for simulation studies with IMEX is included in the
data set then a file with the suffix (.imx) is created. This file contains PVT data in a format
compatible with IMEX and can be referenced as an include file in an IMEX data file.
Select File|Exit to exit WinProp.
Running, Viewing Output and Creating Plots

To run the current data set, select File|Run from the menu (or use F2 key).
The results of the calculations are in a (.out) ASCII file. To view this file with an ASCII text
editor, select File|View output (or use F3 key). The default editor for output viewing is
Windows Notepad. The option is also available to use another editor of your choice. You
can specify which editor to use by selecting Preferences|Editor|User editor select from the
menu. This will open a file dialog box. The desired editor is selecting by identifying the
executable file for that editor.
22 • Tutorial Section User's Guide WinProp

Certain calculation options will create data for plotting. The plot information is in the (.srf) file. To
create these plots with Excel™, select File|Create Excel plots (or type F4). WinProp has its own
Excel™ templates and macros to invoke Excel™ and generate the corresponding plots. These
Excel™ plots are saved in an (.xls) file. If no plot data are available, a message will be issued.
To view an Excel™ plot that you have already created with WinProp, select File|View Excel
plots.
Copying Between Different Data Files

With the MDI implementation of WinProp the user may open as many as eight data files or
associated files (such as the output file) for side by side comparisons or to transfer data
between data files. To transfer calculation options between data sets: open the source and
target files, highlight the desired rows on the data set structure form of the source file and
select Copy from the Edit menu or by pressing the Ctrl C key combination. Next, click on
the row of the data set structure form of the target file to select the insertion location and
select Paste from the Edit menu or type the Ctrl V key combination.
Setting Up a Regression Run

Certain calculation options including the simulation of laboratory PVT experiments allow the
user to optionally enter experimental data which can be used to tune the EOS model. The
Regression Parameters and End Regression forms bracket the calculation options for which
data is entered. Note: All options that appear within the regression section must have at least
one experimental data point. The Regression Parameters form is used to select the specific
EOS component properties for tuning. For calculation options specified prior to the appearance
of the Regression Parameters form the program uses the original component properties. For
options appended after the End Regression form the component properties modified during
regression are used. Note: WinProp only allows one Regression Parameters and one End
Regression form per data set. To perform a second regression calculation first use the Update
component properties feature located under the File menu.
Using the Update Component Properties Feature of WinProp

Quite often the user is in possession of limited information on the composition of the reservoir
fluid. This typically means a breakdown from C1 to C5 with the heavy end lumped as C6+ for
which only the molecular weight and specific gravity information is available. In order to
obtain reasonably accurate results with an EOS the heavy end must be described by more than
one pseudo-component. This step is known as characterization or splitting. Since this
procedure requires approximating a continuous distribution with a number of discrete
components with limited experimental data for the heavy end, the pseudo-components
properties are considered to be approximate and therefore suitable candidates for tuning to
match available PVT experimental data. The splitting - regression sequence needs to be done in
two steps since prior to the splitting calculation the pseudo-components do not exist to enable
various properties such Pc or Tc to be selected for regression. The execution of this two step
process can be done efficiently with the help of the Update component properties feature of
WinProp. The process generally involves the following sequence:

1. Set up the splitting calculation. Add the form for performing the splitting calculation
to the WinProp data file. Open the Component Selection/Properties form. The
compositional analysis up to C5 involves components with known properties. Add
these components by selecting Add Component|LibraryComponent. Open the
Composition form and enter the mole fractions as they appear on the laboratory
report. Ignore the warning message about the sum not being equal to one. Open the
Plus Fraction Splitting form and enter data for the plus fraction.
2. Run WinProp with the data file from step 1. Once the splitting calculation is
performed WinProp writes out the full set of component properties including data
for the pseudo-components in a special output file with the suffix (.rls). Open the
File menu and select Update component properties option. WinProp will then
read the (.rls) file and update the Composition and Component
Selection/Properties forms based on the data in this file.
3. Remove the splitting form from the data set by highlighting the splitting
calculation row on the data set structure form and selecting Edit|Cut from the
menu. Proceed to set up the regression run as described in the section “Setting up
a regression run”.
View the Keyword Data File Created by WinProp

Under the File menu item, selecting View data for current option loads the keywords
corresponding to a given calculation option (or form) in a text window, while the entire
keyword file can be viewed by selecting View data set. This can be a useful aid in
troubleshooting if the results are unexpected or there is difficulty running the program.
Selecting a User-Defined Editor

Under the Preferences|Editor menu item, there are two choices for selecting the device used
for viewing WinProp output: Windows notepad and a user defined editor. The default device
for the user defined editor is the "DOS EDIT" program. To set this to another editor of your
choice, choose the Select user editor option under Preferences|Editor. This will bring up a
file dialog box. Browse to the folder where the executable file for the desired editor is
located. Select the executable file (typically with extension (.exe) or .(com)) for the preferred
editor. The selection made will be honored until a new choice is made.
Editing the Data Set

Editing Data Set Structure
In addition to inserting calculation options as described in the Section “Data Set Structure”,
you can edit the data set by selecting Edit from the menu. The edit operations will apply to the
calculation options that are currently highlighted. The following menu items are available:

Undo This will undo the previous edit function. This menu item is not available
if there is nothing to undo.
Cut This option will cut the options and the data associated with them into the
Clipboard. You cannot cut the Titles/EOS/Units or the Component
Selection/Properties forms.
Copy This option will copy the options and the data associated with them into the
Clipboard.
Paste This option will paste the data from the Clipboard into the current data set.
You can use the Copy and Paste option to transfer information and calculation options within
one WinProp data set or from one data set to another.
Editing Tables
On many forms, you enter data into tables (or grids). For most tables, you can use the menu
item Table to insert a new row or delete rows.
You can highlight the data in different cells with the left mouse button. You can delete, cut
and paste data corresponding to the highlighted cells with the standard Windows keystrokes:
DELETE for delete, CTRL+C for copy, CTRL+X for cut, and CTRL+V for paste. Note
that DELETE clears the data in cells, but does not delete the corresponding rows. Please use
Table|Delete rows if you want to delete rows.
Table Import Wizard

Overview
The Table Import Wizard is designed to assist the user in importing data such as component
properties and laboratory experiment results into WinProp. The wizard is available for the
following forms: Component Selection/Properties, Plus Fraction Splitting, Constant
Composition Expansion, Differential Liberation, Constant Volume Depletion and
Swelling Test. An example is given below illustrating the use of the Table Import Wizard.
Information regarding the specific implementation for the forms listed above may be found in
the “Components”, “Component Splitting and Lumping” and “Laboratory Calculations”
sections of the manual. The wizard supports the following features:
1. Tabular information can be directly imported from Excel™ spreadsheets or ASCII
format files.
2. Entire tables need not be imported. Parts of a spreadsheet/file can be extracted and
imported into WinProp.
3. The regions being imported from the original table need not be contiguous.
4. The table imported into WinProp can be saved as a new file.
5. There is no restriction that the table being imported from has the same column
arrangement as required in WinProp.

6. Unit conversions can be performed on the table before importing it into WinProp.
Unit systems can be selected for the entire table. Units can also be selected for
individual columns.
Using the Table Import Wizard
The Table Import Wizard guides the user through the steps required to import data into
WinProp. The wizard is launched by clicking on a command button labeled Table Import
Wizard on the forms mentioned in the overview. An example illustrating the import of
component property data from an Excel™ file is shown here.
Step 1: Provide file for table import from
In this step the file which contains the table to be imported is identified. This file could be an
Excel™ spreadsheet or an ASCII file. Indicate the desired file type by clicking on one of the
option buttons labeled ASCII or Excel. Click on the Browse... button to locate the file.
Click on Next to continue.

Step 2: Choose a worksheet
This step appears as step 2 if an Excel spreadsheet was selected in Step1. Since a spreadsheet
can have several worksheets, this step requires the identification of the worksheet that contains
the data to be imported. The worksheets are listed in a list box at the top right corner. Once a
worksheet is highlighted, data from that worksheet is displayed as in the example below.

Click on Next to continue.
Step 4: Select regions to be imported and define column names
Step 3 is relevant only when importing from ASCII files and is skipped since this example
involves importing from a spreadsheet. In step 4, the regions from the original table to be
imported are identified and names are defined for all imported columns. Multiple ranges of
columns can be selected, but a common set of rows must be selected for all columns. Before
selecting the data, the table rows and columns can be transposed. If your data is in row-wise
format, it can be transposed to allow definition of data types by column, as required by the
table import wizard.
Column names are selected by clicking on the right mouse button at the column header. This
brings up a pop-up menu containing the available column names. Select the name that
corresponds to the column from the menu.
In the view of Step 4 shown below, the data corresponding to all columns except the Watson
K-factor has been selected, and the column names defined.

Click Next to continue.
Step 5: Review table definition and edit data
Step 5 can be used to review the table selections and edit values in the table before going on
to select the units for the columns. The table can be inverted by clicking the right mouse
button on the table and selecting Invert table from the pop-up menu that appears.
The component table now appears as follows:
Click Next to continue.

Step 6: Choose units of table columns
In this step, the units used in the source table need to be identified. A base unit system is
defined first. Units can then be set for individual columns as required by right-clicking on the
column header and selecting the unit for that column from the pop-up menu. The units
corresponding to the critical properties for this example have been selected as shown below.
It is important to note that selection of units in this step should correspond to the units used in the
original file from which the table is being imported. No unit conversion is done at this stage.
At this point, the table import may be completed by clicking on the Finish button. Any
conversions to the current WinProp unit system will be performed and the data will be
entered into the WinProp table.
To view the table with quantities converted to different units or to save the table to a file,
check on the box labeled Apply unit conversion and click Next to continue.
Step 7: Choose units for table columns to convert data to
In this step, the user has a choice of viewing the table with different units applied. Note that
changing the units in this step does not affect what units will be used to display the data in
WinProp. The table can also be saved to a separate file by clicking on the button labeled
Save converted table to NEW file. In this example, the table from the previous step is
shown after conversion to field units.

Click Finish to exit Table Import Wizard and complete the import of data into WinProp.

Data Set Structure
Overview
This form contains the structure of the data set. This is the first form presented to the user when
WinProp is invoked. The column of the table labeled Forms contains the title for each
calculation form included in the data set. By default the required forms Titles/EOS/Units, and
Component Selection/Properties are pre-selected and cannot be removed. The Composition
form is also required following these forms, thus it is included by default as well.
The data entry form corresponding to a given row can be activated by double clicking on that
row. Data can be entered and edited on each form.
To insert a calculation option: (1) select the row where the new calculation will be inserted by
clicking on that row; (2) select a calculation option from the menu or by clicking one of the
buttons on the calculation option toolbar.
The Inc (Included) column indicates whether or not a calculation option will be executed
when the data set is run. A checkmark in this column indicates that the option will be
included, while an X-mark indicates that the calculation will be excluded. Calculations can be
included/excluded by right-clicking on the desired row and selecting Include Calculation or
Exclude Calculation from the pop-up menu.
User's Guide WinProp Data Set Structure • 31

A “U” in the Stat (Status) column indicates that the data for the corresponding option are
undefined. Once data for a particular form are entered as described above, the “U” will be
cleared from the status column.
The text in the Comments column comes from the Comments text box on each form. These
comments are also printed in the output file for each calculation option.
Editing Data Set

Editing Data Set Structure
In addition to inserting calculation options as described in the Section “Data Set Structure”,
you can edit the data set by selecting Edit from the menu. The menu items apply to the
calculation options that are highlighted. The following menu items are available:
Undo This will undo the previous edit function. This menu item is not
available if there is nothing to undo.
Cut This option will cut the options and the data associated with them into the
Clipboard. You cannot cut the Titles/EOS/Units or the Component
Selection/Properties forms.
Copy This option will copy the options and the data associated with them into
the Clipboard.
Paste This option will paste the data from the Clipboard into the current data
set.
You can use the Copy and Paste option to transfer information and calculation options within
one WinProp data set or from one data set to another.
32 • Data Set Structure User's Guide WinProp

Titles/EOS/Units Selection
Overview
This form is pre-selected by WinProp and appears as the first form in all WinProp data files.
It is used for documenting the run, selecting the unit system and for choosing the equation of
state (EOS) to be used for all calculations included in the data file.
Data Input
Comments
Enter your comments regarding this data set. These comments will be shown in the Data set
structure form.
Title 1, Title 2, Title 3
Enter up to 3 titles to identify the runs.
User's Guide WinProp Titles/EOS/Units Selection • 33

Equation of State
Selection of the equation of state for the oil and gas phases. The default is PR (1978).
PR(1978) Peng-Robinson equation of state with 1978 expression for
constant "a".
PR(1976) Peng-Robinson equation of state with 1976 expression for
constant "a". This is the original equation of state.
SRK(G&D) Soave-Redlich-Kwong equation of state with the constant "a"
proposed by Graboski and Daubert[6].
SRK Original Soave-Redlich-Kwong equation of state.
Units
psia & deg F Pressures in psia and temperatures in ºF.
kPa & deg C Pressures in kPa and temperatures in ºC.
kg/cm2 & deg C Pressures in kg/cm2 and temperatures in ºC.
Feed
Mole The feed on Form Composition is in moles, mole fractions, or
mole percent.
Mass The feed on Form Composition is in mass (e.g. kg), mass
fractions, or mass percent.
When the Mass option is selected, WinProp converts all mass fractions to mole fractions
using the component molecular weights. All outputs will contain the corresponding mole
fractions and not the input mass fractions.
34 • Titles/EOS/Units Selection User's Guide WinProp

Components
Component Selection and Definition

The equation of state requires the following properties for each component critical pressure (Pc),
critical temperature (Tc), acentric factor (ω), and interaction coefficients between different
components (δij). The molecular weight is also required to calculate mass densities. Additional
factors such as the volume shifts τ, and the parameters Ωa and Ωb can also be defined for each
component to enhance the equation of state predictions. A complete description for all of the
properties in the component table is given in the "Component properties" section of this chapter.
To select or edit components, double click on the row Component Selection/Properties of
the data set structure form. This will bring up the Component Selection/Properties form.
You can select components from WinProp’s component library or define your own components
as described below.
Library Components
To choose library components, select Options|Insert library components from the menu.
The following form will be activated:
User's Guide WinProp Components • 35

Select components from the list by clicking on them with the left mouse button. Use the
<Shift> and <Control> keys for multiple selections. Pure hydrocarbon components, light
gases and water may be selected from the library, as well as generalized single carbon
number (SCN) petroleum fractions FC6 through FC45. The specific gravities, molecular
weights and boiling points of the SCN fractions are taken from Whitson (1983). The critical
properties of these fractions are calculated with the Lee-Kesler correlations (Kesler and Lee,
(1976)). The component molecular weights are shown in brackets for each component
primarily to allow the user to select generalized SCN fractions to approximate a heavy end of
known molecular weight. The order in which components are selected depends on the
sequence of mouse clicks. Click on View selection order to view this order. The component
order is important for lumping into pseudo-components, as only components that are adjacent
to one another can be lumped together.
User Component with Known Properties
If you have a component with known critical properties, you can insert this component by
choosing Options|Insert own component|Critical properties. This will activate the
following form:
The critical pressure, critical temperature, acentric factor and molecular weight are required
input. Values will be estimated for any of the OPTIONAL DATA parameter fields that are
left blank. Critical compressibility is used only to calculate critical volume. Critical volume
is used in the calculation of binary interaction parameters (see the section on “Interaction
Coefficients” below). Specific gravity and boiling point temperature are used to estimate
ideal gas enthalpy coefficients. Specific gravity is also used along with the critical properties
to estimate Rackett’s compressibility factor, which is employed in calculating temperature
dependent volume shifts.
36 • Components User's Guide WinProp

User Component with Known SG, Tb and MW
For many heavy hydrocarbon fractions, the measured properties are specific gravity (SG), normal
boiling point (Tb), and molecular weight (MW). These components can be defined by choosing
Options|Insert own component|SG, TB and MW. The following form will be presented:
A minimum of two of the three properties must be entered. If one of the properties is not
entered, it will be estimated using the selected Physical Properties Correlation. Note that
critical properties are calculated from specific gravity and normal boiling point; molecular
weight is used for determination of mass densities only. Thus if you enter SG and Tb, the
critical properties will be unaffected by the choice of Physical Properties Correlation. The
stated ranges of accuracy for the correlations are as follows. Twu: Tb up to 715 °C and SG
up to 1.436 (Twu, 1984). Goossens: MW from 76 to 1685 (C120), Density from 0.63 to
1.08 g/cc and Tb from 33 to 740 °C (Goossens, 1996). Riazi-Daubert: Tb up to 455 °C and
MW from 70 to 300 (Riazi and Daubert, 1980).
For petroleum fractions up to about C20, all three correlations give similar results. For
heavier fractions, the Riazi-Daubert correlation shows larger errors than the other two. The
Goossens correlation gives very good predictions of MW from the other properties for
alkanes up to C120. It should be noted that the form of this correlation limits boiling points
to a maximum of 805 °C, regardless of the molecular weight and specific gravity.
Once the physical properties are known, the critical constants for the component are
determined using the selected Critical Properties Correlation. The ranges of applicability
of the Twu and Riazi-Daubert correlations are as given above. The Lee-Kesler correlation
was developed for Tb up to 650 °C, but is internally consistent for extrapolation above this
temperature (Kesler and Lee, 1976).
For acentric factors, the Lee-Kesler correlation is recommended for petroleum fractions.

Component Properties
After components have been selected or defined, their parameters and properties are shown
on the form Component Selection/Properties. A typical example is illustrated below.
This form contains several tabs. The properties shown on Tab Component are listed in the table
below. Additional explanation regarding some of the parameters is given in the notes following
the table. Use of the temperature dependent volume shift feature is described under “Rackett’s
compressibility factor” in the notes.
Heading Parameter or property

Component Component name (maximum 8 characters)
HC Hydrocarbon flag (=1 for hydrocarbons)
Pc(atm) Critical pressure in atm
Tc (K) Critical temperature in K
Acentric fact. Acentric factor
Mol. weight Molecular weight
Vol. shift Volume translation (dimensionless)
Z (Rackett) Rackett’s compressibility factor
Vc (l/mol) Critical volume in l/mol
Vc (viscosity) Critical volume in l/mol for viscosity calculations
Omega A Ωa EOS parameter
Omega B Ωb EOS parameter
SG Specific gravity (water = 1)

Tb (deg F | deg C) Normal boiling point in °F (field units) or °C (SI units)
Parachor Parachor IFT parameter
Ref. Henry (atm) Reference Henry’s constant in atm
V inf. (l/mol) Molar volume at infinite dilution
P ref. (atm) Reference pressure for Henry’s constant in atm
Enth. Coeff. A Ideal gas enthalpy coefficient A (for units see note below)
Enth. Coeff. B Ideal gas enthalpy coefficient B (for units see note below)
Enth. Coeff. C Ideal gas enthalpy coefficient C (for units see note below)
Enth. Coeff. D Ideal gas enthalpy coefficient D (for units see note below)
Enth. Coeff. E Ideal gas enthalpy coefficient E (for units see note below)
Enth. Coeff. F Ideal gas enthalpy coefficient F (for units see note below)
Heating Value Heating value (for units see note below)
Notes on Component Properties
Hydrocarbon (HC) Flag: Binary interaction parameters between components with HC flags
set to 1 are calculated via a correlation as described in the section on “Interaction coefficients”
below. The interaction parameters between all other pairs of components may be set individually.
Thus, if you wish to set individual interaction parameters between one component and all others,
change the value of the HC flag for that component to 0. Note that the HC flags for CO2 and H2S
have special values and should not be changed.
Volume Shift: The volume translation technique of Peneloux et al. (1982) is available for
improving the prediction of phase density with the equation of state. Volume shift parameters
are set to zero by default. The correlation of Jhaveri and Youngren (1988) can be applied to
calculate volume shift parameters for all components by selecting VolumeShift|Reset to
correlation values from the menu. To remove volume translation for all components select
VolumeShift|Reset to zeros. Temperature dependent volume shifts can also be used by
selecting the check box above the component table. The calculation of temperature dependent
volume shifts is described next under “Rackett’s compressibility factor”. When printing
component properties to the output file or for export to the GEM simulator, the most recently
used volume shift values will be output.
Rackett’s Compressibility Factor (ZRA): Temperature dependent volume shifts are
implemented using a technique similar to that described by Kokal and Sayegh (1990).
Component volume shifts are evaluated at any temperature by taking the difference between
the saturated liquid molar volume of a pure component calculated from the equation of state
and the saturated liquid molar volume calculated using a modified Rackett equation:
1+ (1−Tr ) 2/7
v s = ( RTc / Pc ) Z [RA ]
Rackett’s compressibility factors are available for all library components. For pseudo-
components, Rackett’s compressibility factors are back calculated from the critical properties
and specific gravity using the assumption that the specific gravity is approximately equal to
the saturated liquid density at 60 °F.
Critical Volume: Critical volumes are used only in the calculation of hydrocarbon-
hydrocarbon binary interaction parameters as described below under “Interaction coefficients”.

Critical Volume for Viscosity: Critical volumes are used in the Jossi, Stiel and Thodos
viscosity correlation (Reid et al., 1977) as described in this chapter under “Viscosity
parameters.” These critical volume values are used only for the calculation of viscosity, and
thus may be modified via regression to match experimental viscosity data without affecting
the calculation of any other properties.
Omega A and Omega B: The default values for Ωa and Ωb for the Peng-Robinson
equation of state are 0.45723553 and 0.077796074 respectively. For the Soave-Redlich-Kwong
equation of state, these values are 0.4274802 and 0.08664035 respectively.
Specific Gravity and Normal Boiling Point: Specific gravity is defined as the
liquid density of the component at 60 °F and 1 atm divided by the density of water at 60 °F
and 1 atm. For components with normal boiling points below 60 °F, the liquid density is
taken as the saturated liquid density at 60 °F.
If SG and Tb have been used to calculate critical properties and acentric factors, changing SG
and Tb in the table will not affect the other properties. If you wish to recalculate the
properties of a particular component with revised values for SG and Tb, please delete that
component from the table using Options|Delete component, and insert a new component
with revised values for SG and Tb, using Options|Insert own component|SG, TB and MW.
Parachor: The parachor value is used for calculating interfacial tension. Parachors are
available for all of the library components. For pseudo-components and user components,
parachors are estimated based on molecular weight using a correlation proposed by
Firoozabadi et al. (1988).
Reference Henry’s Constant, Molar Volume at Infinite Dilution and
Reference Pressure: These properties are used in calculating the solubility of
components in the aqueous phase. There are three methods available for specifying these
parameters: (1) Entering nonzero values for these properties in the component table, (2)
entering zero values in the component table to allow internal estimation of Henry’s constants,
(3) entering zero values in the table, but overriding the internal Henry’s constants with user
input values entered for individual flash calculations.
If nonzero values for the solubility parameters are entered in the component table, Henry’s
constants are calculated from:
ln H i = ln H io + ν i∞ (p − p io ) / RT
where the superscript “o” refers to the reference condition. If experimental solubility data is
to be matched using regression, this method for defining the solubility parameters must be
used. Correlation values can be entered in the table by selecting Aqueous Solubility|
Calculate component solubility parameters from the menu.
Methods 2) or 3) will be used if the solubility parameters are all set to zero. This can be done
by selecting Aqueous Solubility|Reset solubility parameters to zero from the menu.
If the reference solubility parameters are set to zero in the component table, Henry’s
constants will be estimated internally for all components for each Oil-Gas-Water flash.
Method 2) may be overridden by specifying component Henry’s constants for individual Oil-
Gas-Water flash calculations.

Ideal Gas Enthalpy Coefficients: The ideal enthalpy at a given temperature T is
calculated from a polynomial expression that takes the following form:
H ideal = H A + H B * T + H C * T 2 + H D * T 3 + H E * T 4 + H F * T 5
where the temperature T is in °R. The ideal enthalpy coefficients HA through HF should be
specified in units to give Hideal in Btu/lb.
Component Heating Values: The heating value of a component is the heat of
combustion assuming the reaction goes to completion i.e. the reaction takes place with excess
oxygen and the final products are carbon dioxide and water. In SI system the units are
kcal/gmol and in Field units are Btu/gmol.
Approximate values have been assigned to the Library components. These values were taken
from the CRC Handbook of Chemistry and Physics, 65th edition, CRC Press Inc, 1984, pages
D275-D280 (see table below).
WinProp will write out the HEATING_VALUES keyword and the associated values to the
.gem output file. This file can then be referenced by a GEM data file using an include
statement or the contents of the .gem file can be copied and pasted at the appropriate location
in the GEM data file.
Currently for pseudo components created by WinProp’s splitting and or lumping options, no
method has been coded for estimating the heating value; accordingly for pseudo components
values of zero are assigned. However heating values for pseudo components can be estimated
based on the values assigned to the library components given the actual composition of the
pseudo component is known. Once these values are estimated simply edit the values in the last
column of WinProp’s component properties form and save the form. For example for pseudo
component c2-c3 assuming a split of 50% c2 and 50% c3 and using the built in values in WinProp
the heating value is calculated by mole fraction averaging as: 0.5*1478.46+0.5*2105.16 =
1791.81 Btu/gmol. Values for other pseudo components such as c4-c6 can be estimated in a similar
manner. For the plus fraction such as C10+ if the breakdown of the carbon number vs. mole
fraction is known then mole fraction averaging can be applied. If the distribution is not known
then assign the value corresponding to the presumed largest mole fraction carbon number, for
example for C10+ this might be C12. The heating value for the library component FC12 of 7722.09
Btu/gmol would then be assigned to C10+.
GEM will calculate and report the heating value of all the well streams in the output file using
the known composition of the stream by mole fraction averaging the entered component
heating values supplied by the user.
Once the HEATING_VALUES keyword appears in a GEM data file a heating value for the
separator gas stream for wells and groups will be calculated and be available for plotting with
RESULTS.
The heating value assigned to the library components in WinProp are shown below.
For the carbon fraction FC7-FC45 the heating value equals 1002.57 kcal/gmol + 157.44
kcal/gmol increment for every carbon number greater than 6. Same values are used for NC6
and FC6 and NC7 and FC7 etc. For pseudo components values of zero will be assigned, as at
present there is no method implemented for estimating these values.

Component Name Heating Value (Btu/gmol)
H2S 0.0
N2 0.0
CO2 0.0
CH4 (or C1) 844.29
C2H6 (or C2) 1478.46
C3H8 (or C3) 2105.16
IC4 2711.54
NC4 2711.54
IC5 3353.66
NC5 3353.66
FC6 3975.91
FC7 4600.28
FC8 5224.64
FC9 5849.00
FC10 6473.36
FC11 7097.73
FC12 7722.09
FC13 8346.45
FC14 8970.82
FC15 9595.18
FC16 10219.54
FC17 10843.91
FC18 11468.22
FC19 12092.63
FC20 12717.00
FC21 13341.36
FC22 13965.72
FC23 14590.08
FC24 15214.45
FC25 15838.81
FC26 16463.17
FC27 17087.54
FC28 17711.90
FC29 18336.26
FC30 18960.63
FC31 19584.99
FC32 20209.35
FC33 20833.71

FC34 21458.08
FC35 22082.44
FC36 22706.80
FC37 23331.17
FC38 23955.53
FC39 24579.89
FC40 25204.26
FC41 25828.62
FC42 26452.98
FC43 27077.35
FC44 27701.71
FC45 28326.07
NC6 3975.91
NC7 4600.28
NC8 5224.64
NC9 5849.00
NC10 6473.36
NC16 10219.54
TOLUENE 3705.97
BENZENE 3097.15
CYCLO-C6 3715.32
H2O 0.0
Example: Consider an 8-components fluid, with the last three components being pseudo
components. In Field units, the heating values as written out by WinProp would result in the
following lines appearing in the .gem output file:
*NC 8 3
*COMPNAME 'CH4' 'C2H6' 'C3H8' 'NC4' 'NC5'
'FRAC1' 'FRAC2' 'FRAC3'
*HEATING_VALUES 844.29 1478.46 2105.16 2711.54
3353.66 0.0 0.0 0.0
Interaction Coefficients
Interaction coefficients (δij) are introduced to account for the molecular interaction between
dissimilar molecules. Their values are generally obtained by fitting the predicted saturation
pressures to experimental data. Interaction coefficients for component pairs are shown on
Tab Int. Coef..
An example is shown below.

Hydrocarbon-Hydrocarbon Interaction Coefficients
The hydrocarbon (HC) components are identified by a value of 1 in the “HC” column on Tab
Component. The interaction coefficients between HC components are calculated from
θ
⎛ 2v1ci/ 6 v1cj/ 6 ⎞
δ ij = 1 −⎜ 1 / 3 1 / 3 ⎟
⎜ v +v ⎟
⎝ ci ci ⎠
where vci is the critical volume of component i, and θ is the hydrocarbon – hydrocarbon
interaction coefficient exponent. It has been shown that a value of 1.2 provides a good match
of the paraffin – paraffin interaction coefficients of Oellrich et al (1981). However, it is
recommended that this value be obtained by matching experimental data (e.g. saturation
pressure data).
To avoid cluttering the table of interaction coefficients, the HC interaction coefficients are
not shown when the form is loaded. To view them, click on Show HC Int. Coef. button. To
hide them, click on Hide HC Int. Coef. button.
With this version of WinProp, it is possible to define multiple HC:HC interaction coefficient
groups, each with its own value of the exponent. HC:HC groups can also be selected as
independent parameters in regression, please see the chapter on “Regression”. The list of groups
currently defined is shown in the list box with the caption HC Int. Coef. Exp.. The entries
include a name and in brackets the value of the exponent. To see the group ID for all HC-HC
pairs on the interaction coefficient table, click on the Show HC-HC Group(s) on grid button.

The value of the exponent for a given group(s) can be changed by invoking a custom form
designed to handle the tasks associated with managing these groups. This form is invoked by
clicking the button on the Int. Coef. tab with the caption HC:HC Groups / Apply value to
multiple non HC-HC pairs…. This form is shown below.
The currently selected group is shown under the Name label. The list of pairs that belong to
this group is shown in the list box labeled Selected pairs. The user can scroll through all
defined groups in the drop down list box under the Name label. The full list of pairs that do
not currently belong to any group can be seen on the list box under the Select pairs frame.
These pairs can be assigned to any defined group(s). If any “orphans” remain when this form
is saved then these are assigned to the default group, i.e. group # 1.
Initially only a single group is created with the exponent value of 1.2. The value of the
exponent can be changed via the text box with the label Exponent value. All HC:HC pairs
initially belong to this group. To create a new group first select the HC:HC option button
under Type and then click on the Create New button. This new group will be assigned the
name HcIntCoefExp-2 with a value of 1.2 for the exponent. For pairs to be assigned to this
new group # 2, group #1 must first relinquish these. This is done by first selecting group # 1
from the group list, identifying the pairs that will be removed (by pressing the left mouse
button while holding the CTRL key down) from the Selected pairs list box and then clicking
on the Delete selection(s) button. These pairs will be removed from group # 1 as reflected in
the revised list in the Selected pairs box. To pick these pairs up for group # 2, change the
name to group # 2, select pairs by highlighting and then pressing the Apply selection(s)
button. At least one pair must be assigned to each group and a given pair can be assigned to a
single group only. To delete a group click on the Delete Group button.

Other Interaction Coefficients
Interaction coefficients between nonhydrocarbons, and between hydrocarbons and
nonhydrocarbons from the WinProp library are displayed in the table. They may be edited in
one of two ways, either directly on the grid, or if a common value is to be assigned to multiple
pairs, say CO2 and all pseudo-components then a faster way is through a special form invoked
by the clicking the button on the Int. Coef. tab with the caption HC-HC Groups / Apply value
to multiple non HC-HC pairs…. Select pairs through the 1st index (single) and 2nd index
[multiple] lists and then click on the Apply selection(s) button. The list of pairs chosen is
shown in the Selected pairs box. Specify the value to be applied in the text box labeled Value
and finally click on the Apply value button. On exiting the form, the interaction coefficient
table should now show the revised value for the pairs selected.
Note that as δij ≈ δji, changing one also changes the other.
Viscosity Parameters
There are two types of viscosity correlation available in WinProp: the Jossi, Stiel and Thodos
(JST) correlation as described in Reid et al. (1977), and the Pedersen corresponding states
correlation as presented in Pedersen et al. (1984) and Pedersen and Fredenslund (1987). The
viscosities of liquid and vapor phases are calculated with the same correlation. The choice of
correlation is made on the Viscosity tab of the Component Selection/Properties form by
selecting one of the option buttons under Viscosity Model Type.
Jossi-Stiel-Thodos Correlation
An example of the data entry form for the JST correlation is shown below.

The JST correlation determines the mixture viscosity from the low-pressure mixture viscosity
according to the following function:
[ ( μ − μ )ξ + 10 ]
* − 4 0.25
= a 0 + a 1ρ r + a 2 ρ 2r + a 3 ρ 3r + a 4 ρ 4r
Where
μ = Oil or gas viscosity in cP or MPa⋅s
μ∗ = Low-pressure viscosity in cP or MPa⋅s
ξ = Group Tc1/6 M-1/2 Pc-2/3 where Tc is in K and Pc is in atm
M = molecular weight
ρr Reduced molar density, ρ/ρc = vc/v
Two options are available for calculating the low-pressure mixture viscosity. The Yoon-
Thodos + Herning-Zipperer method computes low pressure component viscosities according to
a formula developed by Yoon and Thodos and then computes the mixture viscosity according
to the mixing rule of Herning and Zipperer. Both of these formulas are reported in Reid et al.
(1977). The Lee-Eakin method calculates the low-pressure mixture viscosity directly using a
correlation based on the molecular weight of the mixture presented by Lee and Eakin (1964).
The value of ξ is calculated by first obtaining mole – fraction weighted average values for the
mixture critical temperature, pressure and molecular weight.
The mixture critical volume vc is calculated from:
1/ α
⎛ nc ⎞
v c = ⎜ x i v ci
∑ α⎟
⎜ ⎟
⎝ i =1 ⎠
Where α is the mixing exponent parameter, xi is the composition and vci is the critical volume
for viscosity calculation (vc(viscosity) on Tab Component).
α, a0, a1, a2, a3, and a4 are entered on Tab Viscosity. Default values are shown when the form
is first activated.
As well as the correlation coefficients (α, ai) and critical volumes for viscosity (and to a
lesser extent, the critical temperatures and pressures), the JST method depends very strongly
on the density of the mixture predicted by the equation of state. Thus, use of the JST
correlation may result in large errors if the phase densities are incorrect. It is recommended
that the EOS be tuned to match volumetric data before attempting to predict or match
viscosities with the JST correlation.
Pedersen Correlation
The Pedersen viscosity correlation uses the principle of corresponding states to calculate the
viscosity of a component or mixture, knowing the viscosity of a reference substance at the same
conditions of reduced pressure and temperature. The deviation from simple corresponding
states is accounted for by a “rotational coupling coefficient,” α. The viscosity of the mixture is
calculated according to the following formula:
−1 / 6 2/3 1/ 2
μ mix ( P, T ) ⎛ Tc,mix ⎞ ⎛ Pc,mix ⎞ ⎛ MWmix ⎞ ⎛ α mix ⎞
=⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟
μ o (Po , To ) ⎜⎝ Tc,o ⎟
⎠
⎜ P
⎝ c ,o
⎟
⎠ ⎝ MWo ⎠ ⎝ αo ⎠

Where
μ = Viscosity
Tc = Critical temperature
Pc = Critical pressure
MW = Molecular weight
α = Rotational coupling coefficient
The subscript “mix” refers to the mixture property, and the subscript “o” refers to the
reference substance property. The reference substance for the Pedersen model is methane.
The mixture critical temperature and pressure are calculated using mixing rules that are a
function of the component critical temperatures and pressures and mole fractions. The
molecular weight of the mixture is determined from:
(
MWmix = b1 MWwb 2 − MWnb 2 + MWn)
where MWw is the weight fraction averaged molecular weight, and MWn is the mole fraction
averaged molecular weight.
The rotational coupling coefficient is calculated as follows:
α = 1 + b 3 ρ br 4 MW b5
where ρr is the reduced density of the reference substance.
The viscosity of a mixture calculated using the Pedersen model depends strongly on the
critical pressures, critical temperatures and molecular weights of the components, and the
coefficients bi shown in the above two equations.
Two different versions of the Pedersen correlation may be chosen. The one labeled Modified
Pedersen (1987) uses a modification to the methane viscosity equation as described in
Pedersen and Fredenslund (1987). This modification showed improved results for mixture
viscosities up to approximately 10 cP. Each modification has a set of default coefficients.
These coefficients may be modified during regression to match experimental viscosity data.
Aqueous Phase
The Aqueous phase tab is used for setting properties of the water phase for use in multiphase
Oil-Gas-Water calculations. The form is shown below.
Aqueous Phase Salinity
The salinity of the aqueous phase is expressed as NaCl concentration. The units available for
specifying the brine salinity are weight fraction, molarity, grams of NaCl per litre of water,
molarity, and mole fraction. All other water properties are determined from correlations.
The brine salinity is used to adjust the internally estimated Henry’s constants for the library
components N2, CO2, H2S, C1, C2, C3, iC4, nC4, iC5, nC5, nC6, nC7 and nC8 to account for the
salting-out effect. Note that this adjustment is not performed when solubility parameters are
specified in the component table, or when Henry’s constants are entered for individual flash
calculations.

Henry’s Law Constant Correlation
There are two correlations available in WinProp to calculate Henry’s law constant: the
Harvey’s method (1996), and the Li-Nghiem’s method (1986). The effect of salt on the gas
solubility in the aqueous phase is modelling either by salting-out coefficient or the scaled-
particle theory, depending on the component. The choice of Henry’s constant correlation is
made by selecting one of the option buttons in the Henry’s law constant correlation frame in
the Aqueous phase tab. The correlation is set to Harvey’s method (1996) by default.
Activation of Second Set of Component Properties

WinProp supports the specification of a second set of EOS component properties. It is often
difficult for a single EOS description to perform adequately over a wide range of conditions
encountered in reservoir phase behavior modelling. This can be alleviated by the
introduction of a second EOS model that is applied to calculations performed at surface
(separator) conditions, while the first EOS set is used for calculations at reservoir conditions.
Therefore separator data can then be matched separately from other PVT data gathered at
reservoir temperature, for example by CVD and differential liberation experiments.
To activate the second set select Options|Enable Second Set. This should be done after the
component selection is completed. WinProp will duplicate the first set properties for the
second set. The user can toggle between the first and second set using the Set Selection
menu. Certain operations, for example addition or removal of components on the component
form, can be performed only if the first set is active.
Currently critical pressure, critical temperature, volume shift, omega-A, omega-B, interaction
coefficient exponent and interaction coefficients for pairs with a nonhydrocarbon component are

supported for the second set. The user can edit the values of these properties from the default
assignments. The user can also reset back to the original values by selecting Set Selection|Reset
2nd to 1st. The second set parameters can also be used in regression. To use a second set
parameter in regression the user does not have to enable the second set component properties
first. The second set parameters can be selected directly on the Regression Parameters form in
a manner similar to first set properties. The initial value of the property will be set equal to the
corresponding first set parameter.
The second EOS parameter set, when enabled, is used in performing the following
calculations: separator, separator calculation associated with the constant volume depletion
experiment (to determine yields at surface) and in differential liberation experiment when
flashing the residual oil (at atmospheric pressure and reservoir temperature) to standard
conditions (atmospheric pressure and temperature).
GEM Fluid Model Generation and Component Properties

Printing
The EOS model description in WinProp can be written to a file in a format suitable for
CMG's compositional simulator GEM. This file can be imported into a GEM data set using
Builder. The model information includes EOS type, component critical properties, volume
shifts, EOS omega parameters, parachors, aqueous solubility parameters and viscosity model
coefficients. The component properties can also be echoed to the output file.
The option to write out the EOS model may be included in the data set by selecting
Simulator PVT|CMG GEM EOS Model from the menu. A form entitled CMG GEM
EOS Model will be included in the data set. In the File Selection frame on this form there
are two check boxes for printing the component properties. Select the upper check box to
print detailed component properties to the output file, and select the lower check box to write
out the EOS model for GEM. This file will have the same root name as the data file and the
extension (.gem). To complete the model description for GEM, a reservoir temperature must
be specified. If the data set includes a laboratory experiment simulation such as a CCE, CVD
or Differential Liberation calculation, the temperature from the first calculation of this type in
the data set will be taken as the default reservoir temperature, otherwise this field must be
filled in by the user.
There are also options to Write solid model parameters for GEM, and to Write
component heating values for GEM. To use the solid model in GEM, the number of solid-
forming components must be set to one on the “Asphaltene/Wax Modelling” dialog. GEM’s
solid model is used for asphaltene precipitation, not for waxes. To have accurate parameters
for GEM, the reference fugacity for the model should be determined from experimental data
as described in the “Asphaltene/Wax Modelling” section of the User’s Guide. Parameters for
the isothermal precipitation model will always be written for GEM. Temperature-dependent
parameters will only be written if additional onset pressures have been specified with the
reference fugacity calculation.

In the Interaction Coefficient Table frame, the format of the table can be selected as either
upper or lower triangular form.
By default, the aqueous phase solubility parameters are not printed with the other component
properties. To turn on this option, select the check box in the Solubility Parameters frame.
If an Oil-Gas-Water flash is included in the data set before the print options form, the Henry’s
constants and molar volumes at infinite dilution used in the flash will be available for
printing. Optionally, the parameters may be recalculated at a specified pressure and
temperature before printing.
Importing Components with the Table Import Wizard

The Table Import Wizard is a tool designed to assist the user in importing Excel™ or ASCII
format data into WinProp. General instructions regarding use of the Wizard are given in the
“Tutorial” section of this manual. Specific information relating to the import of component
properties is given here.
The Table Import Wizard can be used to append or insert components at the currently
selected row in the component table. The wizard is launched by clicking on the Table
Import Wizard button located on the Component tab. Components can only be imported
when the first set of EOS properties is active. Data for any of the component properties
appearing on the component table may be imported.
When importing component properties, the only specifically required information is a component
name. A further requirement, however, is that a minimum set of data sufficient to estimate any
component properties not imported must be provided. This minimum set of data may be either (a)
two of the following properties: specific gravity, molecular weight or normal boiling point, or (b)
both of critical temperature and critical pressure. Depending on which component properties have
been imported, a form for the selection of physical and critical property correlations required to
complete the component specification may appear when the table import wizard exits. The use of
these correlations is discussed earlier in this chapter under “Component properties”, in the
section on “User components with known SG, Tb and MW.” Once these correlations have
been selected, the process is completed by inserting all imported properties into the table and
calculating the values of all properties that were not imported.
Note that the Table Import Wizard cannot be used to import columns of data for existing
components. The standard Windows cut, copy and paste functions can be used for this purpose.

Common Data Required for All
Options
Overview
This chapter describes the common data required for most calculations. These include
Composition specification, Initial K-values, Output level, and Stability test level. Generally, the
built in default values are used in the calculations. The saturation pressure calculation, which is
common to most laboratory experiment simulation options, is discussed in the next chapter.
Composition Specification
Compositions are entered in moles or in weight units, specified as fraction or percent. Values
are normalized internally. If weight fractions or percents are entered, they are converted
internally to mole fractions. To use weight units, select the appropriate option on form
Titles/EOS/Units. The table on form Composition contains two columns for composition
input. The primary composition corresponds generally to the composition of the oil or gas in
place. Values must be entered for the primary composition. The secondary composition
corresponds normally to the injected fluid. The secondary composition need not be entered and
will default to zero. An example of form Composition is shown below.
User's Guide WinProp Common Data Required for All Options • 53

Several composition sections can be defined in a data set. All calculations following a
composition section will use the composition of that section until the end of the run or another
composition section is encountered. In the following example, the fluid composition from Well
16 is used for a series of calculations. Similar calculations are then performed with the fluid
composition of Well 20.
Composition Used in Calculations
The feed composition used for all calculation options can be

• a mixture of the primary composition and the secondary composition
• the feed from the previous calculation option
54 • Common Data Required for All Options User's Guide WinProp

• the vapor composition from the previous calculation option
• the liquid composition from the previous calculation option
• the composition from Phase n from the previous calculation option
The feed composition is specified from the Combo Box Feed, located on the last tab of most
calculation options. The selection of the feed composition for a two-phase saturation
pressure calculation is shown above.
In this example, the composition that enters into the two-phase calculations is a mixture
containing 80 mole % of the primary composition and 20 mole % of the secondary
composition. When Phase is selected, you enter the Phase Number in the adjacent text box.
Some calculations accept only the Mixed and Previous option. The Combo Box Feed
displays only these items in this case.
Initial K-Values
Initial K-values are required to start most calculations. These can be
• estimated internally from Wilson’s equation (Internal), i.e.
ln K i =5.37 (1 + ωi ) (1 − Tci / T )+ln ( p ci / p)
• from a previous two-phase calculation (Previous)

• from Phase n of a previous multiphase calculation (Phase)
When Phase is selected, the Phase Number is entered in the adjacent text box.
Output Level
The Output level for a normal run is 1. If more information is required, for example the
results of each iteration of a flash calculation, select an Output level value of 2.
Stability Test Level

In phase behavior calculations, the number of phases is generally unknown a priori. WinProp
assumes that the system is initially single-phase and performs a stability test on that system. The
stability test is a calculation that determines whether a system needs to split into additional
phases to achieve stability. The stability test searches the multidimensional Gibbs free energy
surface for stationary points. For a phase to be stable, the Gibbs free energy must be lower than
the value at all stationary points. The Stability test level determines the thoroughness of the
search for the stationary points. Values are from 0 to 4. For most two-phase oil/gas systems,
Level 1 is normally sufficient. For systems with more than two phases, a value of 4 may be
required. The Stability test level is set to its default value when the form for a particular
calculation is first activated. If you suspect that your system may have more phases than those
predicted, increase the level value and rerun the data set. See Nghiem and Li (1984) for a
detailed discussion of stability test calculations.
User's Guide WinProp Common Data Required for All Options • 55

Two-Phase Saturation and Phase
Boundary Calculations
Overview
This chapter describes calculations for mixtures on the phase boundaries:
• Bubble point and dew point calculations
• Phase boundary diagram construction (pressure-temperature, pressure-composition,
temperature-composition and pseudo-ternary)
• Critical-point calculation
• Multiple-contact calculation
The phase boundary calculations can also generate lines of constant phase mole fraction or
lines of constant volume fraction (quality lines).
Saturation Pressure
This option is invoked by selecting Calculations|Saturation Pressure. An example data set
for this option is sat-pressure.dat.
For data entry corresponding to items on tab 2, that is Feed, K-values, Output level and
Stability test level specifications, see the Chapter “Common Data Required for all Options”.
A value of the temperature at which the saturation pressure is to be calculated is required. Enter
a value in the text box labelled Temperature. An estimate of the saturation pressure is also
required; enter a value in the text box labelled Saturation Pressure Estimate. If this is a poor
estimate, ask WinProp to generate internally a better initial guess for saturation pressure
calculation by checking the box Improve saturation pressure estimate. Details of the
calculation techniques can be found in Nghiem et al. (1985). Finally at a given temperature
there are two saturation pressures, the upper and lower values respectively. The upper value
can be a dew point or bubble point fluid, the lower is a dew point fluid. By default the upper
value is calculated as this corresponds to the reservoir saturation pressure at the given
temperature. The lower value can be chosen instead by selecting the button Lower dew point
in the frame labelled Calculation option.
Experimental data related to a saturation pressure calculation that can be matched via
regression are shown on the table on the first tab, Calculations. These include saturation
pressure, liquid and vapor mass densities, compressibilities and viscosities. The weight
assigned to each experimental data value can also be specified.
User's Guide WinProp Two-Phase Saturation and Phase Boundary Calculations • 57
Saturation Temperature
This option is invoked by selecting Calculations Saturation Temperature. An example data
set for this option is sat-temperature.dat.
For items on tab 2, Feed, K-values, Output level and Stability test level specifications, see
the Chapter “Common Data Required for Options”.
A value for the pressure at which the saturation temperature is to be calculated is required.
Enter a value in the text box labelled Pressure. An estimate of the saturation temperature is
also required; enter a value in the text box labelled Saturation Temperature Estimate. If
this is a poor estimate, ask WinProp to generate internally a better initial guess for saturation
temperature calculation by checking the box Improve saturation temperature estimate.
Generally there are two possible values for the saturation temperature at a given pressure.
The larger value corresponds to a dew point fluid whereas the lower value corresponds to a
bubble point fluid. By default the larger value is calculated. The lower value is chosen by
clicking on the button Lower sat. temperature in the frame labelled Common options.
Details of the calculation techniques can be found in Nghiem et al. (1985).
Experimental data related to a temperature pressure calculation that can be matched via
regression are shown on the table provided on tab Calculations. These include saturation
temperature, liquid and vapor mass densities, compressibilities and viscosities. The weight
assigned to each experimental data value can also be specified.
Phase Boundary and Quality Line Calculations

This option is invoked by selecting Calculations|Two-phase Envelope. Example data sets
for this option are envel_2ph-pt.dat (PT diagram), envel_2ph-px.dat (PX diagram) and
envel_2ph-tern.dat (ternary diagram).
The two-phase envelope calculation generates the boundaries between the single-phase and
two-phase regions. The bubble point envelope corresponds to the boundary between a single-
phase liquid region and a two-phase vapor-liquid region; the dew point envelope corresponds
to the boundary between the single-phase vapor region and the two-phase region. There are
two main classes of diagrams that can be generated: X-Y phase diagrams and pseudo-ternary
phase diagrams.
Pseudo-ternary phase diagrams depict the boundaries between single-phase and two-phase
regions in composition space at a fixed temperature and pressure. The results are displayed on
a triangular diagram, where each apex of the triangle corresponds to 100% of one pseudo-
component. Each component in the system is assigned to one of the three pseudo-components.
X-Y phase diagrams are displayed on regular Cartesian coordinates. The types of envelopes
or diagrams that can be generated are:
• Pressure-Temperature (PT) diagram
• Pressure-Composition (PX) diagram
• Temperature-Composition (TX) diagram
58 • Two-Phase Saturation and Phase Boundary Calculations User's Guide WinProp

In the process of constructing the envelope, WinProp also calculates the location of critical
points through interpolation. This is a very efficient method for estimating critical points if
they exist on the portion of the phase envelope being constructed. A direct method of
calculating critical points is also available (see the section on “Critical point calculation”).
A typical PT diagram is shown below:
Gas condensate Phase Envelope

Pressure-Temperature Diagram
14,000
2-Phase boundary Critical
99.000 volume % 95.000 volume %
12,000 90.000 volume % 80.000 volume %
75.000 volume % 70.000 volume %
10,000
60.000 volume % Critical
55.000 volume % 55.000 volume %
50.000 volume % 50.000 volume %
Pressure (psia)
8,000 45.000 volume % 45.000 volume %

40.000 volume % 35.000 volume %
6,000
4,000
2,000
0
-200 0 200 400 600 800
Tem perature (deg F)
Envelope Specification
The type of envelope to be calculated is specified on tab Envelope Specification. First, select
either X-Y Phase Envelope or Pseudo-Ternary Phase Envelope at the top of the tab. This
selection will activate the corresponding data entry area.
X-Y Phase Envelope
For X-Y phase envelopes, you must select which variable to use on the X-axis (independent
variable) and the Y-axis (dependent variable). The choices are Temperature and Composition
for the X-axis and Pressure or Temperature for the Y-axis. For a Pressure-Temperature (P-T)
diagram select Temperature as the independent variable and Pressure as the dependent variable.
For a Pressure-Composition (P-x) or swelling curve select Composition as the independent
variable and Pressure as the dependent variable. Finally for a Temperature-Composition (T-x)
diagram select Composition as the independent variable and Temperature as the dependent
variable. The envelope is generated by taking steps in terms of the independent variable, and
determining the corresponding value of the dependent variable on the phase boundary.
Minimum and maximum values for the X- and Y- variables are specified along with the axis
definitions. The calculation stops when any of these limiting values are exceeded. When
composition is selected as the independent variable, minimum and maximum independent
variable step sizes are also specified, as well as the upper and lower limits for the axis. P-x and
T-x diagrams are generated by adding a fluid defined by the secondary composition on the last
Composition form to the fluid defined as the feed for the envelope calculation.

For P-T diagram the value entered in the Temperature combo box is taken as the initial
starting point for the calculation on the upper saturation pressure curve. Two types of curve(s)
can be generated, line(s) of constant mole fraction of the vapor phase or line(s) of constant
volume fraction vapor phase. The latter are also known as quality lines. These are specified on
Tab 2, “Envelope Construction Controls” on the table in the frame labelled “Quality/Mole
Fraction Lines Specification”. If a value of (x) is chosen for a line, then a value of (1-x) is
automatically selected as well. This ensures that a starting point on the upper saturation pressure
curve at the initial temperature is always selected whether there is a dew point or a bubble
point. This also means that for example if x = 0.0 is selected and the upper saturation pressure is
a bubble point then the program will attempt to trace from the bubble point line (x=0.0) as well
as the lower dew point (for 1-x=1.0). However the chances are that the attempt to trace from the
lower dew point will fail as the algorithm has difficulties starting off from very small pressures.
To select only the starting point corresponding to value (x) check off the box labelled “Select
value from the above table as well as one minus the value in the table”. This implies the
user knows the type of upper saturation pressure, dew point or bubble point. The algorithm will
attempt to generate both the part corresponding to the value (x) as well as (1-x) for all starting
points. For example if x = 0, is chosen then both the bubble and dew point curves will be
generated. All values should be between 0 and 1. A maximum of 25 such lines can appear on a
single plot. By default a single value corresponding to vapor phase mole fraction equal to 0.0 is
pre-selected. If x = 1.0 is selected and both an upper and lower dew point exists, the starting
point on the upper dew point will be selected. If starting points on both upper and lower dew
point curves is desired then check on the box labelled “Trace from all potential starting
points” on Tab 2. The value entered in the Pressure combo box, either a number or the
selection Unknown may be used as the initial guess for saturation pressure at T = Ts if a 2
phase region cannot be found at T= Ts by scanning the interval from Pmax to Pmin. For the
majority of cases a value is not required for the Pressure.
When composition is selected as the independent variable, both pressure and temperature must
be entered, although the value corresponding to the dependent variable will be determined
internally. In the unlikely scenario that this cannot be done the value entered for the dependent
variable will be used as an initial guess in the saturation calculation. The initial composition is
taken as that defined by the Feed specification for the envelope calculation.
The values entered for Mole fraction vapor (Fv) or Volume fraction vapor (Vv) are used to
define which lines on the phase envelope are generated. If a critical point is encountered, the
line corresponding to (1- Fv) will also be calculated. For example, with Fv=1, the entire phase
boundary (starting on the dew point side) will be calculated. If a value is specified for volume
fraction vapor, the quality line corresponding to Vv will be calculated. Again, if a critical point
is encountered, the line corresponding to (1-Vv) will also be calculated. To calculate phase
boundaries, select Fv = 0.0 and/or 1.0 or Vv = 0.0 or 1.0. When tracing lines of constant
volume fraction, an additional stopping constraint can be placed on the calculation by
specifying minimum and maximum allowed values of vapor mole fraction. By default these
values are set to –10 and +10 respectively, thus the calculation will not halt unless large
nonphysical values of the vapor mole fraction are calculated.

Pseudo-Ternary Phase Envelope
The first step in generating the pseudo-ternary phase envelope is specification of the pseudo-
components. When the Pseudo-Ternary option is selected, a grid is displayed listing all of the
components. The primary and secondary compositions are shown to assist the user in
defining the pseudo-components. Components are assigned to pseudo-components by
entering the number 1, 2 or 3 in the column of the table labeled “Pseudo.” Pseudo-component
1 is at the lower left corner of the triangle, 2 is at the lower right, and 3 is at the top.
The diagram is generated by locating the point on the diagram corresponding to the specified
mole or volume fraction vapor for the feed composition. The composition of the phase in
equilibrium with this phase is obtained from the K-values. A step in the construction is taken
by adding fluid with the secondary composition, and the next point is calculated with this
new composition. Note that different pseudoization schemes will result in different
envelopes being generated.
As for the X-Y diagram, minimum and maximum values for the mole fraction of secondary
fluid can be specified, as well as minimum and maximum secondary fluid step sizes.
Pressure and temperature must be specified, as they are fixed for the ternary diagram. Mole
fraction vapor, volume fraction vapor, minimum mole fraction vapor and maximum mole
fraction vapor may be specified as discussed under X-Y Phase Envelopes.
Envelope Construction Controls
Maximum Number of Points
This value corresponds to the maximum number of points calculated on the phase diagram.
Initial Step Size
The Initial step size controls the spacing between the calculated points on the envelope.
Both positive and negative values may be used. For positive values, the diagram is traced
initially in the direction of increasing x-values. For negative values, the diagram is initially
traced in the direction of decreasing x-values. WinProp internally estimates the step size for
subsequent points on the envelope.
Independent Variable Interpolation Points
These correspond to x-values for which you want calculated y-values. Because the step size
in the envelope calculation is automatic, these interpolation values must be entered to force
calculations at desired x-axis values.
Stability Test
WinProp checks the stability of each phase for every calculated point on a phase envelope.
The envelope generation routine can be set to terminate when an instability is detected, or to
continue calculations. Letting the calculation continue along unstable lines is sometimes
useful, as it allows determination of two stable portions of a phase envelope that are
connected by an unstable line.

Cricondenbar/Cricondentherm Calculation
The cricondenbar corresponds to maximum pressure on the PT phase envelope whereas the
cricondentherm corresponds to the maximum temperature. These are estimated in a two-
phase PT envelope construction (see “Phase boundary and quality line calculations”) or
can be calculated directly by selecting Calculations|Cricondenbar/-therm. An example
data set for this option is cricon.dat.
For Feed, K-values, Output level and Stability test level specifications, see the Chapter
“Common Data Required for all Options”. As initial guesses for pressure and
temperature, you can specify Unknown or Previous (value from the previous calculation
option), or type in the value of the initial guess.
Critical Point Calculation

The phase-boundary and quality-line calculations estimate the critical point through
interpolation. This method is efficient and yields both the phase boundary and critical points.
However, if you want a direct calculation or want to match a critical point in a regression
calculation, you should use the Critical Points Calculation option. The critical points
calculation is invoked by selecting Calculations|Critical Points. An example data set for
this option is critical.dat. This option uses the calculation method of Heidemann and Khalil
(1980). The required numerical data are the Lower dimensionless volume limit and the
Upper dimensionless volume limit. These dimensionless volumes are equal to the ratios of
molar volume v over the parameter b of the EOS. All critical points between these two
volume limits are calculated. Default values for these limits are 1.0 and 5.0 respectively.
You can enter the experimental critical pressure and temperature for regression purposes.

Flash Calculations
Overview
Flash calculations determine the split of a system at a given pressure, temperature and feed
composition. The number of phases and the properties for each phase are calculated.
WinProp can perform many types of flash calculations:
1. Two-phase vapor-liquid
2. Three-phase vapor-liquid_1-liquid_2
3. Three-phase vapor-liquid-aqueous
4. Four phase flash calculation (fluid phases only)
5. Multiphase flash calculations with a solid phase
6. Isenthalpic flash calculation
In the above calculations, the fluid phases are modeled with an EOS, except for Calculation No.
3 where the component solubility in the aqueous phase is modeled by Henry's law. Calculation
No. 5 can be used for modelling asphaltene and wax precipitation. Flash calculations
performed in the single-phase region will yield a single-phase system. An option for single-
phase calculation is also available in WinProp and is described in this chapter.
Common input for two-phase flash, multiphase flash and asphaltene/wax modelling
calculations is described below, followed by descriptions of each of the flash types.
Common Input for Two-Phase Flash, Multiphase Flash and

Asphaltene/Wax Modelling Calculations
“Common data required for all options”.
Flash calculations are performed at the pressure and temperature specified in the Text Boxes
labeled Pressure and Temperature. You can perform a series of calculations by specifying
the Pressure Steps, Temperature Steps, or Mole Fraction Steps with the associated number
of steps. The steps can be positive or negative. Step No. 1 corresponds to a calculation at the
specified pressure and temperature or mole fraction. Specifying steps for the primary mole
fraction allows calculations for a number of mixtures of the primary and secondary fluids.
User's Guide WinProp Flash Calculations • 63

When a series of flash calculations have been specified by setting temperature, pressure or mole
fraction steps, plots of the phase properties can be generated. Specification of the phase
properties (maximum of three) to plot is done on tab Plot Control. When plotting is activated,
steps can be specified in one or two of the variables: pressure, temperature and mole fraction. If
steps are specified for only one variable, the plots are generated with that variable as the
independent variable, and the phase property as the dependent variable. Up to 100 steps in the
independent variable are allowed. When steps are specified for two variables, one variable is
treated as a parameter variable, and curves of the phase property are displayed for each value of
the parameter variable. Up to 8 steps in the parameter variable are allowed. If mole fraction
steps are specified, mole fraction is always used as the independent variable. If pressure and
temperature steps are both specified, pressure is used as the independent variable.
Two-Phase Flash Calculations

This option is invoked by selecting Calculations|Two-Phase Flash from the menu. An
example data set is flash-2ph.dat.
For specification of data on the Calculations tab and the Plot Control tab, please see the
section “Common input for two-phase flash, multiphase flash and asphaltene/wax
modelling calculations” at the beginning of this chapter.
The Flash type may be set to either QNSS/Newton or Negative. Selecting QNSS/Newton
specifies that the two-phase flash equations will be converged initially using a Quasi-Newton
successive substitution algorithm, followed by Newton’s method to refine the roots. If the
system is in the single-phase region, properties for that phase will be reported, and k-values
will not be calculated. When the Negative flash is selected, the QNSS algorithm is used
without further refinement of the roots. If the system is in the single-phase region, properties
for two phases will be reported, with one phase being present in a negative (non-physical)
amount. This option allows generation of k-value estimates outside of the two-phase region.
Experimental data to be included in a regression calculation are entered on tab Experimental
and Experimental K-values. Data on tab Experimental include mass densities, mole
fractions, volume fractions, compressibility factors, and viscosity of both the vapor and liquid
phases. Experimental K-values are entered on tab Experimental K-values.
Multiphase Flash Calculations

This option is invoked by selecting Calculations|OGW/EOS Multiphase Flash. An
example data set is flash-3ph.dat.
The type of multiphase calculation to be performed is selected with the Combo Box Flash
type. The 3-phase and 4-phase calculations use the techniques described in Nghiem and Li
(1984). This is a stage wise procedure where the number of phases is gradually increased.
All phases are modeled with an EOS. The number of phases selected from the Combo Box
corresponds to the maximum number of phases. Thus, selection of a 4-phase calculation for a
two-phase system will yield the same results as a two-phase flash calculation.
64 • Flash Calculations User's Guide WinProp

The Oil-Gas-Water (OGW) calculation involve a three-phase calculation where the vapor and
liquid phases are modeled with an EOS while the aqueous phase is modeled with Henry' law.
An example data set is flash-ogw.dat. As the EOS was developed for gas-like hydrocarbon
systems, it may not model accurately the aqueous phase. Li and Nghiem (1986) recommended
the use of Henry's law constants for component solubility in the aqueous phase. The fugacity
coefficient of Component i in the aqueous phase φiw is given by
lnφiw = ln( H i / p)
where Hi is Henry's law constant of Component i. Hi for each component may be entered on
tab Henry's Law. If Hi is not specified, WinProp will estimate it internally. See the
“Components” chapter for more information on Henry’s constants.
Experimental data for 3-phase and OGW calculations may be entered on tab Experimental.
These include mass densities, mole fractions, volume fractions, and viscosities of the
different phases.
When the flash type is set to OGW, experimental data for the solubility of components in the
aqueous phase may be entered on the tab labeled Exp. Solubility. The units available for
specifying the component solubilities are mole fraction, weight fraction, moles per mole of
water, weight per weight of water, SCF per Std. bbl of water and std m3 per std m3 of water.
Values must be entered in all cells in the solubility table. Enter a value of “-1” in the table to
exclude that data point from the regression.
Please note that when regression is being performed on aqueous phase solubility parameters,
all OGW flashes specified within the regression block must be at the same temperature.
WinProp does not accept experimental data for 4-phase calculations.
Asphaltene/Wax Modelling
Theoretical Background
Thermodynamic Model
The precipitation of asphaltene and wax phases is modelled using a multiphase flash
calculation in which the fluid phases are described with an equation of state and the fugacities
of components in the solid phase are predicted using the solid model described below. The
solid phase can consist of one or more components. The approach for modeling asphaltene
and wax precipitation is described in detail in Nghiem et al. (1993, 1996) and Kohse et al.
(2000). The precipitated phase is represented as an ideal mixture of solid components. The
fugacity of a precipitating component in the solid phase is:
v ⎡ p − p tp p * − p tp ⎤
ln f s = ln f s* + s ⎢ − ⎥
R ⎢ T T * ⎥
⎣ ⎦
ΔH tp ⎡ 1 1 ⎤ ΔC p ⎡ ⎛ T* ⎞ ⎤
− ⎢ln⎜ ⎟ − Ttp ⎛⎜ 1 − 1 ⎞⎟⎥
⎢ − ⎥− ⎜ ⎟
R ⎣ T T* ⎦ R ⎢⎣ ⎜⎝ T ⎟⎠ ⎝ T T * ⎠⎥⎦

where fs is the fugacity at pressure p and temperature T, fs* is the fugacity at pressure p* and
temperature T*, vs is the solid phase molar volume of the component, ΔCp is the solid-liquid
heat capacity difference, ΔHtp is the heat of fusion at the triple point, ptp and Ttp are the triple
point pressure and temperature, and R is the universal gas constant.
For isothermal predictions, this equation can be simplified to give:
ln f s = ln f s* + v s (p − p * ) / RT
Characterization of the Solid Forming Components

The crucial step in modeling wax and asphaltene precipitation is the characterization of the
solid forming components, both in solution and in the solid phase. It was found that by splitting
the heaviest components into two components, a non-precipitating and a precipitating fraction,
good quantitative match with experimental data was obtained. This has been independently
verified for both wax and asphaltene precipitation problems.
Irreversible Asphaltene Calculations
WinProp has the capability to separate asphaltene precipitate into reversible and irreversible
parts. This can be useful for simulating laboratory forward or reverse contact experiments with
a series of asphaltene flash calculations.
Asphaltene is described as a reversible solid (S1) and an irreversible solid (S2). The conversion
of S1 to S2 is described by a simple chemical reaction:
S1 ←⎯→
K
S2
The rate of formation of S2 is given by:

r = k 12 C1 − k 21 C 2
where C1and C2 are the molar concentrations of S1 and S2 respectively. At equilibrium, the
rate is zero and the following equilibrium constant can be derived:
k 21 C1
K= =
k 12 C 2
The mole fraction of reversible solid relative to the total amount of solid is:
C1 K
x1 = =
C1 + C 2 K + 1
and the mole fraction of irreversible solid is
C2 1
x2 = =
C1 + C 2 K + 1
The procedure for simulating forward and reverse contact experiments is as follows:
The first stage of the experiment can be modeled using the solid flash with the first stage oil and
gas mixture. The total amount of solid precipitate will be determined from the thermodynamic
model. At the completion of this calculation, the amounts of reversible and irreversible solid
(x1 and x2) can be calculated from the above equations with a user-specified value of K. K = 0
indicates that all of the solid is irreversible, K = 1 gives equal amounts of reversible and
irreversible solid, and K >> 1 implies that the solid is essentially all reversible.

For backward contacts, the feed to the next flash calculation is defined by taking the liquid plus
the reversible solid, and combining it with injection gas. The irreversible solid is removed from
the system for this flash.
For forward contacts, the equilibrium vapor phase with no asphaltene is combined with fresh
oil. Therefore, for forward contacts, the degree of irreversibility will not affect the calculations.
Input Data - Asphaltene/Wax Modelling
You can model asphaltene or wax precipitation by selecting Calculations|Asphaltene/Wax
Modelling. The approach is described in detail in references cited above. It is recommended
that you go through the example data sets solid-asph1.dat, solid-phenanthrene.dat, solid-
wax.dat and solid-asph2.dat to get familiar with the approach.
Additional plotting options are available on the tab Plot Control for Asphaltene/Wax
modelling. If X-Y Plots is selected, the amount of solid in terms of weight percent
precipitated can be plotted in addition to three other phase properties.
Selecting Pseudo-Ternary Phase Diagram allows creation of a triangular diagram, displaying
the results of flash calculations in terms of phase split (e.g. liquid-vapor, solid-liquid-vapor, solid-
liquid, etc.) along dilution lines. The first step is to assign each component to one of three
pseudo-components by entering the number 1, 2 or 3 in the column labeled “Pseudo” in the table.
Pseudo-component 1 is at the lower left apex of the triangle, 2 is at the lower right and 3 is at the
top. Definition of the dilution lines is done by first selecting which two pseudo-components will
be held at a fixed ratio along each dilution line. For example, setting pseudo-components A to 1
and B to 2 indicates that the base of the dilution lines will be along the bottom of the diagram,
between apexes 1 and 2, and the lines will terminate at the top of the diagram at apex 3. The
molar ratios of the two pseudo-components along each dilution line are then defined by entering
the mole fraction of pseudo-component B for each desired line in the table under Dilution Line
Definition. The number of flashes desired on each dilution line must also be specified.
On Tab Ref. State, the following information is entered:
Calculation Method Identifier
The three-phase flash algorithm performs flash and stability calculations in an alternating
sequence. The calculation begins with a stability test on the single-phase fluid. If the phase is
unstable, a two-phase flash calculation is performed, followed by a stability test on the
converged two-phase system and so on. Three calculation methods are available. They differ
in the sequence in which the stability tests are performed. In Method 1, the stability test is
performed first with respect to the solid phase. In Method 2 (default), the stability test is
performed with respect to all fluid phases prior to a stability test with respect to the solid phase.
Method 3 is a special case of Method 1; with Method 3, a stability test on the converged two-
phase fluid-solid system is not performed. Thus, Method 3 is more efficient but not as rigorous
as Method 1. For most cases, Methods 1 and 2 converge to the same results. In exceptional
cases, it has been found that only one method converged while the other one failed.

Number of Solid Forming Components
Of the Nc total components, the user may specify the last N1 as the number of solid forming
components. The default is set to 1, that is only component number Nc can precipitate. Once
this number is specified in the text box provided, the component number and name for all the
precipitating components are shown on the first and second columns of the table on this tab.
Depending on the method selected for computing the reference fugacity, columns 3-5 of this
table will also be updated automatically.
Reference Fugacity (ln (solid fugacity (atm)))
Four options are available for specifying the reference fugacity through the Reference
fugacity combo box:
CALCULATE The reference fugacity at the specified pressure and temperature is set
equal to the fugacity of the solid forming component after the system has
converged to a single liquid phase or a two-phase vapor-liquid system.
LCORRELATE This is used for wax only. The reference fugacity at the specified
pressure and temperature will be correlated with the pure component
liquid fugacity at the same pressure and temperature.
PREVIOUS Use the value for the reference fugacity from a previous multiphase
solid flash calculation.
USER INPUT This selection implies that the value of the natural logarithm of the
reference fugacity in units of atmospheres as well as the corresponding
reference pressure and temperature will be input by the user for each
precipitating component on the table provided. The user must select this
option before the values can be entered in the table
If the reference fugacity specification is set to CALCULATE, solid onset pressures for the
same mixture but at different temperatures may be specified in the Additional Onset Points
table. ΔCp and ΔHtp (optionally vs) can be calculated so the solid model will match these onset
points.
Additional Onset Points
Solid onset pressures at different temperatures may be used to calculate parameters in the
solid model for performing temperature-dependent precipitation predictions.
The requirements for doing this calculation are:
• Two, three or four solid precipitation onset pressures at different temperatures must be
known for one fluid composition.
• The solid phase must be modelled with a single component, as is normally done for
asphaltene precipitation modelling.
The pressure and temperature for one of the onset points must be entered on the Calculations
tab as the pressure and temperature for the flash. This will be used as the reference condition,
and will define the reference fugacity. Calculation of the other parameters will depend on the
number of additional onset points entered, as described below. Normally vs is adjusted to
match a known amount of solid at a given condition (bulk precipitation experiment)
otherwise it will default as described under Solid-Phase Molar Volume.

• 1 additional onset point – ΔCp is set to the user-input value or defaults to zero. ΔHtp is
calculated to match the specified onset point.
• 2 additional onset points – ΔCp and ΔHtp are calculated to match the specified onset
points.
• 3 additional onset points – ΔCp, ΔHtp and vs are calculated to match the specified onset
points. This is not normally done, as it is preferable to use vs to match a bulk
precipitation experiment.
Reference Pressure (psia | kPa | kg/cm2)
This corresponds to the reference pressure for calculating reference fugacity. This pressure is
required only if a reference fugacity is actually entered. If Field units is selected enter value
in psia, for SI units in kPa and for modified SI units in kg/cm2. When the CALCULATE,
PREVIOUS or LCORRELATE options are selected for the reference fugacity, the
reference pressure is set internally by the program and need not be entered on the table.
Reference Temperature (°C for SI or °F for field units)
This corresponds to the reference temperature for calculating the reference fugacity. This
temperature is required only if a reference fugacity is actually entered. When the
CALCULATE, PREVIOUS or LCORRELATE options are selected for the reference
fugacity, the reference temperature is set to appropriate values internally by the program and
need not be entered on the table.
Solid-Phase Molar Volume (l/mol)
This corresponds to the component solid-phase molar volume for the calculation of the
component solid-phase fugacity. If the molar volume is not specified, the following value is
assigned:
• If the reference fugacity option is CALCULATE, the solid-phase molar volume is
calculated from the EOS, unless 3 additional onset points have been specified.
• If the reference fugacity option is LCORRELATE then the molar volume is
obtained from a correlation by Won (1986).
• If the reference fugacity option is PREVIOUS, the solid-phase molar volume from
the previous calculation is used.
• If a value for the reference fugacity is entered, the solid-phase molar volume is
calculated from the EOS.
Heat Capacity (cal/K/mol)
This corresponds to the component solid-liquid heat capacity difference for calculation of the
component solid-phase fugacity. If this quantity is not explicitly specified for each
precipitating component, the following value is assigned:
• If the reference fugacity option is CALCULATE, the solid-liquid heat capacity
difference defaults to zero, unless 2 or more additional onset points have been
specified.
• If the reference fugacity option is LCORRELATE then the heat capacity
difference is obtained from a correlation by Pedersen (1991).

• If the reference fugacity option is PREVIOUS, the solid-liquid heat capacity
difference from the previous calculation is used.
• If a value for the reference fugacity is entered, the solid-liquid heat capacity
difference defaults to zero.
Heat of Fusion (cal/mol)
This corresponds to the component heat of fusion for the calculation of the component solid-
phase fugacity. If this quantity is not explicitly specified for each precipitating component,
the values are obtained from a correlation by Won (1986).
Triple Point Pressure (psia | kPa | kg/cm2)
If the triple point pressure for each precipitating component is known then these may be
specified under the column heading Triple Pres. If Field units is selected enter value in psia,
for SI units in kPa and for modified SI units in kg/cm2. If the triple point pressure is not known
then the default is a value of zero, which is realistic for high molecular weight compounds.
Triple Point Temperature (°C for SI or °F for field units)
If the triple point temperature for each precipitating component is known then these may be
specified under the column heading Triple Temp. If not known then the values are estimated
from an internal correlation that was developed by Won (1986).
Ratio of reverse over forward rate for conversion to irreversible solid
This is the equilibrium constant “K” described above under “Irreversible Asphaltene
Calculations”.
Single-Phase Calculation
A flash calculation in the single-phase region yields a single-phase system. However, if the
fluid is known a priori to be single phase, its properties can be calculated directly with the
single-phase calculation option. This option is invoked by selecting Calculations|Single-
phase Fluid. Please be advised that WinProp will assume single-phase for all calculations
even if the fluid is multiphase. An example data set for this option is singlephase.dat.
Isenthalpic Flash Calculations

Theoretical Background
Isenthalpic flash calculations correspond to finding the temperature, phase splits (phase mole
fractions) and phase compositions, given the pressure, composition and enthalpy of the feed,
together with the net enthalpy added to the system (Agarwal et al, 1988).
For isenthalpic flash calculations, in addition to the material and phase equilibrium relations
applicable to isothermal flash calculations, there is an energy balance equation, i.e.
np nc
( )
g n p ≡ H − H spec = ∑ Fj ∑ y ij h ij − H spec = 0
j =1 i =1

where Hspec is the specified molar enthalpy of the system and hij is the partial molar enthalpy
of Component i in Phase j which is also obtained from an EOS.
Two schemes for isenthalpic flash calculations are discussed below. The final scheme is a
hybrid of these two schemes.
Scheme 1
Scheme 1 consists of performing a series of multiphase isothermal flash calculations by
adjusting the temperature to satisfy the energy equation. In other words, the temperature is
varied in an outer loop, and the isothermal flash equations are solved in an inner loop.
Techniques for solving the multiphase isothermal flash equations are taken from Nghiem and
Li (1984) and Nghiem et al (1985).
The isenthalpic flash calculations are initiated by an isothermal flash calculation at the
specified feed composition z, the specified pressure p and an initial guess for temperature,
T(0). A new temperature T(1) is then determined from the energy equation by assuming that
the phase mole fractions, compositions and specific enthalpies are constant. With T(0) and
T(1), a secant method for solving the energy equation is set up in the outer loop.
As discussed later, Scheme 1 does not work for systems with a degree of freedom equal to
unity, e.g. one-component two-phase system, two-component three-phase system.
Scheme 2
Scheme 2 basically follows Michelsen's approach (Michelsen, 1987), but the implementation
is different. This scheme is a stage wise procedure where the system is assumed to be
initially single-phase, and where the number of phases is increased if necessary between
iterations. Furthermore, this scheme attempts to converge the material balance equation, the
energy balance equation and the equilibrium equation in a sequential manner. This method
also works for systems with a degree of freedom equal to unity.
Special Considerations
Isenthalpic flash calculations are more complex than isothermal flash calculations because of
the lack of the a priori knowledge of temperature (and phases) and because of the presence of
narrow boiling mixtures. The implications of these two factors are discussed in the following.
Phase Information
Since temperature is not known a priori in isenthalpic flash calculations, the traditional
stability analysis of the Gibb's free-energy surface (Nghiem and Li, 1984) cannot be used to
determine the number of phases that actually exist at convergence. A stability analysis can
only give the number of phases at the initial temperature estimate, which may not be the same
as the number of phases at convergence. This leads to the appearance and disappearance of
phases during the iterative process. This does not create any difficulties for Scheme 1 but
could cause convergence problems for Scheme 2.
Narrow-Boiling Systems
Narrow-boiling systems are those where the enthalpy changes drastically for a small change
in temperature during phase transition. Although many multicomponent fluids exhibit this
behavior, a single-component fluid in the two-phase region and two-component fluid in the
three-phase region are extreme examples of narrow-boiling mixtures.

From the phase rule, the degree of freedom F of a system with nc components and np phases is
F = nc+ 2 - np
Thus for a single-component system in the two-phase region, F = 1. This implies that, if the
pressure is fixed, the two-phase temperature is also fixed. In other words, pressure and
temperature are dependent on each other in the two-phase region. The enthalpy for this
system is determined by the phase split in the two-phase region. The same analysis applies to
a two-component system in the three-phase region.
Effect of Narrow-Boiling Systems on the Calculations
Scheme 1 is not applicable to systems with a degree of freedom equal to unity (e.g. one-
component two-phase systems, two-component three-phase systems) because it attempts to
satisfy the energy equation by adjusting the temperature. For these systems, the energy
equation can only be satisfied by adjusting the phase split. Otherwise, Scheme 1 works for
any multicomponent systems with nc ≥ 3 even if they exhibit narrow-boiling behavior.
Calculation Procedures
A hybrid scheme, where five scheme-2 iterations are performed for every scheme-1 iteration, is
very stable and robust. Of course, only Scheme-2 is used for one and two component systems.
Input Data - Isenthalpic Flash
Add this option to your data set by selecting Calculations|Isenthalpic Flash. A number of
examples are provided in the template test bed. These cases are named flash-isenth1.dat
through flash-isenth3.dat and can be found under the template (.tpl) directory. For Feed, K-
values, Output level and Stability test level specifications, see the Chapter “Common Data
Required for all Options”.
Flash calculations are performed at the pressure specified in the Text Box labeled Pressure.
Enter a value for the enthalpy in the text box labelled Enthalpy. In the Text Box labeled
Temperature, enter an initial guess for the temperature. This initial guess for the
temperature is required input and must be specified by the user.
As detailed above under the calculation method identifier section of the theoretical
discussion, two methods are implemented to solve the nonlinear set of equations
corresponding to isenthalpic flash. A hybrid scheme where five scheme-2 iterations are
performed for every scheme-1 iteration is very stable and robust and is the default choice.
The integer number entered in the text box labeled Calculation Model indicates the number
of iterations of scheme 2 to be used for every iteration of scheme 1. A value of zero therefore
implies the selection of Scheme1 exclusively. A value equal to or greater than 101 will be
interpreted as the selection of Scheme 2 alone.

Three-Phase Boundary Calculation
Background
For systems that exhibit three-phase behavior, there exist conditions where one of the phase
mole fractions goes to zero. Under these conditions, there are two phases in equilibrium with
an infinitesimal amount of a third phase. The locus of all these conditions corresponds to a
three-phase boundary. Nghiem and Li [21] describe calculation techniques for constructing
the three-phase boundary; these are extensions of the two-phase boundary calculations
described in a separate chapter. You can calculate the following envelopes:
• Pressure-Temperature (PT) diagram
• Pressure-Composition (PX) diagram
• Temperature-Composition (TX) diagram
Input Data
The three-phase boundary calculation is invoked by selecting Calculations|Three-phase
Envelope. Examples of three-phase PT envelope and PX envelope are in envel_3ph-pt.dat
and envel_3ph-px.dat respectively. This calculation requires good initial guesses for
convergence. Therefore the pressure, temperature, and K-values must be obtained from a
previous three-phase flash calculation near the boundary as in envel_3ph-pt.dat, or entered by
the user as in envel_3ph-px.dat.
Envelope Specification Tab
Specify the type of envelope (PT, PX, or TX) to be calculated by selecting the variables for the
x- and y-axes on this tab. For the PT diagram the composition is fixed. The composition is
determined based on the data entered on the form Composition and the feed specification
entered on Tab Feed/Output/Stability. For the PT envelope, also specify the first point to be
calculated by entering a value for the x-variable and an estimate for the y-variable in the combo
boxes labelled Pressure and Temperature respectively. The x-variable and y-variable are also
called independent and dependent variables respectively. The choices for the combo box for the
y-variable are: Previous, or enter a value explicitly. For PX and TX diagrams the composition
changes as the envelope is traversed. The x-axis variable in these cases is the mole fraction of
the secondary fluid. The initial value of this mole fraction is as defined by the feed specification.
For the PX diagram, enter the initial guess for the pressure in the combo box labelled Pressure.
Also enter a value for the temperature (fixed) in the combo box labelled Temperature.
User's Guide WinProp Three-Phase Boundary Calculation • 73

Similarly for the TX diagram, enter an initial guess for the temperature in the combo box
labelled Temperature and a value for the pressure (fixed) in the combo box labelled
Pressure.
For all cases an initial guess for the mole fraction of either the vapor phase or the second
(intermediate) liquid phase is also required. For the boundary corresponding to zero vapor
phase, enter a value for the “second liquid” or intermediate phase mole fraction. For the
boundary corresponding to zero second liquid phase, enter a value for the vapor phase mole
fraction initial guess. If Use values from previous calculations is selected, WinProp will
calculate the boundary corresponding to the phase with the lowest mole fraction (in the
previous calculation) equal to zero.
Defaults for the maximum and minimum values for the x- and y-variables can be overridden
by entering values in the appropriate text boxes. The calculations stop when the maximum or
minimum values are exceeded or when the maximum number of points has been calculated
(see Envelope Construction Controls Tab). The calculations will also stop if the mole
fraction of any phase falls outside the limits specified by the values in the text boxes
Minimum phase mole frac and Maximum phase mole frac. The default values of –10 and
10 for the minimum and maximum are chosen such that the calculation will not stop unless
large non-physical values of the phase mole fractions are encountered.
The Tab Envelope Specification corresponding to envel_3ph-px.dat is shown below:
74 • Three-Phase Boundary Calculation User's Guide WinProp

Envelope Construction Controls Tab
Maximum Number of Points

This value corresponds to the maximum number of points calculated on the phase diagram.
Initial Step Size
The Initial step size controls the spacing between the calculated points on the envelope.
Both positive and negative values may be used. For positive values, the diagram is traced
initially in the direction of increasing x-values. For negative values, the diagram is initially
traced in the direction of decreasing x-values. WinProp internally estimates the step size for
subsequent points on the envelope.
Average Number of Iterations
This value is used to adjust the distance between two consecutive points on the diagram. The
distance is increased if the actual number of iterations is less than the entered values, and is
decreased in the opposite case.
Independent Variable Interpolation Points
These correspond to x-values for which you want calculated y-values. Because the step size
in the envelope calculation is automatic, these interpolation values must be entered to force
calculations at desired x-axis values.
User's Guide WinProp Three-Phase Boundary Calculation • 75

Initial K-Values Tab
The estimates of the K-values for the first point on the boundary can be from a previous
calculation, or entered in the appropriate table as shown in the above figure.
76 • Three-Phase Boundary Calculation User's Guide WinProp

Component Splitting and Lumping
Overview
Our experience shows that two representations of the components are normally required in
the modelling of the phase behavior of reservoir fluids. In the first stage, the fluid system is
represented by a large number of components (e.g. C1, C2, C3, ..., C29, C30+). Simple
calculations such as saturation pressure calculations are performed on this many-component
system to verify the adequacy of the EOS. We found that in most cases the EOS can predict
accurately the saturation pressure with only minor adjustment to the Hydrocarbon Interaction
Coefficient Exponent (HICE). See the chapter entitled “Regression” for more details. This
many-component representation is not practical for compositional simulation because of the
excessive run time and memory requirements. The second stage involves the lumping of the
many-component system into fewer components (e.g. 10).
Reservoir fluids typically consist of pure, well-defined components such as CO2, N2, C1, C2,
etc., and many hundreds of heptanes and heavier components (C7+). The laboratory analysis of
a reservoir fluid includes generally a gas chromatograph analysis of the C7+ fraction into Single
Carbon Number (SCN) fractions up to C30+ for example. Characterization of the C7+ fraction as
a number of pseudo-components is accomplished using WinProp’s Plus Fraction Splitting and
Component Lumping calculation options.
If a full extended analysis is available with mole fraction, MW and SG or Tb given for each
SCN fraction, the SCNs may be entered as user components directly on the Component
Selection/Properties form. If a complete analysis is not available, the Plus Fraction Splitting
calculation is used to define a distribution function relating mole fractions to molecular weights
of the C7+ fraction.
Three distribution functions are available in WinProp: exponential, two-stage exponential,
and gamma distribution. The implementation of the distribution functions depends on the
experimental data available.
If a partial extended analysis is given (e.g. only MW and mole fraction of the SCN fractions)
and one of the exponential distribution types is selected, the splitting calculation does not use
the distribution function. SG and Tb values for the SCN fractions are determined from
correlations based on the SG and MW of the plus fraction. Subsequently, critical properties
of the SCNs may be generated. After the splitting, the SCNs representing the C7+ fraction can
be lumped into fewer components based on K-values estimated from Wilson's correlation
using the Lee-Kesler mixing rules, (Lee and Kesler [15]).
User's Guide WinProp Component Splitting and Lumping • 77

If a partial extended analysis is given and the gamma distribution is selected, the α parameter
in the distribution is determined by minimization to obtain the best fit of the distribution to
the experimental data. At this point, the analysis may be extended by using the distribution
function to generate mole fraction and molecular weight data for SCNs beyond the last
fraction in the experimental analysis. SG, Tb and critical properties of the SCNs may be
generated and lumping to fewer components may be done as for the exponential distribution
case. Alternatively, the gaussian quadrature technique may be used to determine MW and
mole fractions of the pseudo-components from the distribution function. Correlations are
then used to generate the SG, Tb and critical properties of the pseudo-components directly,
rather than using mixing rules.
If no extended analysis is available, i.e. only mole fraction, SG and MW of the C7+ fraction
are known, the parameters in the chosen distribution function are adjusted to match the
known data. The distribution function is then used to generate SCN mole fraction and MW.
Once this is done, the characterization may proceed as described for the partial extended
analysis cases above. Due to the larger number of adjustable parameters in the gamma
distribution, the α parameter must be specified if no extended analysis is available. If it is not
input by the user, the program will estimate a value for this parameter.
The Component Lumping calculation may be specified in a data set if the SCNs were not
lumped within a splitting calculation, or to further reduce the number of components. The
lumping scheme may be input by the user, or the program can generate the pseudo-
components using an internal algorithm. We recommend specifying a lumping scheme based
on the K-values of the many-component system at a prevailing condition in the reservoir, e.g.
the saturation condition.
Characterization of Multiple Related Samples

Multiple related samples can be characterized using the gamma distribution and gaussian
quadrature techniques as described by Whitson et al [40]. This results in a single set of C7+
fraction pseudo-components for all samples. Plus fraction MW and SG for each sample are
matched by determining the correct mole fractions of each pseudo-component for the sample.
Data for each sample is entered in exactly the same manner as for single sample characterization.
The same type of data need not be entered for each sample; i.e. an extended analysis may be
entered for one sample and only plus fraction SG, MW and mole fraction for another sample.
Splitting the "Plus" Fraction

This option is invoked be selecting Characterization|Plus Fraction Splitting. An example
data set for this option is split-mwsg_plus.dat.
General splitting model controls are entered on Tab General of the Plus Fraction Splitting
calculation form as described below.
78 • Component Splitting and Lumping User's Guide WinProp

Distribution Function Type
Three choices are available for the distribution function for splitting the plus fraction:
Exponential Exponentially decreasing function appropriate for gas
condensates and lighter fluids
2-Stage Exponential Approximation to the gamma function suitable for black oil
type fluids
Gamma Three-parameter gamma distribution suitable for all fluid types
Number of Fluid Samples

If the gamma distribution is chosen, up to 8 related fluid samples may be characterized
simultaneously. If the exponential distributions are chosen, this text box is not enabled.
First Single Carbon Number in Plus Fraction
Enter the carbon number of the lightest SCN in the plus fraction (e.g. enter 6 to characterize a
C6+ fluid fraction).
Number of Pseudo-Components
The SCNs can be used as is in subsequent calculations or lumped into pseudo-components
right after the splitting procedure. The following options are available:
No lumping The SCNs will be used as is.
Determined internally WinProp will estimate internally the number of pseudo-
components for the plus fraction.
Input value Specify the desired number of pseudo-components.
When using the gamma distribution and gaussian quadrature without extended analysis, the
number of pseudo-components cannot be estimated via correlation and will be set equal to 3.
Lumping Method
Log(K) lumping is available when characterizing a single sample with any of the distribution
functions. Gaussian quadrature lumping may be used with the gamma distribution, and is
required for characterizing multiple samples. Log(K) lumping defines pseudo-components as
having equal ranges of log(K). Gaussian quadrature lumping defines pseudo-components via
analytical integration of the gamma distribution.
Critical Properties Correlation
Three correlations are available to calculate the critical properties of the SCNs.
1. Lee-Kesler (Kesler and Lee [12])
2. Riazi (Riazi and Daubert [34])
3. Twu (Twu [36])
On the Distribution Tab, parameters relating to the chosen distribution are entered. Three of
these properties are common to both exponential and gamma distribution types, as follows.

SCN Fraction MW Interval
This corresponds to the interval in molecular weight for each single carbon number group. For
the gamma distribution, if a variable MW is selected this value is ignored. The default is 14.026.
“Bias” Parameter for SCN MW End Points
This parameter is used for setting the minimum molecular weight for the plus fraction
distribution. A value of 0 means that the minimum MW will be equal to the normal alkane
MW of the same carbon number as the first SCN fraction in the plus fraction. A value of 1
means that the minimum MW will be equal to the normal alkane MW of one lower carbon
number than the first SCN fraction in the plus fraction. The default value is 0.75.
Distribution Function Cutoff
This parameter is used in determining the number of pseudo-components for lumping. This
calculation requires specification of a maximum SCN number. Setting the cutoff to 1.0 means
that the maximum SCN number will be set equal to the last SCN number in the analysis. This
often leads to over-prediction of the required number of pseudo-components. Setting the cutoff
less than 1.0 indicates that the maximum SCN number will be taken as the one at which the ratio
of the sum of the individual SCN mole fractions to the total plus fraction mole fraction exceeds
the cutoff. The value should be less than 1. The default is 0.95.
Parameters specific to the exponential distributions are:
Mole Fraction of Component Preceding Plus Fraction
This value is used to set the “Y-Axis” intercept of the two-stage exponential distribution
function. For C6+ fraction characterization, this value should be set equal to the mole fraction
of the C5 components, for C7+ fraction characterization, this value should be set equal to the
mole fraction of the C6 components, etc.
“Y” Axis Intercept of the Distribution Function
This is usually set equal to the mole fraction of the component preceding the plus fraction
(default).
Parameters specific to the gamma distribution are:
SCN MW Interval Type
When fitting the gamma distribution to extended analysis data, the SCN fractions can have
fixed or variable intervals in molecular weight. Choosing Constant sets the MW interval
equal to the value entered under SCN fraction MW interval. Choosing Variable (match
mole fraction) or Variable (match weight fraction) indicates that the upper MW boundary
of the SCN fraction is varied until either the experimental mole fraction or the experimental
weight fraction (default) of the SCN is matched.
Eta Parameter (Minimum MW in Distribution)
The eta (η) parameter specifies the minimum molecular weight in the gamma distribution. By
default, it will be calculated as described under “Bias” parameter for SCN MW end points.

MW of Heaviest Pseudo-Component
The choices for molecular weight of the heaviest pseudo-component are No Restriction,
Internal Default or entering a value. Specifying No Restriction implies no upper limit in
MW on the gamma distribution, and is not recommended. It leads to prediction of very high
molecular weights for the heaviest pseudo-component. The default setting obtained by
selecting Internal Default sets the heaviest pseudo-component MW equal to 2.5 times the
MW of the plus fraction. If multiple samples are used and No Restriction is selected, it will
automatically be reset to Internal Default.
SG-Tb-MW Correlation
When Gaussian quadrature is used with the gamma distribution, the following correlations are
available for determining pseudo-component boiling point from specific gravity and molecular
weight.
1. Twu (Twu [36])
2. Goossens (Goossens [7])
3. Riazi (Riazi and Daubert [34])
The controls available for determining gamma distribution parameters by minimization are:
Residual Value
The choices for residual value depend on what is selected under SCN MW interval type. The
residual value setting indicates what experimental data for each SCN is used in defining the error
function to be minimized. The choices are Molecular Weight, Mole Fraction and Weight
Fraction. If a constant MW interval is chosen, then molecular weight is not available as a choice
of residual value. Similarly, if a variable MW interval is chosen to match the mole fraction, then
mole fraction is not available as a choice of residual value. The default is to vary the MW interval
to match the weight fraction of the SCN, and adjust the distribution α parameter to minimize the
error function defined in terms of the molecular weights.
Residual Type
The choices for residual type are Sum of Squares, Chi Square Goodness-of-Fit Test or
Sum of Scaled Squares. The default is sum of squares. For most applications, the difference
in minimization results between the residual types will be small.
Final SCN Fraction Data
The residual calculation can be specified to include or not include the data from the final
SCN fraction in the analysis.
On each Sample Tab, the properties of the plus fraction are entered. The number of sample
tabs appearing is set according to the Number of Fluid Samples entered on the General tab.
If extended analysis data is available from a true or simulated boiling point (distillation) analysis,
the data can be entered in the table on the Sample tab. In column 2 enter the mole fraction of
each fraction. In column 3 enter the average molecular weight of the fraction. Note that if any
extended analysis data are to be entered, mole fraction and molecular weight are required for
each cut. If data is available then values for the specific gravity can be entered in column 4 and
normal boiling point in °C in column 5. Please note that if data for normal boiling point is

entered then data for specific gravity must also be entered. Sample data sets with extended
analysis data are split-mw_analysis, split-mwsg_analysis and split-mwsgtb_analysis.
Number of SCN Fractions
If this entry is left blank, the value will default to the number of fractions in the analysis, or to
25 if there is no extended analysis. If the exponential distributions are used with extended
analysis, and a value for number of SCN fractions is entered, it will be ignored. If the gamma
distribution is used with extended analysis, and a value for number of SCN fractions is
entered that is greater than the number of fractions in the analysis, the analysis will be
extended using the distribution function to the specified SCN number.
MW+
Molecular weight of the plus fraction must be entered in the text box unless extended analysis
data is given.
SG+
Specific gravity of the plus fraction must be entered in the text box unless SG data is given in
the extended analysis table.
Z+
Mole fraction of the plus fraction must be entered in the text box unless extended analysis
data is given.
If one of the exponential distribution function types is selected then the following data entry
box will be available:
Slope
This is the slope of the exponentially decreasing curve of the distribution function. If not
specified then it is determined internally based on data for a typical oil.
If the gamma distribution function is selected then the following data entry box will be available:
Alpha
This parameter is analogous to the slope parameter used for the exponential distribution types. If
α>1, the distribution has a peak in mole fraction for an SCN greater than the initial SCN in the
distribution. If α=1, the gamma distribution reduces to an exponential distribution, and if α<1 the
function decreases more rapidly than an exponential distribution. In general, α is larger for
heavier fluids, and smaller for lighter fluids. The normal range is from 0.5 to 2.5. If extended
analysis data is available and α is not specified, it is determined by minimization to best fit the
experimental data. If extended analysis data is not available and α is not specified, an estimate is
determined internally based on plus fraction SG and MW.
Importing Extended Analysis Data with the Table Import

Wizard
The Table Import Wizard is a tool designed to assist the user in importing Excel or ASCII
“Tutorial” section of this manual. Specific information relating to the import of extended
analysis data is given here.

The Table Import Wizard can be used to append or insert extended analysis data at the
currently selected row in the extended analysis table. The wizard is launched by clicking on
the Table Import Wizard button located on any of the Sample tabs. Data for any of the
columns appearing in the table may be imported.
Note that the Table Import Wizard cannot be used to import columns of data for existing SCN
fractions. The standard Windows cut, copy and paste functions can be used for this purpose.
Numerical Cleaning of Mud-Contaminated Samples

This option can be used to determine the original composition of reservoir fluids from mud-
contaminated samples. WinProp uses a skimming method, subtraction method or a
combination of both methods, depending on the user’s input. On any of the Sample tabs in
the Plus Fraction Splitting interface, the user decides if that sample needs to be numerically
cleaned by checking “Conduct Contaminated Sample Analysis”. If the sample needs to be
cleaned, the level of mud contamination should be entered in the text box if it is available. On
a separate Mud Info tab, the user needs to provide additional information about the mud,
including the first and last SCN in the mud (required) and the mud composition (optional).
An example interface for the Mud Info tab is shown below. Please see the template data set
mudclean_split.dat for example data input.
First and Last Single Carbon Number in the Mud

The first and last SCN in the mud must be entered in the text box on the Mud Info. Tab.

Mud Composition Table
If the mud composition data is available, the data can be entered in the table on the Mud Info
tab. In column 2 enter the mole fraction of each mud fraction. In column 3 enter the average
molecular weight of that mud fraction. The Table Import Wizard button can be used to append
or insert mud composition data at the currently selected row in the mud composition table.
Level of Contamination
This parameter can be input under each Sample tab, if available. The level of mud
contamination is expressed as the weight fraction of the mud. If this parameter is available and the
mud composition is also provided, a direct subtraction method will be used to numerically clean
the contaminated sample. If this parameter is not available but the mud composition is provided, a
combination of the skimming method and subtraction method will be used to estimate the level of
contamination first, and then numerically clean the contaminated sample. If there is no
information about the level of contamination and mud composition, WinProp can use the
skimming method to numerically clean the contaminated sample based on the first and last SCN
in the mud.
Lumping of Components
This option is invoked by selecting Characterization|Component Lumping. An example
data set for this option is lumping.dat. An example interface for this option is shown below.

Two options are available to the user in specifying the lumping method: explicitly entering the
lumping scheme or relying on the internal algorithm to determine the number of pseudo-
components. This algorithm is documented in Appendix B. The lumping method selection is
made with the radio buttons located under the Lumping Method label. The user-defined scheme
is specified in the table shown on this form. The first column shows the component name from
the many-component system. For information purposes, the primary and secondary compositions
are shown in the second and third column. The lumping scheme is specified by clicking the left
mouse button in the fourth column. Clicking the first time on the i-th row sets the lumping of
Component 1 to Component i of the many-component system into Pseudo-Component 1 of the
fewer-component system. Clicking the second time on the j-th row sets the lumping of
Component i+1 to Component j of the many component system into Pseudo-Component 2 to the
fewer component system, and so on. The Undo button undoes the last mouse click. The Reset
button clears the current lumping scheme. The user has control in selecting the last component Nl
in the original list of the Nc component system that will be involved in the lumping. That is
component 1 in the list through component Nl will be lumped. This selection is made through the
group up to component combo box.
The critical properties of the pseudo-components are estimated using the mixing rules of Lee
and Kesler [15].
Transferring Results to Other Data Sets

The results of the splitting and lumping calculation options are component properties and
compositions that can be used in subsequent calculations. For example, when these
calculations are made with file test1.dat, WinProp will generate a file called test1.rls as well
as the standard output test1.out. The file with the (.rls) extension contains the component
properties and composition in a format that can read back in by WinProp. This is achieved by
selecting File|Update component properties. Three forms will be updated:
Titles/EOS/Units, Component Selection/Properties, and Composition. Calculation
options can then be inserted from the menu. After these calculation options have been
defined, use File|Save as... to save this file with a different name, e.g. test2.dat if desired. A
similar procedure applies to the Regression option.

Laboratory Calculations
Overview
WinProp performs the following laboratory calculations:
1. Recombination of separator oil and gas
2. Compressibility measurements
3. Constant composition expansion
4. Differential liberation
5. Separator test
6. Constant volume depletion
7. Swelling test
Descriptions of the above laboratory procedures can be found in Pedersen et al. [29] and McCain
[17]. You can also include experimental data in these calculations for regression purposes.
Convention for Experimental Data Input

Many experimental data are entered in tabular form. You are required to enter data for all
pressures or mixtures. For missing data, enter "-1.0" in the corresponding cell. The program
will ignore all negative data in the regression. WinProp will put "-1.0" into empty cells
corresponding to pressures or mixtures that have values in some other cells.
You can also enter a negative sign ("-") in front of any piece of data to exclude it from the
regression.
Recombination of Separator Oil and Gas

Overview
When downhole samples of hydrocarbon fluids are not available, the separator oil and gas are
recombined to obtain a representative sample of the reservoir fluid. The recombination is
performed at the separator gas-oil ratio (GOR) in the laboratory.
For the recombination calculation, the ratio of oil and gas volumes needs to be converted to a
molar ratio. This allows the wellstream molar composition to be calculated from the known
separator oil and gas molar composition. The conversion of GOR to a molar ratio requires
the densities of the two streams to be known. The calculated recombined fluid composition is
therefore sensitive to the values assigned to the oil and gas densities. Normally the densities
are calculated from the equation of state (EOS). While the EOS based gas density is reliable,
User's Guide WinProp Laboratory Calculations • 87

the EOS calculated oil phase density is generally not as accurate. A number of options in
addition to the EOS are therefore provided for specifying the densities. These are
1) Entering the densities directly and
2) Use of the Alani-Kennedy correlation for calculating the oil phase density and
Dranchuk et al. [4] correlation for calculating the gas phase density.
Further discussion of these correlations follows in the next section.
A key concern is the quality of the compositional data collected in the field for the recombination
calculation. A fast and reliable way of evaluating the consistency of the data is through a
graphical technique, known as the Hoffman plot [9]. This plot is created by plotting the logarithm
of the product K-value times pressure versus a component characteristic factor, F. If the data is
good, that is the oil and gas samples are reasonably in equilibrium at the separator conditions and
the measurement of the oil and gas compositions is generally error free, then the points for
components C1-C6 should fall on a straight line. Compositions corresponding to components N2
and C7+ are generally not measured as accurately. The parameter, F, is defined as follows:
(log Pc − log Pa ) ⎡ 1 1⎤
F= ⎢ − ⎥
⎛ 1 1 ⎞ ⎣ Tb T ⎦
⎜⎜ − ⎟⎟
⎝ Tb Tc ⎠
Where
Pc = critical pressure,
Tc = critical temperature,
Pa = atmospheric pressure,
Tb = normal boiling point and
T = Temperature
Input Data
Invoke the Recombination calculation option by selecting Lab|Recombination from the
menu. An example data set is recombine.dat. The separator pressure, temperature and gas-
oil ratio are the required inputs to be specified in the text boxes under the frame labelled
Separator conditions. The compositions of the separator oil and gas are also required and
are entered on the form Composition, with the oil entered as the primary composition and the
gas as the secondary composition.
The default method is to calculate the oil and gas densities from their respective compositions
and the separator pressure and temperature using the equation of state (EOS). Generally, the
EOS calculated oil density is not reliable. Therefore, if an experimentally determined value
for the oil density or oil specific gravity is available, enter it directly instead. In the case of
specific gravity, select the button Specific gravity entered and enter a value in the adjacent
text box. If the oil density is available select the Mass density entered button and enter a
value in the adjacent text box in the units stipulated. A third choice is to use some model
other than the EOS to predict the oil density. Since the composition is known the Alani and
Kennedy correlation is a good choice. To use this method select “From Alani Kennedy
correlation...” button and enter values of the C7+ specific gravity and molecular weight. This
88 • Laboratory Calculations User's Guide WinProp

method is considered to be quite accurate even for highly volatile oils. The authors used
experimental density data to develop a cubic equation for the oil molar volume:
v 3 − (R (T + 460) / P + b )v 2 + av / P − ab / P = 0
where,
v = Molar volume, ft3/lbmol
T = Temperature, F
P = Pressure, psia
R = 10.7335, (psia) (ft3/lbmol)/R
The parameters a and b depend on the temperature and on component specific constants; for
pure compounds a and b are given by:
a = λe n / (T + 460 )
b = m(T + 460) + C
The values of λ, n, m and C are available in the literature for common compounds, see for
example Danesh [3]. For the C7+ fraction, a and b are obtained from an equation with the
specific gravity and molecular weight as well as the temperature being the inputs. Provision
is made to enter the specific gravity and molecular weight of the C7+ fraction on the
Recombination form. The values of a and b for the mixture are determined by molar
averaging. Please refer to reference [3], page 76-77 for more extensive presentation of this
material including an example calculation.
For the gas density the EOS value is reliable. However, a value may be entered directly or
calculated from the entered compressibility factor. A third option is to use the correlations of
Dranchuk, Purvis and Robinson [4]. Two methods are available for calculating the pseudo-
critical temperature and pressure: Kay’s rule and the Wichert and Aziz correlation [42].
The Hoffmann plot for the recombination can be generated by selecting the checkbox labelled
Perform Hoffmann, Crump, Hocott (HCH) Test at the bottom of the form.
The gas and oil are not in equilibrium from an EOS calculation viewpoint. Thus, a separator
calculation on the recombined fluid will not give the measured gas-oil ratio or oil and gas
compositions.
Another approach for doing recombination is to use the Separator calculation, and through a
trial-and-error approach find the fraction of gas in the gas/oil mixture that will give the
measured gas-oil ratio. The composition of the gas and oil are entered as the primary and
secondary compositions on Form Composition. The feed is specified on the second tab of
the Separator calculation by selecting the mole fraction of the primary fluid.

Compressibility Calculation
Overview
This option calculates the single-phase compressibility as defined by the following equation:
c = −1 / V(∂V / ∂P )
You invoke this option by selecting Lab|Single-phase Compressibility. An example data set
for this option is compress.dat. Note that in the output file, compressibilities are reported under
column headings labelled “global” and “liquid”. For the case where the mixture is single phase
at the given pressure and temperature these two values will be the same since the global and
liquid composition are identical. For the case where there are 2 phases, the compressibility
under “global” is the overall mixture (oil and gas) compressibility calculated using the equation
valid for single phase and the value under the “liquid” column is the oil phase compressibility.
Input Data
Once the primary fluid (usually oil) and secondary fluid (usually gas) compositions have been
entered on the Composition form, compressibilities for any number of fluids defined by
combining the oil and gas streams in different proportions can be determined. On tab 1,
Calculations, enter the temperature and on the table below enter for each mixture the initial
pressure, the pressure increment, the mole fraction of the secondary fluid in the mixture and
the number of pressure steps. The experimental compressibilities can be entered on the table
provided on tab 2, Experimental. Note that this table accommodates all the mixtures defined
on the previous tab. If a given experimental value is not available, enter a value of –1.0.
In the example data set compress.dat, compressibility calculations are carried out for four
fluid mixtures. For each mixture, the compressibility of the fluid is calculated for three
pressures equal to 24000 kPa, 25000 kPa and 26000 kPa respectively.
Constant Composition Expansion

Laboratory Procedure
A sample of the reservoir fluid is placed in a laboratory cell. Pressure is adjusted to a value
equal to or greater than the initial reservoir pressure. Temperature is set to the reservoir
temperature. Pressure is reduced by increasing the volume of the cell in increments. No gas
or liquid is removed from the cell.
At each step, the pressure and total volume of the reservoir fluid (oil and gas) are measured.
Additional data that can be determined include the liquid phase volume, oil and gas densities,
viscosities, compressibility factors or single phase compressibility above the saturation
pressure. The procedure is also called flash vaporization, flash liberation, flash expansion or
constant mass expansion.

Input Data
You invoke this option by selecting Lab|Constant Composition Expansion. Alternatively
add the option by clicking on the CCE button on the options toolbar. An example data set is
cce.dat. Enter data on tab 1, Pressure Levels.
For a description of the data entry related to the saturation pressure fields, please refer to the
section entitled “Saturation pressure”.
The reservoir or experimental temperature is entered in the text box labelled Temperature. The
pressure levels of CCE test are entered on the table provided under column 1 labelled Pressure.
Enter values starting with the highest pressure to the lowest. At least one value is required.
The following experimental data can be entered for regression for this option:
For a bubble point fluid:
1) Relative total volume ( total fluid volume at current pressure / fluid volume at
saturation conditions) above and below saturation conditions, dimensionless
quantity,
2) Liquid saturation as a percentage (volume occupied by the liquid phase / total cell
volume * 100) above and below saturation conditions, dimensionless quantity,
3) Oil viscosity above and below saturation conditions in cP,
4) Gas viscosity below saturation pressure in cP,
5) Gas compressibility factor below saturation conditions (dimensionless),
6) Oil compressibility factor above and below saturation conditions (dimensionless),
7) Gas density below saturation conditions, in units of kg/m3 for SI units and lbm/ft3
in field units,
8) Oil density above and below saturation conditions, in units of kg/m3 for SI units
and lbm/ft3 in field units,
9) Single phase oil compressibility, at and above saturation conditions, in units of
1/kPa for SI units and 1/psia in field units.
For a dew point fluid:
1) Relative total volume ( total fluid volume at current pressure / fluid volume at
saturation conditions) above and below saturation conditions, dimensionless
quantity,
2) Liquid saturation as a percentage ( volume occupied by the liquid phase / total cell
volume * 100) above and below saturation conditions, dimensionless quantity,
3) Oil viscosity below saturation conditions in cP,
4) Gas viscosity above and below saturation pressure in cP,
5) Gas compressibility factor above and below saturation conditions (dimensionless),
6) Oil compressibility factor below saturation conditions (dimensionless),
7) Gas density above and below saturation conditions, in units of kg/m3 for SI units
and lbm/ft3 in field units,

8) Oil density below saturation conditions, in units of kg/m3 for SI units and lbm/ft3 in
field units.
If experimental values are not available at all pressure levels for a given data type, a value of
-1.0 may be entered for the unknown values. Please see also the section on “Convention for
experimental data input”. For a given piece of data if the corresponding (predicted) value
cannot be calculated, for example single phase compressibility for a dew point fluid, then that
specific piece of data will not be included in regression.
Differential Liberation
This procedure is generally performed for a black-oil fluid to simulate the conditions
encountered in the reservoir. The sample of reservoir liquid in the laboratory cell is brought
to the bubble point pressure, and the temperature is set to the reservoir temperature.
Pressure is reduced by increasing the cell volume. All the gas is expelled from the cell while
pressure is held constant by reducing the cell volume. The gas is collected, and its quantity and
specific gravity are measured. The process is repeated in steps until atmospheric pressure is
reached. The temperature is then reduced to 15 °C or 60 °F, and the volume of the remaining
liquid is measured. This corresponds to the residual oil from the differential liberation.
Each of the values of liquid volume in the cell is divided by the volume of the residual oil to
obtain the relative oil volume or formation volume factor, Bo. The compressibility of the gas
(Z-factor), the gas density and the formation volume factor of gas (Bg) are also measured.
The total volume of gas removed during the entire process is the amount of gas in solution at the
bubble point. The solution gas-oil ratio (Rs) is calculated by dividing the total volume of gas by
the volume of residual oil. The solution gas at any lower pressure is obtained by subtracting the
sum of gas removed down to the pressure of interest from the total volume of gas removed.
A schematic of the differential liberation process is shown below:
Gas off All gas
displaced
Gas
Gas
Gas
Oil
Oil
Oil
Oil
Oil
Hg
Hg Hg
Hg Hg
P 1 = P sat P 2 < P sat P 2 < P sat P 2 < P sat P 3 < P 2 < Psat

Input Data
This option is invoked by selecting Lab|Differential Liberation or by selecting the DIFF
LIB button on the options menu. An example data set is diflib.dat. Also the data set, matbal-
bo.dat illustrates consistency checks calculations for the differential liberation experiment. You
enter data on Tabs Pressure Levels, Consistency Checks and Feed/Kvalues/Output
level/Stability test level/Standard Conditions.
On Tab 1, Pressure Levels, for a description of the data requirements for the saturation
pressure related fields, specifically the saturation pressure entered on the first row and first
column of the main differential liberation table and the check box labeled improve
saturation pressure estimate, please refer to the section entitled “Saturation Pressure”.
The standard conditions are entered on Tab 3. The default values are 14.696 psia and 60 °F
or 101.325 kPa and 15.56 °C.
The basic data required on the tab Pressure Levels are the temperature and the pressure
levels. Enter the reservoir temperature in the text box labeled Temperature. Enter the pressure
levels in column one of the main table. At least one pressure level must be specified in
addition to the saturation pressure. Note that row one is reserved for the saturation pressure.
The specified pressures on row two and subsequent pressures may be higher than the
saturation pressure. However, for rows 2 and greater specify the pressures from the highest
value to the lowest. Do not leave any empty rows.
Quite often experimental data such as oil specific gravity (SG), oil formation volume factor
(FVF), solution gas-oil ratio (GOR), gas Z-factor, gas formation volume factor, gas specific
gravity, oil and gas viscosities as well as properties of the residual oil are available from the
laboratory. These data may be used in WinProp in two ways:
1) Material balance and consistency check calculations to evaluate the quality of the
data and
2) In regression to tune the EOS model to match the observed data.
Generally, material balance calculations would be done first to evaluate the data prior to the
regression calculation. The required data for performing an overall material balance are the
gas oil ratio at each step, the specific gravity of the gas at each step, the specific gravity of the
oil at saturation conditions, oil formation volume factor at saturation conditions and the
residual oil specific gravity. For component material balances the gas phase composition at
each stage is also required. Please note that in going from reservoir temperature and standard
pressure to standard temperature and pressure, it is assumed that no gas will be evolved. The
component balance calculates the composition of the oil phase in the cell at each stage of the
experiment. These data are entered on Tab 2, Consistency Checks. The data fields required
to be filled for overall material balance calculations are shown in cyan. For component
material balance in addition to the data for performing the overall material balance, the gas
composition for each step of the differential liberation experiment is also required. These
fields are shown in yellow. Since some of the data measured in the laboratory can be used for
both regression and for material balance calculations, a button on Tab 2 labeled, Copy Main
Table Contents is provided to avoid having to specify the same data twice on the main table
on Tab 1 and the consistency checks table on Tab 2. The pressure values however have to be
entered on the main table on Tab 1. Therefore if the experimental data are initially entered on
the main table, then clicking on the command button Copy Main Table Contents will copy

the common data from the main table to the consistency checks table. If sufficient data is
entered for the material balance then WinProp will automatically perform that calculation.
Similarly if sufficient data is entered for component material balance then that calculation
will be performed by WinProp. However the user has the option to suppress the consistency
or material balance checks by checking off on the check box labeled Perform consistency
checks if sufficient data is entered on Tab 2.
Data for regression can be entered on columns 2 through columns 9 of the main table on Tab 1
as well as the residual oil specific gravity… and API gravity text boxes on Tab 1. For a given
property such as GOR if experimental data is not available for a given pressure, then enter a
value of -1.0 for that row. A table below the main table on Tab 1 can be used to assign weights
to the different types of data entered. Please see also the section on “Convention for
experimental data input”. If data has been entered on Tab 2 that the user would also like to
use for regression purposes then clicking on the button labeled Copy Consistency Checks
Table will copy the data in fields common to both tables. The table import wizard may also be
used to import data from an ASCII or Excel format file into the main table on Tab 1. To invoke
the table import wizard, click on the button labeled Table Import Wizard.
On Tab 1 there is a checkbox labeled Scale ROV and GOR to oil shrinkage and cum. Gas
released relative to bubble point. Selecting this option will enable calculation of oil shrinkage
as the ratio of oil volume to saturated oil volume, and cumulative gas released as the ratio of
standard volumes of gas liberated to saturated oil volume. If the Differential Liberation
calculation is not being used in regression, this option will generate a plot of these quantities vs.
pressure when the Excel plots are generated, in addition to the normal Relative Oil Volume and
Gas-Oil Ratio plot. If regression to experimental data is being performed, the experimental
values are converted to oil shrinkage and cumulative gas released, and the regression is done on
these quantities. The regression summary table will show the match to the scaled quantities, and
the regression summary plots will show the fit to both the scaled and un-scaled quantities. The
advantage of this technique is that the EOS will not be penalized for poor prediction of the
residual oil density, which is a quantity that will never be encountered in the field.
Constant Volume Depletion

This procedure is usually performed for a gas condensate to simulate the conditions
encountered in the reservoir. The sample of reservoir liquid in the laboratory cell is brought
to the dew-point pressure, and the temperature is set to the reservoir temperature.
Pressure is reduced by increasing the cell volume. Part of the gas is expelled from the cell
until the volume of the cell equals the volume at the dew point. The gas collected is sent to a
multistage separator. The process is repeated for several pressure steps. A schematic of the
constant volume depletion process is shown below:

Gas off
Gas Gas Gas

Gas
Gas
Oil
Oil
Hg Oil Hg
Hg Oil
Hg
Hg
P 1 = P sat P 2 < P sat P 2 < P sat P 2 < P sat P 3 < P 2 < Psat
Input Data
You invoke this option by selecting Lab|Constant Volume Depletion from the menu or by
selecting the CVD button on the options toolbar. An example data set is cvd.dat. For
illustration of consistency checks calculations on CVD experimental data, see the template
case, matbal-gc.dat. You enter data on Tabs Pressure Levels, Consistency Checks,
Separator and Feed/K-values/Output level/Stability test level.
On tab 1, Pressure Levels, enter the reservoir or CVD test temperature in the text box labeled
Temperature. For this test, an initial guess for the saturation pressure is required. This value is
entered on row 1 and column 1 of the main table on Tab 1. The program can use this value
directly in a saturation pressure calculation or refine the guess with a stability test. The latter
choice is selected by checking off the check box labeled improve saturation pressure estimate.
Further details are provided in the section entitled “Saturation Pressure”. The only other
required data are the values of the pressure steps. These are entered in the column labeled Pres.
on the main table provided on Tab 1. The first row of this table is reserved for the saturation
pressure. Enter values from highest pressure to the lowest pressure starting on row 2. Do not
leave any empty rows. Columns 2 through 4 are to be used for entering experimental data which
can be used for regression. On the column labeled Cum Gas produced (%), enter the percentage
recovery, that is total moles removed as a percentage of the initial moles (at saturation pressure)
charged to the cell. On the column labeled Liq. Sat (% of CVS) enter the percent of the cell
volume occupied by the liquid phase at each pressure step, relative to the volume occupied at
saturation conditions. For fluids with a dew point, at saturation pressure, this value is 0.0. For
volatile oils which exhibit a bubble point enter a value of 100 at the saturation pressure. On the
column labeled Gas Z factor enter the gas phase compressibility factor at each pressure. For a
given property such as Gas Z factor if experimental data is not available for a given pressure, then
enter a value of –1.0 for that row. A table below the main table on Tab 1 can be used to assign
weights to the different types of data entered. Please see also the section on “Convention for
experimental data input”. If data has been entered on Tab 2, Consistency Checks, that the user
would also like to use for regression purposes then clicking on the button labeled Copy

Consistency Checks Table will copy the data in fields common to both tables. The table import
wizard may also be used to import data from an ASCII or Excel format file into the main table on
Tab 1. To invoke the table import wizard, click on the button labeled Table Import Wizard.
Material balance calculations can be used to check the quality of the laboratory data collected.
The overall material balance can be used to determine the total mass of the gas and liquid phases
and their densities as a function of pressure. If the compositional analysis of the gas phase from
each stage is also available then the liquid phase composition at each stage can also be
calculated. These data are entered on Tab 2, Consistency Checks. The required data for
performing an overall material balance are the cumulative percent recovery at each pressure step,
the Z factor of the gas at each pressure step, the specific gravity of the gas at each pressure step
and the liquid saturation at each pressure step. The data fields required to be filled for overall
material balance calculations are shown in cyan. For component material balance in addition to
the data for performing the overall material balance, the gas composition for each step of the
constant volume depletion experiment is also required. These fields are shown in yellow. Since
some of the data measured in the laboratory can be used for both regression and for material
balance calculations, a button on Tab 2 labeled, Copy Main Table Contents is provided to
avoid having to specify the same data twice on the main table on Tab 1 and the consistency
checks table on Tab 2. The pressure values however have to be entered on the main table on Tab
1. Therefore if the experimental data are initially entered on the main table, then clicking on the
command button Copy Main Table Contents will copy the common data from the main table
to the consistency checks table. If sufficient data is entered for the material balance then
WinProp will automatically perform that calculation. Similarly if sufficient data is entered for
component material balance then that calculation will be performed by WinProp. However the
user has the option to suppress the consistency or material balance checks by checking off on the
check box labeled Perform consistency checks if sufficient data is entered on Tab 2.
A brief description of the material balance calculations for CVD follows below. For more
detailed information please refer to Whitson and Torp [41].
Assume as a basis 1 mole of initial fluid charged to the CVD cell. The total mass in the cell
at a particular stage k, denoted as ntk is then equal to:
i=k
n tk = 1 − ∑ Δn pi
i=2
where Δnpi is the incremental moles of vapor produced from the cell during stage i. In terms
of the table entries, Δnpi is the difference in the values of “gas produced %” expressed as
fraction between stage i and stage (i-1). Note the initial stage (saturation conditions) is being
denoted as stage 1. The corresponding material balance equation for a component j is:
i=k
n tk z jk = z j1 − ∑ Δn pi .y ji
i=2
where zjk is the overall composition of the fluid remaining in the cell at stage k and yji is the
composition of the vapor phase removed from the cell at stage i. For density calculations the
mass and volume of each phase in the cell is required. The cell volume can be calculated
from the knowledge of initial fluid properties:

Z RT
Vcell = 1
P1
For gas condensates the gas compressibility factor Z1 is generally available, for volatile oils,
however, the bubble point density is usually measured. Provision is made to enter Z factors
only in WinProp. The measured bubble point density can be used together with the real gas
law (PV=nZRT) to obtain the required Z factor. At each stage the liquid volume in the cell is
measured and reported as the liquid saturation. The liquid volume in the cell, can then be
calculated as:
VLk = S Lk .Vcell
From a volume balance, the vapor volume is then Vvk = (1-SLk).Vcell. Using the real gas law, the
corresponding moles of vapor in the cell at stage k are calculated as nvk = pk.Vvk/ZkRT. The
composition of the liquid phase remaining in the cell at each stage k can now be computed as:
n tk .z jk − n vk .y jk
x jk =
n tk − n vk
The compositions calculated in this manner are analyzed by plotting the corresponding
logarithm of K values versus a component characterization factor, F, known as the Hoffman
plot. WinProp will automatically create this plot if component material balance calculations
are performed, which will be done if the required data is entered by the user.
The densities of the liquid and vapor phases can also be calculated from a mass balance [41].
The multistage separator conditions and standard conditions are entered on Tab Separator.
Enter stages from the highest pressure down to the lowest pressure. A maximum of 8 stages
excluding stock tank are allowed. The multistage separator does not include the stock tank
conditions which are entered as Standard conditions. A lower carbon-number component
and an upper carbon-number component are also specified. The molecular weight of
components between those two is computed at each pressure level. This enables the tracking
of the molecular weight of the plus fraction during the depletion process.
You can also enter experimental data on mole % of gas produced, liquid dropout (% liquid
saturation), and gas compressibility factor for regression purposes. Please see also the section
on “Convention for experimental data input”.
Separator Test
The reservoir fluid is sent to a multistage separator where the pressure and temperature are
selected to optimize liquid production. The last stage of the separator corresponds to the
stock tank.
A schematic of a conventional three-stage separation process is shown below:

GAS (1) GAS (2) GAS (ST)
1 st STAGE 2 nd STAGE 3 rd STAGE

P1 , T1 P 2, T2 P 3, T3
OIL to stock tank
The overall gas-oil ratio, the stock-tank specific gravity or API, and the oil formation volume
factor Bo are measured.
The implementation of the Separator option provides for considerable flexibility in
modelling separation strategies which do not conform to the conventional scheme described
above. This is often encountered with gas condensate fluids. Each separator has the
limitation of a single required input and two outputs corresponding to the vapor and liquid
streams. However the liquid output need not feed the next separator and the gas output is not
limited to join the gas product stream. For a given separator one of these output streams can
potentially become a product stream or feed a separator downstream. Recycling is not
allowed. The user can also specify new product streams aside from oil and gas such as LPG.
The oil and gas product streams however must always be present. Quantities that can be used
for regression calculation such as GOR will always therefore be defined.
Two examples via schematics are shown below of alternative separator calculations. In the
first case the oil product stream is made up of contributions from the liquid phase from the 3
separators. This is essentially a reversal of the conventional case where the gas product
stream is made up of the vapor phase from all the separators. In the second case a third
product stream labeled as LPG is defined.
GAS
FEED 1st STAGE 2 nd STAGE STOCK-TANK

P1 , T1 P 2, T2 P s , Ts
OIL
GAS
LPG
FEED 1 st STAGE 2 nd STAGE STOCK-TANK

P1 , T1 P 2, T2 P s , Ts
OIL

Input Data
This option is invoked by selecting Lab|Separator or alternatively by selecting the SEP
button on the options toolbar. An example data set is separator.dat.
Specification of the separator stage conditions and stage data for performing Hoffmann plots
and material balance calculations is done on tab 1, Separators. Initially there are 2 columns
corresponding to the saturation conditions and stock tank conditions in the table on tab 1. The
minimum data requirements are the temperature and pressure for each defined “stage”. For
the saturation column, the reservoir temperature is required along with the known saturation
pressure or an initial guess for the saturation pressure. The program will calculate the
saturation pressure. The user-supplied value will be used directly as an initial guess in the
saturation pressure calculation or the user-supplied value will be refined further via a stability
test prior to the saturation pressure calculation being invoked. The default is to refine the
initial value as indicated by the check box labelled improve saturation pressure estimate.
For the stock tank, the default values for the temperature and pressure are shown on the table.
The user may edit these values.
The Liquid to and the Vapor to rows indicate the destination of the liquid and the vapor
stream from each stage. When there is only one stage, “stock tank,” then these destinations
have to be the “oil” product stream and the “gas” product stream since these 2 streams have
to be present in all cases. For reporting volumes, conditions other than the stock tank
pressure and temperature can be selected for each product stream. These are to be specified
in the table labelled Product Streams Reporting Table. To add a separator, select a cell in
the column where you want the new stage to be inserted and click on the button labelled
Insert sep. To delete a separator, highlight the appropriate column(s) and click on the button
Delete sep. The highest separator stage should be added first followed by lower pressure
stages to the stock tank. The default destination for the liquid phase is as feed to the next
separator downstream while the default for the vapor phase is the “gas” product stream.
Once all the separators are added and the conditions specified then the destinations can be
changed, possibly defining a new product stream such as an LPG or intermediate product
stream. This is done through a drop down combo box which pops down by double clicking
or entering data on the appropriate cell of the stream destinations table. Once added, such a
stream will also have an entry added to the Product Streams Reporting Table. An example
of the interface is shown below:

For overall material balance calculation and Hoffmann plots the required data are the specific
gravity of the gas removed from each separator stage, the gas oil ratio (with respect to stock tank
oil) at each stage, the stock tank API, the density at the saturation conditions and the oil formation
volume factor at saturation conditions. For component material balance calculations the
composition of the gas stream from separator stage is required as well. The GOR values
correspond to the amount of gas liberated and not gas in solution. The formulation of the material
balance equations is based on the fact that the mass or moles placed at the start of the experiment
must equal the mass of the residual oil plus the mass of gas removed from the cell [18].
M init − ∑stages M gas − M resid = 0
Assuming a basis of 1 stb of residual (stock tank) oil, then
M resid = 1(stb) * 0.158987( m3 / stb) * ρ stc ( kg / m3)
M init = 1(stb) * B o ( rb / stb) * ρ s ( kg / m3)
k
M gas = 0.034514 R s k (scf / stb) * λk
The above equations all yield mass of initial in place fluid, gas removed and residual oil in
units of kg. The gas oil ratio appearing in the expression for the gas removed in stage k is the
liberated GOR and λk is the specific gravity of the gas coming out of solution in stage k. ρstc
is the stock tank density of the oil and ρs is the saturated fluid density. Bo is the formation
volume factor at saturated conditions.

The experimental data for regression are entered on tab 2, Experimental Data. The three
experimental data values available for regression are the overall solution gas oil ratio, the oil
formation volume factor and the residual oil API gravity.
Swelling Test
LABORATORY PROCEDURE
This experiment provides information on the fluid behavior under gas injection processes.
When a gas is injected into a reservoir, it can go into solution and swell the oil, i.e. the
volume of the oil becomes larger. Measurements of this effect can be performed as follows.
The reservoir oil is loaded in a cell, and the temperature is set at the reservoir temperature.
The bubble point of the oil and the corresponding volume are measured. A small amount of
injection gas is transferred into the cell. A new saturation pressure is determined and a new
saturation volume recorded. This process is repeated until the upper bound of injection-gas
concentration is reached or the saturation pressure of the fluid is equal to the estimated
injection pressure.
A constant composition expansion experiment may be performed for each mixture of
injection-gas and oil in the above process.
Input Data
This option is invoked by selecting Lab|Swelling Test or alternatively by clicking on the
SWL TEST button on the options toolbar. An example data set is swelling.dat. Enter data
on Tabs Mixtures and CCE.
The required data on Tab 1, Mixtures, include the temperature at which the experiment is
performed and an initial guess for the saturation pressure of the oil at the specified
temperature. If the Improve saturation pressure estimate box is checked this value will be
refined further via a stability test. For additional details refer to the section entitled
“Saturation Pressure”. The original oil is labelled as mixture #0. The initial guess for
saturation pressure entered in the text box Saturation pressure is also shown on the table on
Tab 1 to be used to specify the data for the other mixtures. The oil and gas compositions are
entered on the Composition form as primary and secondary fluids respectively.
The data on Tab 1, Mixtures, corresponding to template case swelling.dat is shown below.

On the table provided for specifying mixture properties, the first column corresponds to the
mole fraction of injection gas, and the second column corresponds to the saturation pressure
estimate of the injection-gas and oil mixture. The row corresponding to the original oil, that
is with mole fraction equal to zero, is added automatically by WinProp. The saturation
pressure estimate value appearing in the table for this row is taken from the Saturation
Pressure Estimate text box. Additional data for at least one mixture is required on this table.
Enter data for these mixtures in consecutive rows starting with the smallest value of the gas
mole fraction to the largest value. A guess for the corresponding saturation pressure is
required for each mixture. As data is added to the table, the total number of mixtures defined
is indicated by the label No of swelling experiments. Insert or remove rows from this table
by accessing the Table menu. The above example shows a case with 5 mixtures.
For regression purposes, the experimental saturation pressure data and/or swelling factor
(volume of swelled fluid at saturation pressure/volume of original fluid at saturation pressure)
may be entered in the third and fourth columns respectively. Either of the two properties may
be assigned a weight greater than the default of 1.0 reflecting the relative importance of the data
to the process for which the EOS model is being developed or the relative accuracy of the
measurements. Please see also the section on “Convention for experimental data input”.
If required, the pressure levels of a constant composition expansion process are entered on
Tab CCE. The CCE experiment will be performed at the entered pressures for each of the
mixtures stipulated. The CCE Excel plots are generated automatically if pressures are
specified for the CCE experiment.

Importing Laboratory Experiment Data with the Table Import
Wizard
The Table Import Wizard is a tool designed to assist the user in importing Excel or ASCII
“Tutorial” section of this manual. The Wizard can be used to import data for the following
laboratory experiments: Constant Composition Expansion, Differential Liberation,
Constant Volume Depletion and Swelling. Specific information relating to the import of
data for these calculations is given here.
For the Constant Composition Expansion and Swelling calculations, the Table Import
Wizard can be used to append or insert data at the currently selected row in the table. Data
for any of the columns in the table may be imported.
For the Constant Volume Depletion and Differential Liberation calculations, the Wizard
will insert data at the currently selected column. Again, data for any of the rows may be
imported.
An important feature of the Wizard, which is particularly useful for laboratory experiment
data, is the ability to transpose rows and columns during the import process. This feature can
be used to convert row-wise data into the column-wise format that the wizard requires. Note
that the Table Import Wizard cannot be used to import data for existing rows or columns.
The standard Windows cut, copy and paste functions can be used for this purpose.

Multiple Contact Miscibility
Calculations
Overview
The design of gas or solvent injection processes often involves a multiple-contact calculation to
study the vaporization or extraction process. There are two methodologies to analyze the gas
drive mechanism and miscible process in WinProp. Traditionally, with cell-to-cell simulation,
a pseudo-ternary diagram is generated from the calculations to help with the interpretation of
the results. Most gas or solvent injection floods operate in a regime where true miscibility is
not achieved, rather near miscible conditions are realized. High recoveries can be achieved
even though miscibility is not truly realized. As compared to conditions required for
miscibility, operation in this regime translates to lower operating costs as compression costs
increase with pressure and feedstock costs increase with the solvent enrichment level. These
are known as vaporizing/condensing processes (Zick [44]), and the resulting ternary diagram has
an hourglass shape. By analyzing the ternary diagrams from the MCM option in conjunction
with slim tube or core flood experiments, optimal operating conditions or solvent composition
can be determined. Please refer to Nutakki et al. [25] for a detailed discussion of this subject.
Besides the pure vaporizing or pure condensing processes, there is a combined drive
mechanism that has features of both vaporizing and condensing drives. In such a system, the
crossover tie line controls the development of miscibility, instead of initial oil tie line or
injection gas tie line. Geometric construction in the composition space is used to locate
all the key tie lines.
The MCM option in WinProp is used to calculate the minimum miscibility pressure (MMP) or
first contact miscible pressure (FCM) for a given oil and solvent at a particular temperature or
the minimum miscibility enrichment level (MME) required for multiple or single contact
miscibility at a given temperature, pressure, oil composition, primary and make up gas
compositions. Users can select the Cell-to-Cell simulation method or the Tie Line method to
calculate MMP or MME.
For both methods, the minimum miscibility pressure may be determined for a given solvent
composition by entering a range of pressures to be tested. Conversely, the minimum rich gas
enrichment level may be determined to achieve miscibility at a specified pressure by entering
a range of rich gas mole fractions to be tested. In both cases, the program reports the MMP or
MME if found and the mechanism by which miscibility is achieved, that is vaporizing or
condensing drive mechanism, or the combined vaporizing and condensing drive mechanism.
If FCM is within the entered pressure limits then it is reported as well. For the MMP
User's Guide WinProp Multiple Contact Miscibility Calculations • 105

calculation, the program divides the entered pressure range into 400 equally spaced intervals.
The calculation begins with the lowest pressure (Pmin) terminating at the maximum pressure
(Pmax) or at the FCM pressure. Similarly for the MME calculation, the entered mole fraction
range is divided into equally spaced intervals, and the calculation terminates at the maximum
solvent enrichment level, or at the enrichment level which gives first contact miscibility at the
specified pressure. The results are output based on the pressure step, or mole fraction step,
used to specify the range and at the pressure corresponding to the MMP or MME. If Cell-to-
Cell method is used, the ternary diagrams will also be output. If Tie Line method is used,
detailed liquid/vapor composition, as well as the k-value for each key tie line will be output.
Data Input
The multiple-contact calculation option is invoked by selecting Calculations|Multiple
Contacts or by selecting the MCM button on the options toolbar. Example data sets for this
option are mcm-condensing.dat, mcm-vaporizing-co2.dat, mcm-combined-H95-8lean-
mmp.dat and mcm-Z12-5-mme.dat etc. The required data include the temperature, entered in
the text box on Tab 1, Conditions and a pressure or alternatively a pressure range for the
calculation. For calculation at a single pressure, enter the value in the text box Pressure. To
specify a pressure range enter the minimum pressure, Pmin, in the text box labelled Pressure
and enter a value for pressure step, Pstep, and the number of pressure steps, Nsteps. The
maximum pressure, Pmax = Pmin + Pstep *Nsteps. The user needs to select one of the calculation
methods: Cell-to-Cell simulation or Tie Line method. The other required data are the oil
composition entered on the Composition form, the primary and make up gas compositions
entered on Tab 2, Composition, the make up gas fraction or range of fractions and the
pseudoization scheme for the ternary diagram entered on Tab 2, Composition as well. For
calculation at a single solvent enrichment level, enter a value between 0.0 and 1.0 in the
Make-up gas fraction text box. The default value for the make-up gas fraction is zero,
implying the solvent composition equals the primary gas composition. In this case the make-
up gas composition is not required and values of zero can be entered. To specify a range of
make-up gas mole fractions, enter the minimum value in the Make-up gas fraction text box,
enter a value for the Make-up gas fraction step and for the No. of make-up gas fraction
steps. If Cell-to-Cell simulation is selected, the pseudoization scheme need to have a value
of 1, 2 or 3 to group a given component into the first, second or third pseudo-component
respectively. The pseudoization scheme is used in the post-processing step, which is just for
ternary plots; the actual calculations are done with the full set of components.
Note that if a range of pressures is specified (MMP calculation), only one solvent
composition may be entered. That is the Make-up gas fraction step must be 0.0 and the No.
of make-up gas fraction steps must be 1. Similarly for the MME calculation where a range
of make-up gas fractions is specified, only one pressure value may be entered.
The following steps are used in the calculation (the points referred to by letter are shown on
the diagram following step 4).
1. A solvent is first formed by mixing a primary gas (e.g. dry gas) with a specified
mole fraction of make-up gas (e.g. LPG). The compositions of the primary and
make-up gases, and the fraction of make-up gas are entered on Tab Composition.
The oil composition is specified on the form Composition.
106 • Multiple Contact Miscibility Calculations User's Guide WinProp

2. Solvent is added to the oil such that the solvent to oil molar ratio increases by a
specified value for each mixture. This solvent increment ratio is entered on Tab
Conditions as Solvent increment ratio. The default value is 0.01. Flash
calculations are performed for a maximum of 100 mixtures of solvent and oil. If
no two-phase region is detected, the process is judged to be first contact miscible
and the calculations stop. In the event that a two-phase region is encountered, the
calculation procedure proceeds to Steps 3 and 4.
3. Using the first point (A) in the two-phase region detected in Step 2, all liquid is
removed. The remaining gas is combined with the original oil in the gas oil ratio
RATIO:(1-RATIO) to form B1. The value of RATIO is entered on Tab Conditions
as Equilibrium gas/original oil mixing ratio (default value: 0.10). A flash
calculation is performed, and the liquid is removed. The procedure is repeated.
This simulates a vaporizing or extraction process, and generates the portion of the
phase envelope marked B. A maximum of 50 flash calculations is performed.
4. Again, using the first point (A) in the two-phase region detected in Step 2, all
vapor is removed. The remaining liquid is combined with the original solvent in
the solvent liquid ratio RATIO:(1-RATIO) to form C1. A flash calculation is
performed, and the vapor is removed. The procedure is repeated until the oil
cannot be enriched further or after a maximum of 50 flash calculations are
performed. This process simulates a condensing gas drive process, and generates
the portion of the phase envelope marked C.
Heavy
B Oil
C
C1
B2
C2
B1
Critical Point
Light Dry Gas Solvent Intermediate

Pseudo-Ternary Diagram

If Cell-to-Cell simulation is selected, the last column of the table on Tab Composition needs
to have a value of 1, 2 or 3, which determines the grouping of components into three pseudo-
components for the ternary diagram. In the following example:
N2 and C1 belong to Pseudo-Component 1; IC5, NC5, NC6 and FC20 belong to Pseudo-
Component 3, while the remaining components belong to Pseudo-Component 2. The
resulting ternary diagram from this multiple contact calculation is shown below, where the
bottom left apex corresponds to Pseudo-Component 1, the bottom right apex corresponds to
Pseudo-Component 2 and the top apex represents Pseudo-Component 3.
108 • Multiple Contact Miscibility Calculations User's Guide WinProp

Oil/Rich Solvent Multiple Contact Study
Ternary Diagram
100
90
mol % of pseudo component 3 80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
m ol % of pseudo com ponent 2
Vapor Liquid Gas Oil

Regression
Overview
The regression feature of WinProp can be used to “tune” the equation of state to match
experimental measurements. The parameters used in the regression are component properties
and interaction coefficients. Most of the calculation options of WinProp allow experimental
data to be entered for regression purposes.
WinProp uses the regression procedure of Agarwal et al. [2]. From the specified list of
parameters, the procedure orders the parameters such that the most sensitive parameters are used
first. The regression is performed on a small number of parameters at a time. The default is to
use a subset of 5 parameters, although this number can be modified. Once a parameter reaches
the maximum or minimum value allowed or does not contribute any longer to improving the
match, it is replaced by the next parameter that has not been used from the ordered list. Thus, a
large set of parameters can be specified, and WinProp will regress on a small number of
parameters at a time, working from the most sensitive parameters to the least sensitive parameters.
Organization of the Input Data

A sample data set structure is shown in the following:
User's Guide WinProp Regression • 111

Example data sets for regression begin with the word regress. There are 16 template cases
that involve regression from regress-blackoil1.dat through regress-separator.dat. Please
refer to the introduction section for a brief description of each of these data files.
Note the forms named Regression Parameters and End Regression in the “Forms” column.
The calculation options between these two forms contain experimental data for regression. The
form Regression Parameters is inserted by selecting Regression| Start while the form End
Regression is included by selecting Regression|End. The experimental data are entered on the
appropriate tables or text boxes in each calculation option. A weight is associated with each data
item or group of data. The weights wi are used to assign a degree of importance to each data
point. The default value is 1.0. A larger value gives more importance to the data while a lesser
value gives less importance. The regression is performed by minimizing the objective function
F = ∑ [w i (x i , calc −x i , meas ) / x i , meas ]
2
where xi,calc and xi,meas correspond to the calculated value and measured value respectively.
To exclude any measured value from the regression, precede it with a negative sign ("-").
Please see the section on “Convention for experimental data input.”
All calculations before the form Regression Parameters use the parameter values before
regression. All calculations after the form End Regression form use the parameter values
after regression. For the calculation options that are included in the regression, the output and
plots contain both results before and after regression.
In the above example, the CMG GEM EOS Model option was used to print component
properties before and after the regression (see the section on “GEM fluid model generation
and component properties printing”).
Parameter Selection
Component properties for regression are selected on tab Component Properties of the
Regression Parameters form.
112 • Regression User's Guide WinProp

Select or unselect the component properties by clicking on the grid. Clicking the first time
selects the property. Clicking a second time unselects that property.
If temperature dependent volume shifts have been activated on the component form, then
volume shift will not be available as a regression parameter. Non-zero values of the aqueous
phase solubility parameters, reference Henry’s constant and molar volume at infinite dilution,
must be set on the component form to enable these variables as regression parameters.
The mole fraction of the secondary stream used to define the feed for calculation options can
be selected as a regression variable be clicking the checkbox below the grid.
Interaction coefficients are selected as regression parameters on tab Interaction Coefficients.
The interaction coefficients between hydrocarbon components are calculated from the
equation described in section “Interaction coefficients” in the Chapter “Components”. The
HC-HC Int. Coef. Exponent is an important parameter for matching reservoir fluid saturation
pressure. The list of HC-HC groups, defined earlier via the Component
Selection/Properties form is shown in the list box under the frame with the caption
Hydrocarbon Groups. To select specific groups as regression parameters, first select the
option button labeled Select from list and then highlight entries from the list by holding
down the CTRL key and clicking with the left mouse button. The interaction coefficients
involving non-hydrocarbon components are selected by clicking on the grid.
Parameters specific to the viscosity correlations are selected on the tab Viscosity Parameters.
As discussed in the “Components” chapter, there are two types of viscosity correlations
available in WinProp: Jossi-Stiel-Thodos (JST) and Pedersen. When JST is being used, the
correlation coefficients and the component critical volumes for viscosity are available to be
selected as regression parameters. When the Pedersen correlation is active, only the correlation
coefficients appear as possible regression variables on this tab. Both correlations also depend
on the component critical pressures, critical temperatures and molecular weights. By leaving
these values fixed, however, and regressing only on the parameters appearing on the viscosity
parameters tab, the process of matching experimental viscosity data can be completely
decoupled from the process of tuning the EOS to PVT data.

Second set EOS parameters can be specified as regression variables in the same way as the first
set. The user can toggle between the component properties and interaction coefficient tables
belonging to the first and second set through the set selection menu. To activate second set
when the first set is active select SetSelection|Second Set. The second set regression variables
currently supported are the critical pressure, critical temperature, volume shift, omega A, omega
B, interaction coefficient exponent and the binary interaction coefficients for pairs with a non-
hydrocarbon species. The user does not need to enable the second EOS set through the
Component Selection/Properties form to specify second set regression parameters. The
second set is activated automatically when a second set regression variable is selected. The
default variable bounds for a given property are the same regardless of which set the component
belongs to. The selection of bounds is discussed in more detail below. The grouping feature
discussed below can also be used for the second set parameters.
Automatic Regression Parameter Selection

For users with limited experience in tuning equation of state parameters to match experimental
data, a facility is provided to automatically select regression parameters based on the types of
experimental data entered in the calculation options within the regression block. To use this
feature, enter all of the calculation options and all experimental data that you wish to match. Insert
the Regression Parameters and End Regression forms into the data set as discussed earlier in
this section. On the Regression Parameters form, click the checkbox labelled Select regression
parameters based on entered experimental data above the parameter selection grid. WinProp
will select a combination of critical properties of the heavy end pseudocomponents, volume shift
parameters, hydrocarbon binary interaction parameter exponents and viscosity parameters to be
adjusted during regression, depending on the experimental data entered.
The automatic parameter selector will not remove any parameters already selected by the
user. Also, once the automatic parameter selection process is complete, you may add or
remove regression parameters manually.
Grouping Regression Variables

It is possible to treat a given property, say critical pressure, for a group of components (for
example all pseudo-components) as a single variable under regression with the grouping feature
of WinProp. The initial value of each member of the group and the lower and upper bound will
in general be unique. To ensure that the individual bounds for each member are honored,
WinProp recalculates the lower and upper bound for the reference component (reference
component is the first component specified for the group) replacing the default or user specified
bounds. The grouping feature is particularly useful when it is desired to maintain a certain
trend or symmetry or avoiding regressing on a variable with a small mole fraction.
During regression, all members of a group may be varied either by equal increments or by
equal ratios. Using the equal increment method means that each variable in the group is
incremented or decremented by the same amount during a regression iteration. The equal
ratio method indicates that each variable in the group is increased or decreased by the same
fraction of its original value during a regression iteration. Parameters that have zero initial
values cannot be used with the equal ratio method. Selection of the method is done on the
Regression Controls tab. The default is to use equal increments.

To activate grouping select Grouping|Start group selection and select the components to be
included in the group by clicking on the appropriate grid cells for a particular property such
as acentric factor. Instead of the X to indicate a selection, for a group member a group id
such gr #1 will be assigned. Once all the members are selected click on a different column or
select End group selection from the Grouping menu. To delete a group click on all the
individual cells defining the group or select Grouping|Delete group and then click on a cell
corresponding to any member of the group. To edit a group, erase the existing definition of
the group by deleting the group, and start again.
The Component Properties tab for a regression run specifying the critical pressures and volume
shifts for the last 4 components in the plus fraction as grouped variables is shown below:
Regression Variable Bounds

On tab Variable Bounds a summary table showing the initial value, the lower bound and the
upper bound for each regression variable currently selected are shown. Column 1 shows the
variable number. If the component is a member of a group then the group id is shown. A
description of the variable is given in column 2. Whether the variable belongs to the first set or
second set is indicated here. Column 3 shows the initial value of the variable. This value cannot
be edited here. It can only be modified on the Component Specification/Properties form.
For each variable, WinProp sets a default lower and upper bound. For most properties, the
maximum change allowed is 20% above or below the original value. For the hydrocarbon
interaction coefficient, other interaction parameters and volume shifts, the bounds are set
according to limits found appropriate for typical petroleum fluids. For hydrocarbon components,
these bounds are modified to ensure that certain trends are maintained: as the molecular weight
increases critical temperature and acentric factor increase while the critical pressure decreases.

To give experienced users the flexibility to restrict the variation of certain component
properties and allow larger changes in others, however, the default variable bounds can be
edited on this table. As mentioned above, changing the bound of a group member may lead
to the bound for the reference component of the group (first group component in the list) to
be adjusted automatically. The user can revert to the WinProp defaults for the bounds by
clicking on the Reset to Default Bounds button.
Regression Control Parameters

On Tab Regression Controls, parameters for the numerical methods and grouping options
are entered. Under Numerical Controls the following information is entered:
Convergence tolerance If the change in the objective function between two iterations,
or the absolute value of the objective function, is less than this
value, the regression stops.
Maximum number of The regression stops after the specified number of iterations.
iterations
Number of simultaneous Number of parameters to be regressed on at one time. The

regression parameters default value is 5. If the number of regression parameters is
less than this number, the former will be used instead. Note
that increasing this value can significantly increase the run
time for the regression.
Under Grouping Controls an option is given to specify how the members of a group are
varied during regression. Selecting Vary group variables by equal increments specifies
that a change Δx will be applied to all group members as xnew = xold + Δx. Selecting Vary
group variables by equal ratios specifies that all group members will be multiplied by a
common factor as xnew = xold x FΔ. The default method is to vary the group members by
equal increments.
Transferring Results to Other Data Sets

The results of the regression option are component properties that will be used in subsequent
calculations. If calculation options are appended after the End Regression form then the
component properties used will correspond to values modified by the regression procedure.
However, it is prudent to examine the results of the regression calculation before proceeding
further. This can be done easily using WinProp’s Update component properties feature. For
example, when a regression is performed with a file named regress.dat, besides the standard
output regress.out, WinProp also outputs a file named regress.rls. This (.rls) file contains the
component properties from the regression process in a format readable by WinProp.

The contents of the (.rls) file can be used to update the component properties in the current data
set by selecting File|Update component properties. Three forms: Titles/EOS/Units,
Component Specification/Properties and Composition forms are updated. The Regression
Parameters and End Regression forms can now be removed from the file, and prediction of
phase behavior using the tuned model can be performed. To keep a record of the work done
use File|Save as... to save this file with a different name, e.g. regress1.dat. Note that a number
of back to back regression runs can also be performed in this way with same data but using
different regression variables. A similar procedure applies to Plus Fraction Splitting and
Component Lumping in terms of updating component properties.

Compositional Grading
Overview
The compositional grading phenomenon refers to a variation in fluid composition with depth
in a reservoir. As depth increases the mole fraction of light components decreases, density
increases and GOR decreases. Near critical oils and volatile fluids exhibit the largest
compositional grading effects, while black oils have the least variation in properties with
depth. Compositional grading is reduced if the system is highly undersaturated.
Assessment of compositional grading is important in estimation of fluid in place,
initialization of reservoir simulators and consideration of production alternatives. For
example, when considering gas injection in a reservoir with compositional grading the
solvent composition required to achieve miscibility will vary with depth. There are two
model formulations available for performing the compositional gradient calculation: the
isothermal model or the thermal model.
The isothermal compositional gradient calculation solves the gravity/chemical equilibrium
problem. Given the composition and pressure at a reference depth, the composition and pressure
at any other specified depth can be determined. The saturation pressure at the specified depth is
also calculated. If there is transition from bubble point to dew point saturation conditions over
the calculation interval, the GOC depth will be estimated. This is done with a simple halving
algorithm to locate the depth at which the transition from bubble point to dew point occurs. This
ultimately requires saturation determination in the vicinity of the critical point, which can cause
failure of the saturation calculation. The GOC calculation continues until an interval of 0.1m is
reached or until the saturation calculation fails. For this reason, the accuracy to which the GOC
depth was determined is reported in the summary table. Formulation of the problem and the
required solution algorithms are given in Whitson and Belery [39].
The thermal model incorporates the effect of the geothermal temperature gradient on the
compositional gradient. Thermal diffusion effects as well as the variation of fluid properties
as a function of temperature can be included in the model. As for the isothermal model, the
location of the GOC will be estimated if it exists. When the temperature is not constant, the
system is not in equilibrium. The model solves for a stationary state, or zero mass flux
condition, as described in Hoier and Whitson (SPE 63085).
Please note that the equation of state must predict a single-phase system for the reference
composition at the reference pressure. If the system is unstable, the calculation cannot be
performed. If experimental data indicate that the initial condition should be stable, some
EOS tuning may be required before the compositional gradient calculation can be carried out.
User's Guide WinProp Compositional Grading • 119

With the default output level of 1, only the summary table is shown in the output (.out) file.
This gives the reservoir pressure, saturation pressure, density and two key mole fraction
values as a function of depth. With output level 2, for each depth the full phase property
table and the saturation calculation results are printed in addition to the summary table.
When the detailed output is requested it will be printed in the order the calculation is carried
out which is described below.
The calculation is carried out in the following order:
1. The first depth level above the reference depth is calculated, using the reference
conditions as the initial guess for the calculation.
2. Continuing for each depth level from the first calculation to the top of the interval,
each calculation is performed using the previous converged results as the initial
guess.
3. The first depth level below the reference depth is calculated, using the reference
conditions as the initial guess.
4. Continuing for each depth level from the calculation in step 3 to the bottom of the
interval, each calculation is performed using the converged results from the
previous calculation as the initial guess.
Data Input
Example data sets for the compositional grading calculation are given in compgrad-blackoil.dat
and compgrad-voloil.dat. For field units, temperature is entered in °F, pressure in psia and
depth in feet. For SI units, temperature is entered in °C, pressure in kPa and depth in meters.
“Common Data Required for all Options”.
Specification of the primary calculation options is done on tab General. Enter the reservoir
temperature at the reference depth in the text box Reference Temperature. In the text box
Reference Pressure enter a value for the pressure corresponding to the reference depth entered
in text box Reference Depth.
Enter the depth to the top and bottom of the formation in text boxes Depth to Top and Depth to
Bottom respectively. The total height of the fluid column as defined by these depths is divided
by the number of calculation intervals specified in the text box No. of Calculation Intervals to
determine the evenly spaced points at which the calculation is performed. The default value is
ten. If the user desires the calculation to be performed at certain specific depths, these can be
entered in the table provided. Enter each depth in the column headed Depth Value.
The user can monitor the composition changes with depth for a given component or a range
of components. This information will be printed in the summary table in the output file.
When a range is selected the mole fractions of the specified components are summed and the
total reported. For the first component or range of components to be tracked select the lower
and upper limits through the combo boxes located next to the label Key Component 1. For
the second key component or range select the lower and upper limits through the combo
boxes located next to the label Key Component 2. The upper component must have a
component index greater than or equal to the index for the lower component.
120 • Compositional Grading User's Guide WinProp

The thermal model data is specified on tab Thermal. To activate the thermal model check
the box labelled Use Thermal Model. The temperature gradient imposed is constant and is
entered in the textbox labelled Temperature Gradient. Entering a positive value for the
thermal gradient implies increasing temperature with depth. The units are °F/ft for field units
or °C/m for SI and modified SI. Various models for calculating the thermal diffusion
coefficients can be selected. In addition, constant thermal diffusion coefficients terms for
each component can be entered in the table labelled Thermal Diffusion Coefficient Terms.
Note that values entered in this table are not the thermal diffusion coefficients usually defined
in the literature, but are the terms identified as Ft in Hoier and Whitson (SPE 63085). This
table can also be used to enter multiplying factors for each component which will multiply
the thermal diffusion coefficients calculated from the chosen model.
CMG’s GEM compositional simulator allows input of tables of composition vs. depth for
initialization of the reservoir via the keyword *ZDEPTH. The results of the compositional
grading calculation can be written out with this keyword in the format expected by GEM.
The data will be written to a file with the same root name as the data file and the extension
(.gmz). This option is activated by selecting the check box labeled “Write GEM *ZDEPTH
keyword with composition vs. depth data …”.
User's Guide WinProp Compositional Grading • 121

STARS PVT Data Generation
Overview
You can use this option of WinProp to generate the complete PVT data required by CMG’s
steam and additives thermal simulator STARS. The data which may be generated includes:
1. Initial composition data
2. Liquid component densities, compressibility and thermal expansion coefficients,
plus nonlinear mixing function data for density
3. Liquid component viscosity tables or correlation coefficients, plus nonlinear
mixing function data for viscosity
4. Simple analytical correlation for component vapor-liquid K-values
5. Tabular gas-liquid K-values
6. Tabular liquid-liquid K-values
7. Tabular solid-liquid K-values
8. Gas-liquid and liquid-liquid K-values at surface conditions
Use of the STARS PVT Generation Option

At any stage in a WinProp data file (before or after regression for example) a basic STARS
component description can be generated based on the current WinProp component
information and the currently specified mixture composition. This option is invoked by
selecting Simulator PVT|CMG STARS PVT Data. The data is written out to a special file
with the input data file root name and extension (.str). Examples are included in the WinProp
template directory as stars-vl_kvalues.dat, stars-vlaq_kvalues.dat, stars-vls_kvalues.dat and
stars-comp_props.dat to illustrate the use of this option. Please refer to the introduction
section for a brief description of each data file.
The data written out to the (.str) file may be imported directly into ModelBuilder for all of the
calculation options except the Gas-Liquid and Solid-Liquid K-Value Tables option. Please
see the discussion below for details.
User's Guide WinProp STARS PVT Data Generation • 123

Input Data (STARS)
Tab Calculation Type of the CMG STARS PVT Data form allows the selection of one of
four options: Basic STARS PVT data (default), Gas-Liquid K-Value Tables, Gas-Liquid and
Liquid-Liquid K-Value Tables, or Gas-Liquid and Solid-Liquid K-Value Tables. Input data
for each of these options is described below. At the end of this section, the options for
plotting the component K-values are described.
Basic STARS PVT Data
Selection of this option allows calculation of all of the required pure component properties for a
STARS fluid model. When the Basic STARS PVT Data option is selected, the tabs Basic PVT
Controls and Density/Surface Controls are activated. The following data may be entered on
these tabs.
Reference Conditions
Reference pressure and temperature corresponding to STARS keywords PRSR and TEMR are
entered here. Based on small deviation from reference condition, perturbation method is used to
obtain the compressibility and first/second thermal expansion coefficients required by the
STARS liquid density model. Pressure-temperature cross coefficient for liquid density is
obtained by density optimization method (see Density Optimization Range). The liquid density
in STARS is equivalent to that given by WinProp at the reference state.
Component Viscosity Model
Pure component viscosities can be calculated using the currently selected WinProp viscosity
model or using the two-parameter corresponding states (CS) model of Teja and Rice. The CS
model uses the component acentric factor as an interpolating parameter, with the viscosities
of ethane (C2) and eicosane (C20) used as reference values. If the WinProp viscosity model is
used, two calculation techniques are available: 1) “match dead oil” or 2) “scale viscosities”.
Option 1 will use WinProp’s viscosity model to calculate the viscosities of all components
that are liquid at the reference pressure and the specified temperature in the table, then
calculate the apparent liquid viscosities of the gaseous components using STARS mixing
rule. Option 2 will locate 2 temperatures for each component at which the component is in the
liquid state. The viscosities at these two temperatures are extrapolated over all temperatures
in the table. Option 1 will give more accurate intermediate component viscosities, whereas
option 2 will give smoother curves. With any of the component viscosity model options, the
component viscosities are scaled by the viscosity of the mixture calculated using the WinProp
viscosity model. This ensures that the STARS viscosity model and the WinProp viscosity
model give the same results for the specified mixture composition at the reference conditions.
Component Viscosity Format
The viscosity information for STARS can be written out as Andrade correlation coefficients
only if the two-parameter corresponding states model is used. If the component viscosity
versus temperature/ pressure table is used, any of the component viscosity models can be
selected. If the tabular output is selected, the component viscosities are scaled by the
WinProp mixture viscosity as described under Component Viscosity Model for each
temperature/pressure in the table. For the tabular output, minimum and maximum
temperature limits and the number of temperature steps must be input. The minimum and
124 • STARS PVT Data Generation User's Guide WinProp

maximum pressure limits and the number of pressure steps can be input at the user’s option.
A maximum of 40 steps for temperature or pressure may be specified.
Viscosity and Density Nonlinear Mixing Controls
For mixture viscosity and density calculations, functions can be defined describing the
nonlinear effect of the composition of one key component on these properties. For each
property, one key component may be selected from the component list and minimum and
maximum mole fractions of that component specified. The nonlinear mixing function values
are calculated such that the STARS property model gives the same result as the WinProp
model over the specified composition range of the key component, with the ratios of all other
components kept fixed.
K-Value Correlation Option
K-Value correlation coefficients can optionally be output with the other basic STARS PVT
data. The correlation coefficients are derived from Wilson’s equation, which combines
Raoult’s law and the definition of acentric factor with a simple vapor pressure equation. Note
that these coefficients are not adjusted to match WinProp’s equation of state flash
calculations, and should be regarded as approximations which will be valid at low pressures
only. If K-value tables are being generated, the generation of correlation coefficients should
be turned off, as only one form of K-value data should be entered in a STARS data set.
Surface Conditions
Surface pressure and temperature corresponding to STARS keywords PSURF and TSURF
are entered here. The STARS default for these values is 101 kPa and 16.85 C. The surface
conditions are used for reporting well rates and accumulations in terms of standard densities.
Values can be entered in the Pressure and Temperature text boxes, and a button is provided
to reset the text boxes to the STARS default values.
Density Optimization Range (P, T)
Density optimization range: minimum/maximum pressure and temperature defining the expected
range of P and T in the STARS simulation are entered here. The default values are 400~40000
kPa and 30~330 C. The density optimization range is used for matching EOS/Experimental
density with densities calculated using STARS mixing rule.
Surface Flash Method
There are two options available in WinProp for specifying how STARS will perform the flash at
surface conditions for production reporting. One option is to Segregate components according
to K-values, corresponding to the STARS keywords *SURFLASH *SEGREGATED. For all
oleic components, this means that a component will be in the oil phase if its gas-liquid K-value is
less than one, otherwise it will be in the gas phase. The other option is to Use the K-value flash,
corresponding to the STARS keywords *SURFLASH *KVALUE.
For both of these options, K-values at surface conditions must be determined. The check
boxes labelled Calculate gas-liquid K-values at surface conditions and Calculate gas-
liquid and liquid-liquid K-values at surface conditions can be selected to force Winprop to
output K-values calculated at the specified surface pressure and temperature. If Calculate
gas-liquid and liquid-liquid K-values at surface conditions is selected, user can specify

either oleic or aqueous as the reference phase for each component (Tab: Henry Const. / Ref.
Phase). If these check boxes are not selected, K-values will be determined from the
correlations or tables. If K-value correlations are being used, the K-values at the surface
temperature will be calculated from the correlations. If K-value tables are being used, surface
K-values will be interpolated from the tables provided the surface conditions lie within the
pressure and temperature range of the tables. If the surface conditions lie outside the range of
the tables, the K-values corresponding to the pressure and temperature closest to the surface
conditions will be used, that is the tables will not be extrapolated.
Gas-Liquid K-Value Tables
The Gas-Liquid K-Value Table option is used to generate gas-liquid K-values for
hydrocarbon components, and optionally for a water component as well. Hydrocarbon and
light gas components are all assumed to be oleic. That is, the K-value is defined as the gas
phase mole fraction of the component divided by the oil phase mole fraction of the
component. If water is present as a component in the system, it is defined as an aqueous
component, and the gas-liquid K-value is defined as the gas phase mole fraction of water
divided by the aqueous phase mole fraction of water. In this case, the aqueous phase mole
fraction of water is assumed to be equal to one.
K-values are calculated using a two-phase negative flash which allows generation of K-
values outside of the two-phase region. See the section on “Flash Calculations” for more
details. There are limits in pressure and temperature beyond which the negative flash will be
unable to converge. These limits normally lie quite far from the two-phase boundary, except
near the critical point of the mixture. K-values which lie outside the range of convergence of
the negative flash are estimated by linear extrapolation. Values which have been extrapolated
are marked in the tables with the notation “<extrap.>”.
Following the last K-value table in the (.str) file, a map entitled “Comparison of WinProp
(W) and STARS K-value (S) phase split calculations” is given. At each pressure and
temperature specified for the tables, the phase split determined from WinProp’s flash
calculation is compared to the phase split calculated from the STARS K-value tables which
have been generated. For example, the notation <W: LV,S: LV> indicates that WinProp’s
equation of state flash has determined there is a Liquid-Vapor phase split (W: LV), and that a
flash done with the K-values from the STARS tables has produced the same result (S: LV).
This map allows a check on the phase behavior which will be predicted when the K-value
tables are used for flash calculations. Differences between WinProp’s results and the STARS
K-value results may be due to extrapolation of K-values, selection of water component
options, or use of the K-value threshold as discussed below.
When the Gas-Liquid K-Value Table option is selected, the tab K-Value Controls is
activated. The following data may be entered on this tab.
Pressure Data
The pressure data consists of an initial pressure, pressure step, and number of pressure steps.
K-values are written out starting with the initial pressure, and continuing for the specified
number of pressure steps, incrementing the pressure by the specified pressure step for each
calculation. A maximum of 20 and a minimum of 2 pressure steps may be specified. The
maximum number of table entries (number of pressure steps multiplied by the number of
temperature steps) is 300.
Temperature Data
The temperature data consists of an initial temperature, temperature step, and number of
temperature steps. K-values are written out starting with the initial temperature, and
continuing for the specified number of temperature steps, incrementing the temperature by
the specified temperature step for each calculation. A maximum of 50 and a minimum of 2
temperature steps may be specified. The maximum number of table entries (number of
pressure steps multiplied by the number of temperature steps) is 300.
Composition-Dependent K-Value Controls
The dependence of component K-values on the concentration of a single key component can
be determined by WinProp and output in the form of composition-dependent k-value tables.
Currently two of STARS composition dependence options may be enabled using WinProp:
(1) global mole fraction of the key component and (2) Hand’s rule using the ratio of the mole
fraction of the key component to the mole fraction of the heaviest oleic component. The input
data in each case is the same: selection of the key component from the component list,
specification of the minimum and maximum global mole fractions of the key component, and
specification of the number of mole fraction steps. A K-value table will be generated for each
component for each of the specified mole fraction steps. When Hand’s rule is used, the
heaviest hydrocarbon component in the system must be the first component in the component
list. Please see the STARS User’s Guide for more information on Hand’s rule.
Water Component Options
The option to Use STARS default gas-liquid K-values for water causes no K-value table to
be written out for the water component, allowing STARS internal defaults to be used. Note
that when the phase split map is generated, the k-values from the default correlation are used.
Use WinProp calculated gas-liquid K-values for water results in output of a table for the
water component with the equation of state determined k-values. The option labelled Don’t
allow water component to vaporize causes a table with all zero entries to be output for the
water component. This last option can be used even when water is not present in the WinProp
component list.
Minimum K-Value Threshold
The Minimum K-Value Threshold allows specification of a minimum value to be used in the
K-value tables. Any number smaller than this will be replaced by the threshold value. The
default value of 1.0E-16 will be used if this entry is left blank.
Gas-Liquid and Liquid-Liquid K-Value Tables
The Gas-Liquid and Liquid-Liquid K-Value Table option is used to generate gas-liquid and
liquid-liquid K-values for hydrocarbon components and the water component. A water
component must exist in the WinProp component list to use this option. User can specify either
oleic or aqueous as the reference phase for each component. In Tab (Henry Const./Ref.
Phase), user can select or unselect the component by clicking on the grid. Selected
component is defined as an aqueous component and unselected component is defined as an
oleic component. Water is always defined as an aqueous component. The gas-liquid K-value is
defined as the gas phase mole fraction of the component divided by the reference phase mole
fraction of the component. For the liquid-liquid K-value calculation: if the reference phase is

aqueous, it is defined as the oleic phase mole fraction of the component divided by the aqueous
phase mole fraction of the component. If the reference phase is oleic, it is defined as the
aqueous phase mole fraction of the component divided by the oleic phase mole fraction of the
component. Water is always defined as an aqueous component, thus the gas-liquid K-value is
defined as the gas phase mole fraction of water divided by the aqueous phase mole fraction of
water and the liquid-liquid K-value is defined as the oil phase mole fraction of water divided by
the aqueous phase mole fraction of water.
Generation of the gas-liquid and liquid-liquid K-value tables is done simultaneously using the
Oil-Gas-Water flash, which models the aqueous phase with Henry’s Law and the vapor and
liquid phases with the equation of state. See the section on “Flash Calculations” for more
details. If a stable oil-gas-water system exists at a specified pressure and temperature, all of the
gas-liquid and liquid-liquid K-values are defined and may be calculated directly. If one or more
of the three phases does not exist, a two-phase negative flash using Henry’s Law for one phase
is attempted. Following this flash, a split of the hydrocarbon phase is attempted using the
negative flash with the EOS for both phases. At the end of this process, K-values for all of the
phases which have been located are calculated, and the remaining K-values are extrapolated.
As described under Gas-Liquid K-Value Tables, the map entitled “Comparison of WinProp
(W) and STARS K-value (S) phase split calculations” is again generated. An additional
phase indicator (A) indicating the aqueous phase is used. Differences between the WinProp
and STARS K-value calculated results may exist for the reasons described in the section on
Gas-Liquid K-Value Tables, and also because the step-wise two-phase negative flash
procedure may give slightly different results than the simultaneous three-phase flash which is
used as the basis for the WinProp phase split results.
The only differences in input data as compared to the Gas-Liquid K-value Tables option are
that Hand’s rule is not available as a composition-dependent K-value option and an additional
water component option may be selected: Use WinProp calculated liquid-liquid K-values
for water. This allows generation of a table for calculating the amount of water in the liquid
hydrocarbon phase. The default is to not allow any partitioning of water into the oil phase.
Gas-Liquid and Solid-Liquid K-Value Tables
The Gas-Liquid and Solid-Liquid K-Value Table option is used to generate gas-liquid K-
values for hydrocarbon components and solid-liquid K-values for the solid-forming
components. A water component cannot exist in the WinProp component list when this
option is used. Hydrocarbon and light gas components are all assumed to be oleic. That is, the
gas-liquid K-value is defined as the gas phase mole fraction of the component divided by the
oil phase mole fraction of the component. The solid-forming components are also assumed to
be oleic, thus the solid-liquid K-values are defined as the mole fraction of the component in
the solid phase divided by the mole fraction of the component in the liquid phase.
The solid-liquid K-values are used with the partial equilibrium reaction keywords in STARS.
Note that the complete keyword specification for use of the solid-liquid K-values is not
written out to the (.str) file. Before importing into ModelBuilder or including in a STARS
data set, the required keywords must be added to the k-value specification. Please see the
STARS documentation for details.

Generation of the gas-liquid and solid-liquid K-value tables is done simultaneously using the
Asphaltene/Wax Modelling method described in the “Flash Calculations” section. As for
the Gas-Liquid and Solid-Liquid K-Value Tables, if a stable three-phase system exists at a
specified pressure and temperature, all of the gas-liquid and solid-liquid K-values are defined
and may be calculated directly. If one or more of the three phases does not exist, a two-phase
negative flash using the solid model for one phase is attempted. Following this flash, a split
of the hydrocarbon fluid phase is attempted using the negative flash with the EOS for both
phases. At the end of this process, K-values for all of the phases which have been located are
calculated, and the remaining K-values are extrapolated.
As described under Gas-Liquid K-Value Tables, the map entitled “Comparison of WinProp
(W) and STARS K-value (S) phase split calculations” is again generated. An additional
phase indicator (S) indicating the solid phase is used. Differences between the WinProp and
STARS K-value calculated results may exist for the reasons described in the section on Gas-
Liquid K-Value Tables, and also because the step-wise two-phase negative flash procedure
may give slightly different results than the simultaneous three-phase flash which is used as
the basis for the WinProp phase split results.
The only differences in input data as compared to the Gas-Liquid K-value Tables option are
that Hand’s rule is not available as a composition-dependent K-value option and none of the
water component options are enabled.
Feed and K-Value Plotting Controls
On the tab labelled Feed/Plot Controls, the feed composition can be specified along with
some other controls as described in the section on Common Data Required for All Options.
On this tab the check boxes for plotting the component K-values can also be selected.
Depending on the calculation option selected, both the gas-liquid and liquid-liquid K-values
may be plotted. The results are always shown as log of the component K-values plotted
against pressure, with a separate plot generated for each temperature in the table.

Process Flow
Overview
This option can simulate processes which may not conform to any of the standard laboratory
options such as differential liberation or constant volume depletion. The user can use this
option to custom design a plant or surface separation scheme. Keep in mind that no pressure
drops are allowed between units and there are no heat losses between units. In addition, no
recycling is allowed in the system.
There are 6 different unit types to choose from. The table below summarizes the
characteristics of each unit type.
Unit type Max. # Max. # Quantity determined

of inputs of outputs
Saturation pressure cell 1 1 Saturation pressure

Saturation temperature cell 1 1 Saturation temperature
Equilibrium cell 10 2 Vapor -liquid phase splits,
compositions
Constant volume 10 2 Vapor -liquid phase splits,
equilibrium cell compositions*
Mixing cell 10 1 Composition, flow rates
Splitting cell 1 10 Composition, flow rates
*For the constant volume equilibrium cell the flow rates and the compositions of the vapor
and liquid output streams are determined by the following procedure. The equilibrium
compositions and volumes of the vapor and liquid phases are determined by the flash
calculation. An amount of the vapor phase is purged so that the total volume of remaining
vapor and liquid equals to the volume of the feed stream. The purged amount of the vapor
phase is reported as the vapor phase flow rate. The remaining vapor and liquid phase in the
cell is combined and reported as the output liquid phase composition and flow rate.
User's Guide WinProp Process Flow • 131

For the process units, four pieces of information are required in addition to the destination of
the output streams: unit name, unit type, pressure and temperature. For the saturation
pressure cell, the entered value of the pressure will be used as the initial guess for the
saturation pressure. A good initial guess is required to ensure convergence. For the
saturation temperature cell, the entered temperature will be used as the initial guess for the
saturation temperature. Note that the user does not need to specify "output streams"
explicitly. An "output stream" is defined as an exit stream from a unit that is not an inlet
stream to another unit or to a product stream. These "output streams" are identified internally
by the program.
For input streams the required information is the unit name to which the stream is directed,
the composition, flow rate, pressure and temperature. An input stream is defined as meeting
two criteria simultaneously: (1) it is an inlet stream to a unit and (2) it is not an exit stream
from some other unit in the calculation.
Data Input - Process Flow
Tab Input Streams is used to add, delete or edit input streams. To define a new stream click
on the Add button. The Stream name field will be filled with the string INSTR- followed
by a number reflecting the total number of streams defined. The Stream name field cannot
be edited by the user. The Composition field will show the default choice of PRIMARY.
By default the Primary mole fraction field will show the value of 1.0 and be disabled. The
primary composition entered on the most recently defined composition form is echoed on the
composition grid. The composition grid is disabled for edits by default. The following table
shows the ways in which the composition may be specified for an input stream and the
controls involved.
132 • Process Flow User's Guide WinProp

Type How to select or enter Status of primary Status of
mole fraction text composition grid
box
Composition entered as primary Select PRIMARY from the Disabled Disabled

feed under the last composition composition drop down list
form
Composition entered as Select SECONDARY from the Disabled Disabled

secondary feed under the last composition drop down list
composition form
Composition obtained by Select MIXED from the Enabled Disabled

mixing primary and secondary composition drop down list. This
feed compositions entered on will enable the primary mole
the last composition form fraction text box. Enter the mole
fraction of the primary feed stream
in this box
User defined composition Select USER INPUT from the Disabled Enabled
composition drop down box. This
will enable the composition grid.
Enter values directly on this grid
Enter the flow rate, pressure and temperature in fields labeled Flow rate, Pressure and
Temperature respectively. The flow rate can be specified on a molar or volumetric basis. The
default is molar rates. Use the menu labeled Flow Units to select Molar or Volumetric basis.
If SI units are being used then the molar rates should be kmol/time and volumetric rates in
m3/time whereas for Field units the molar rates are in lb-mole/time and volumetric rates are in
ft3/time. The final required piece of information is the name of the unit to which the input
stream is directed. Enter the name of the unit or select from one of the units already defined
through the drop down combo box labeled Input to. If the name of the unit is entered then this
unit will be automatically created as a splitting unit. The user can set the properties of this unit
subsequently by locating the appropriate record on tab 2, Process Units.
To move between the defined input stream records click on the VCR type navigation arrows
on the data control labeled Input Stream on the left bottom corner of the tab. The fields for
a particular record can be edited by first loading the record via the data control and then
entering new values on the corresponding text boxes such as flow rate etc. The changes will
be saved by moving to a new record or by clicking on the OK button To delete an existing
input stream use the data control to locate the record and then click on the Delete button. To
save changes made on the tabs on the form press the OK button. The Cancel button will
close the form without saving any of the changes.
User's Guide WinProp Process Flow • 133

Tab Process Units is for managing process units. To delete an existing unit use the VCR type
navigation keys on the data control labeled Units to locate the desired unit and then click on the
Delete button. Any Input to field of input streams referencing the deleted unit will be cleared
to the null string. If the deleted unit was cited as the destination of one or more output streams
from other unit(s) then those destination fields will be cleared to the empty string as well. To
add a unit click on the Add button. This will result in a new record with the default name of
UNIT- followed by a number representing the total number of units defined to that point. The
unit type selected will be a SPLITTER by default. The Pressure and Temperature fields as
well as destination fields will be left blank to be filled by the user. The user has one
opportunity to edit the name field. Once the unit name text box is highlighted and then the
focus lost the unit name cannot be edited. Alternatively, by moving to another record the unit
name field cannot be edited subsequently. To enter the destinations of the output streams click
on the button labelled Destinations…. This will open an appropriate dialog box depending on
the unit type. For a splitting unit, for example, there can be a maximum of 10 output streams.
The user is required to enter the destination of each of these streams and the fraction of the total
flow assigned to each stream. If the user enters a new unit name in the destination combo box
then that unit is created automatically by the program.
Tab Product Streams is for specifying the reporting conditions for predefined product
streams such as OIL and GAS. There are 3 other predefined product streams in addition to
OIL and GAS; these are named PR-STR3, PR-STR4 and PR-STR5. The user can reference
any or all of these product streams in specifying the destination of an output stream from a
particular unit. When a product stream is chosen as a destination, the corresponding record
will be written to the data file. The block of keywords will be something like this:
*STREAM 'OIL'
*PRESSURE 20.0
*TEMPERATURE 50.0
The user cannot delete or add a product stream record. The reporting conditions can be
specified individually for a given product stream. Locate the appropriate product stream
using the navigation arrows on the data control labeled Product Streams and edit the
pressure or temperature values appearing in the respective text boxes.
134 • Process Flow User's Guide WinProp

Black-Oil PVT Data Generation
Overview
This option can be used to generate the PVT data for simulation studies with CMG’s black-
oil simulator IMEX as well as other commercially available black-oil simulators. In the latter
case, some of these simulators implement the Extended Black-Oil Formulation. In addition
to the standard black-oil parameters an additional parameter, the condensate gas ratio, often
denoted as Rv is added to account for oil component vaporization in the gas phase at reservoir
conditions. WinProp can generate PVT data for the extended black-oil model. Unlike
models for CMG’s own simulator IMEX the data is presented in a “generic” format. The
keywords do not exactly correspond to a specific simulator.
The calculations should be done once an EOS model is obtained for the oil, generally through
characterization of the heavy end followed by regression to match the available data. The
PVT data is written out to a file with the root name corresponding to the input-data-file and
with the extension (.imx). For example if the input file name is test.dat, the PVT data file
will be test.imx. If the PVT data is designed for IMEX then it may be referenced as an
include file in an IMEX data set or opened with ModelBuilder. If the PVT data is targeted at
some other simulator then the information in the .imx file may require editing prior to use in
the specific simulator of choice.
A total of thirteen different fluid component models may be specified with IMEX. At
present, WinProp can be used to generate six of those models, namely Black-Oil, Pseudo-
miscible with chase gas, Pseudo-miscible without chase gas, Gas-Water, Gas-Water with
Condensate and Volatile Oil. Please refer to the IMEX user guide for more information on
these fluid models.
For PVT data aimed at one of IMEX’s models, the following information is written out to the
output file:
1. The *PVT *BG|*EG|*ZG 1 keyword and associated table (1 is always written out
for the table number) are written for the oil models. The columns of this table are
pressure, gas-oil ratio, oil formation volume factor, gas formation volume factor |
gas expansion factor | gas Z-factor, oil viscosity and gas viscosity. For the pseudo-
miscible option with chase gas, the solution gas always remains in solution. The
solution gas-oil ratio is fixed and input through a field on the Solvent tab (writes
out keyword *GORINT). The bubble point pressure versus solution gas-oil ratio
curve in the table belongs to the chase gas. This is NOT taken into account when
values are written to the PVT table. The total amount of solution gas is the value
User's Guide WinProp Black-Oil PVT Data Generation • 135

given by *GORINT and the dissolved chase gas given by the Rs vs. bubble point
pressure curve.
For the Gas-Water model, a *PVTG *BG|*EG|*ZG table is written. The columns
of this table are pressure, gas formation volume factor | gas expansion factor | gas
Z-factor and gas viscosity.
For the Gas-Water with Condensate table, the *PVTCOND *BG|*EG|*ZG table is
written with columns: pressure, gas-oil ratio, condensate-gas ratio, oil formation
volume factor, gas formation volume factor | gas expansion factor | gas Z-factor, oil
viscosity and gas viscosity. For this option, a series of *BGUST|*EGUST|*ZGUST
and *VGUST tables are also written, giving the formation volume factor and
viscosity of the gas at saturation pressures lower than the corresponding mixture
pressures given in the *PVTCOND table. BOT tables are not generated for this
option, as the oil is assumed to be saturated at all times.
For the Volatile Oil option, either the PVTCOND or PVTVO table can be written.
Using the PVTCOND table with associated *BGUST|*EGUST|*ZGUST and
VGUST tables allows non-linear behavior of undersaturated gas to be modeled.
Using PVTVO allows a simpler linear treatment of undersaturated gas properties
by specifying only saturated gas and dry gas formation volume factors and
viscosities. The *PVTCOND table specification is the same as for the Gas-Water
with Condensate model, including use of *BGUST|*EGUST|*ZGUST and VGUST
tables. The *PVTVO *BG|*EG|*ZG table is written with columns: pressure, gas-
oil ratio, condensate-gas ratio, oil formation volume factor, gas formation volume
factor | gas expansion factor | gas Z-factor, oil viscosity, gas viscosity, dry gas
formation volume factor | dry gas expansion factor | dry gas Z-factor and dry gas
viscosity. *BOT tables are allowed with either table type for the volatile oil option.
The units for these properties are indicated in the output file and are the same as in
IMEX. Field, SI and modified SI units are supported.
2. Water phase properties are optional. The keywords written out are *REFPW,
*BWI, *CW, *VWI, *CVW and *DENSITY *WATER.
3. Gas phase density at surface conditions, *DENSITY *GAS or *GRAVITY *GAS.
4. Oil phase density at surface conditions, *DENSITY *OIL. Pressure dependence of
oil viscosity, *CVO. Oil compressibility at the original oil bubble point pressure
*CO, or *BOT tables for the undersaturated oil may be output. Not required for
the gas water option.
5. For the pseudo-miscible fluid models a *PVTS *BS table. The entries of the table
are pressure, solvent water ratio, solvent expansion factor, solvent viscosity and
mixing parameter between solvent and oil. The solvent density is written out with
the keywords *DENSITY *SOLVENT. The mixing parameter between solvent
and gas is written out with the *OMEGASG keyword. If the pseudo-miscible
model with chase gas is chosen then the initial solution gas-oil ratio is written with
keyword *GORINT.
136 • Black-Oil PVT Data Generation User's Guide WinProp

To generate the PVT data for the IMEX black-oil model the following information is required:
1. Composition of oil and, if the swelling curve is to be generated, the gas
composition. These are entered on the Composition form. Oil is entered as the
primary fluid and gas is the secondary fluid. Note: For gas water option enter the
gas composition as the primary fluid on the composition form.
2. The reservoir temperature and a guess for the saturation pressure of the original oil.
These are entered on tab 2 of the Black-Oil PVT Data form. For gas water option
only the reservoir temperature is required.
3. At least one pressure step for the differential liberation experiment on the grid with
the label No. of pressure levels on tab 3, Pres. levels. For gas water option, these
are pressures at which properties gas formation volume factor and gas viscosity are
to be calculated. The differential liberation experiment is not performed for the gas
water option.
4. The number of separators excluding the stock tank and the operating conditions on
tab 3. A maximum of 8 separators may be specified. For gas water case only the
standard (stock tank) conditions are required.
5. If the swelling curve is to be generated then the composition of the injection gas is
entered on the Composition form as the secondary fluid. If the solution gas is to be
used for swellling calculation, then select the appropriate option button on Tab 5, “Gas
Properties” under the frame labelled “injection gas composition for swelling test”. On
the grid labeled No. of swelling experiments on tab Pres. levels enter the mole
fraction of the gas, initial guess for the saturation pressure of the oil/gas mixture and
the saturation pressure flag. For gas water option these data are not required.
6. Water phase properties may be input by the user directly on tab 4 or alternatively
estimated from built in correlations. This data is optional.
7. For the pseudo-miscible options the solvent composition can be the secondary fluid
on the Composition form or values entered on tab Solvent properties. The oil
solvent mixing ratio as a function of pressure is entered on the grid provided on this
tab. These values are echoed as column 5 of the *PVTS table. The remaining
entries of this table, that is the solvent water ratio, the solvent expansion factor and
solvent viscosity will be calculated by the program. Note: add the water component
from the library for the solvent solubility in the aqueous phase calculations. Enter a
composition of zero for the water component. The fields for entering the solvent gas
mixing parameter and the minimum solvent saturation are on tab Solvent properties.
If the pseudo-miscible with chase gas option is selected then the initial solution gas-
oil ratio text box on this tab is enabled and a value is required.
8. For the Gas-Water with Condensate option, the method for calculating oil phase
properties (Bo and GOR) must be selected on the Oil properties tab. Oil phase
properties can be obtained by flashing a sample of the oil phase at each depletion
pressure through the user defined separators (Method of Whitson and Torp) or
alternatively from material balance equations (Method of Coats).

For PVT data aimed at an extended black-oil model, the following information is written out
to the output file:
1. The *PVTO keyword and associated table. Typical output is shown below.
*PVTO
** solution pressure, oil oil
** GOR(2) psia FVF(1) vis,cp
** ------------------------------------------
0.2606 515.00 1.2279 0.16615 Saturated
1115.00 1.2158 0.17475
1915.00 1.1996 0.18621
2715.00 1.1834 0.19768
3515.00 1.1673 0.20914
5000.00 1.1372 0.23043
6034.82 1.1163 0.24526
6500.00 1.1069 0.25192
0.5045 1115.00 1.3730 0.14572 Saturated
1915.00 1.3503 0.15714
2715.00 1.3275 0.16856
3515.00 1.3048 0.17998
5000.00 1.2626 0.20118
6034.82 1.2332 0.21595
6500.00 1.2199 0.22259
0.8261 1915.00 1.5462 0.12408 Saturated
2715.00 1.5150 0.13452
3515.00 1.4839 0.14497
5000.00 1.4262 0.16436
6034.82 1.3859 0.17787
6500.00 1.3678 0.18394
1.1532 2715.00 1.7100 0.10950 Saturated
3515.00 1.6720 0.11872
5000.00 1.6015 0.13582
6034.82 1.5523 0.14774
6500.00 1.5302 0.15310
1.4574 3515.00 1.8505 0.10135 Saturated
5000.00 1.7735 0.11634
6034.82 1.7198 0.12679
6500.00 1.6956 0.13149
1.6255 5000.00 1.8713 0.10344 Saturated
6034.82 1.8290 0.11189
6500.00 1.8100 0.11568
1.7044 6034.82 1.8751 0.10689 Saturated
6500.00 1.8590 0.11031
1.7399 6500.00 1.8768 0.10845 Saturated
The columns of this table are the gas-oil ratio (GOR), pressure, oil formation
volume factor, and oil viscosity. For each GOR value the first row shows the
saturated fluid values. For a GOR of 0.186 mscf/stb for example, the saturation
pressure is 515 psia, the formation volume factor equals 1.1689 and the viscosity is
0.16615 cP. Second and subsequent rows of data for a given GOR define the
undersaturated curves for the oil formation volume factor and viscosity as a
function of pressure as specified in column 2.

1. PVTG (gas phase properties) and associated table. Typical format is shown below:
*PVTG
** pressure, solution, gas gas
** psia CGR(4) FVF(3) vis,cp
** ------------------------------------------
515.00 0.000597 5.73365 0.01262 Saturated
0.000000 5.73597 0.01263 Dry gas
1115.00 0.001038 2.37473 0.01441 Saturated
0.000597 2.37631 0.01441 Under saturated gas
0.000000 2.37845 0.01440 Dry gas
1915.00 0.005019 1.27344 0.01926 Saturated
0.000000 1.28504 0.01900 Dry gas
2715.00 0.020711 0.90464 0.02658 Saturated
0.000000 0.92555 0.02472 Dry gas
3515.00 0.057092 0.75257 0.03598 Saturated
0.000000 0.76634 0.02993 Dry gas
5000.00 0.186452 0.69119 0.06067 Saturated
0.000000 0.62956 0.03785 Dry gas
6034.82 0.265054 0.69762 0.07772 Saturated
0.000000 0.57894 0.04261 Dry gas
6500.00 0.300389 0.70479 0.08562 Saturated
0.000000 0.56185 0.04464 Dry gas

2. The columns of this table are the pressure, the condensate gas ratio, the gas
formation volume factor and viscosity respectively. The first row corresponds to
saturated values. Subsequent rows show the properties of the mixture of saturated
gas and dry gas. These combinations are done such that the mixtures correspond to
condensate gas ratios that are specified at lower pressures. For example at a
pressure of 1800 psia there is one row for undersatured gas with a CGR of 0.00104
stb/mscf which is the CGR ratio at the previous pressure value of 1100 psia.
3. The stock tank densities of the oil, gas and water phase as well as the water phase
properties.
To generate the PVT data for the extended black-oil model the following information is required:
1. Composition of oil and, if the swelling curve is to be generated, the gas composition.
These are entered on the Composition form. Oil is entered as the primary fluid and
gas is the secondary fluid. The injection gas composition can alternatively be chosen
to be the solution gas. The selection is made on Tab 5 “Gas Properties”.
2. Selection of the PVT Experiment. For black-oils, differential liberation
corresponds the best to the depletion process occurring in the reservoir. For light
oils differential liberation or constant volume depletion may be chosen. For gas
condensates the constant volume depletion experiment is appropriate. The PVT
experiment provides samples of the gas and oil phase which are then flashed
through the user defined separators to obtain the oil and gas properties. This
choice is made on Tab 1 of the Write BLACK-OIL PVT data form.
3. Selection of the method for calculating oil phase properties. Oil phase properties can
be obtained by flashing a sample of the oil phase at each depletion pressure through the
user defined separators (Method of Whitson and Torp) or alternatively from material
balance equations (Method of Coats). This choice is made on Tab 1 of the form.
4. Option for calculating oil phase properties above the original saturation pressure. If
values for the oil and gas properties are required for pressures greater than the
original saturation pressure than a choice of three techniques is available. Option 1
is to simulate a swelling test to extend the curves. This requires the injection gas
composition. This method generally works well for black-oils. Option 2 is to
extrapolate the curves while honoring certain relationships between the parameters.
For black-oils (but generally not for light oils and condensates) there is a linear
relationship between oil phase formation volume and GOR. There is also a linear
relationship between oil density and viscosity. Option 3 is to simply extrapolate the
curves individually without assuming any specific relationship between the
parameters. Option 3 appears to be the only viable option for light oils and gas
condensates.
These are entered on tab 2 of the Black-Oil PVT Data form.
6. At least one pressure step for the differential liberation experiment or constant
volume depletion experiment on the grid with the label No. of pressure levels on
tab Pres. levels.

tab 3. A maximum of 8 separators may be specified.
8. If the swelling curve is to be generated then the composition of the injection or
solution gas is entered on the Composition form. On the grid labeled No. of swelling
experiments on tab Pres. levels enter the mole fraction of the gas, initial guess for the
saturation pressure of the oil/gas mixture and the saturation pressure flag.
estimated from built in correlations.
PVT data can also be generated for a commercial black oil simulator, not IMEX. This format
is referred to as format 2, with format 1 corresponding to IMEX. There are four “models” in
this case. Model 1 writes out differential liberation and separator calculation results
separately, that is differential liberation data is not adjusted for surface (separator) conditions.
Model 2 writes out the “corrected” differential liberation data. Model 3 is for simulating an
oil water system. The differential liberation data is not corrected for surface conditions for
model 3. Model 4 corresponds to a gas water system. PVT data for a black oil simulator
written in format 2, the following information is written out to the output file:
1. The *BOTAB 1 keyword and associated table (1 is always written out for the table
number) for models 1-3, including oil water and BGTAB 1 for gas water option.
For models 1 and 2, this is followed DOS WTOS and PSAT keywords and the
corresponding values. DOS is the density of saturated oil at reservoir temperature
and the original oil saturation pressure in units of gm/cc. WTOS is the molecular
weight of the oil in gm/gmol and PSAT is the saturation pressure of the original oil
in psia or kPa units. For the oil water option, model 3, the BOTAB keyword is
followed by DOB WTRO and GR keywords and the corresponding values in a
new line. The values are the density of the residual oil from differential liberation
experiment in gm/cc, molecular weight of the residual oil in gm/gmol and gas
gravity of the solution gas. For the gas water option, model 4, the BGTAB
keyword is followed by the GR keyword and a value for the gas gravity. Typical
results for model 1 are shown below:
BOTAB 1
C** VALUES IN TABLE DIFLIB RESULTS, NOT CORRECTED FOR
C** SURFACE CONDITIONS
DOS WTOS PSAT
0.5897 99.48 2179.86
2. The columns of the BOTAB table for models 1 and 2, are the saturation pressure,
gas-oil ratio, oil formation volume factor, gas formation volume factor, gas gravity,
oil viscosity and gas viscosity. The table is arranged with highest pressure first and
the lowest pressure last in monotonic order. The units for these properties are
indicated in the output file. For model 1 where the entries in the BOTAB table are
not adjusted for surface conditions, the values shown correspond to those calculated
by the differential liberation test. For model 2 the values in the table have been
corrected for surface conditions. For model 3, Oil Water option, the values in the
BOTAB have not been adjusted for surface conditions. Since gas properties are not
required the columns of the oil water table are saturation pressure, gas oil ratio, oil
formation volume factor and oil viscosity. The columns of the BGTAB table are the
pressure, gas formation volume factor and gas viscosity. Typical results for model 1
are shown below:
C** pressure, solution oil gas gas oil gas
C** psia GOR(2) FVF(1) FVF(3) gravity vis,cp vis,cp
C** --------------------------------------------------------------------
PSAT RS BO BG GR VO VG
3970.15 1.5087 1.8045 0.74298 0.85325 0.20414 0.0303
3726.70 1.3440 1.7254 0.78048 0.83804 0.22407 0.0283
2872.26 0.8910 1.5086 0.98604 0.79643 0.30972 0.0224
2179.86 0.6192 1.3788 1.30766 0.77723 0.40449 0.0189
2100.00 0.5915 1.3651 1.35951 0.77610 0.41726 0.0186
1850.00 0.5094 1.3242 1.55392 0.77425 0.46041 0.0177
1600.00 0.4334 1.2864 1.81437 0.77564 0.50903 0.0168
1350.00 0.3625 1.2510 2.17750 0.78143 0.56684 0.0160
1100.00 0.2959 1.2174 2.71317 0.79374 0.61839 0.0154
850.00 0.2325 1.1851 3.57349 0.81701 0.67266 0.0147
600.00 0.1707 1.1528 5.16455 0.86209 0.74204 0.0141
3. For models 1-3 the undersaturated oil formation volume factors and oil viscosities
curves as a function of pressure for each saturation pressure. These are defined by
a table with columns corresponding to saturation pressures as shown on the
BOTAB table and rows corresponding to pressure elevation above the saturation
pressure i.e. dp = p-psat. For each pressure a value for the formation volume factor
and a value for the oil viscosity divided by the corresponding values at saturation
pressure is shown. Typical results are shown below:
PSAT 3970.15 3726.70 2872.26 2179.86 2100.00 1850.00 1600.00
1350.00 1100.00 850.00 600.00
DP BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC
BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC BOFAC VOFAC
BOFAC VOFAC
243.44 0.9921 1.02010 0.9925 1.02042 0.9937 1.02213 0.9945

1.02421 0.9946 1.02449 0.9949 1.02541 0.9952 1.02642 0.9954
1.03114 0.9957 1.03619 0.9960 1.03787 0.9963 1.03973
1097.89 0.9645 1.09065 0.9662 1.09209 0.9714 1.09979 0.9753

1.10918 0.9757 1.11044 0.9770 1.11461 0.9782 1.11914 0.9794
1.14044 0.9807 1.16320 0.9819 1.17077 0.9831 1.17917
1790.29 0.9422 1.14781 0.9448 1.15017 0.9534 1.16273 0.9597

1.17804 0.9604 1.18009 0.9624 1.18688 0.9645 1.19428 0.9665
1.22902 0.9685 1.26613 0.9704 1.27847 0.9725 1.29216
1870.15 0.9396 1.15441 0.9424 1.15686 0.9513 1.16999 0.9579

1.18598 0.9586 1.18812 0.9608 1.19522 0.9629 1.20294 0.9650
1.23923 0.9670 1.27800 0.9691 1.29089 0.9713 1.30519
2120.15 0.9315 1.17505 0.9347 1.17783 0.9448 1.19271 0.9523

1.21084 0.9531 1.21327 0.9555 1.22132 0.9579 1.23007 0.9603
1.27121 0.9626 1.31517 0.9650 1.32978 0.9674 1.34599

2370.15 0.9234 1.19569 0.9270 1.19880 0.9383 1.21543 0.9467
1.23571 0.9475 1.23842 0.9503 1.24741 0.9530 1.25720 0.9556
1.30319 0.9582 1.35233 0.9609 1.36866 0.9636 1.38679
2620.15 0.9154 1.21633 0.9193 1.21977 0.9318 1.23816 0.9410

1.26057 0.9420 1.26356 0.9450 1.27351 0.9480 1.28433 0.9509
1.33518 0.9538 1.38949 0.9568 1.40755 0.9598 1.42759
2870.15 0.9073 1.23697 0.9116 1.24074 0.9253 1.26088 0.9354

1.28543 0.9365 1.28871 0.9398 1.29961 0.9430 1.31146 0.9462
1.36716 0.9494 1.42666 0.9526 1.44643 0.9559 1.46838
3120.15 0.8992 1.25761 0.9039 1.26171 0.9188 1.28360 0.9298

1.31029 0.9309 1.31386 0.9345 1.32570 0.9381 1.33859 0.9416
1.39914 0.9450 1.46382 0.9485 1.48532 0.9521 1.50918
0.8911 1.27825 0.8962 1.28268 0.9123 1.30633 0.9242 1.33515

0.9254 1.33901 0.9293 1.35180 0.9331 1.36572 0.9369 1.43112
0.9406 1.50098 0.9444 1.52421 0.9483 1.54998
4. For options 1 and 3 the oil properties of the original oil as calculated by flashing
through the user defined separator battery. Typical output is shown below:
C** SEPARATOR TEST DATA
SEPTEST 1
PVTTABLE 1
PSATF BOF
2179.86 1.3447
P T GOR BOSTG GR
300.00 75.00 0.42 1.0788 0.7100
200.00 75.00 0.03 1.0654 0.7588
100.00 75.00 0.04 1.0484 0.8849
14.70 60.00 0.08 1.0000 1.3454
To generate the PVT data for the black-oil model, format 2, the following information is
required:
1. Composition of oil and, if the swelling curve is to be generated, the gas
composition. These are entered on the Composition form. Oil is entered as the
primary fluid and gas is the secondary fluid. Alternatively the user can choose to
use the solution gas at the original oil saturation pressure as the injection gas. This
option can be selected from tab 5, “Gas Properties” under the frame “injection gas
composition for swelling test”. For gas water option enter the gas composition as
the primary fluid on the composition form.
These are entered on tab 2 of the Black-Oil PVT Data form. For gas water option
only the reservoir temperature is required.
3. At least one pressure step for the differential liberation experiment on the grid with
the label No. of pressure levels on tab Pres. levels.
tab 3. A maximum of 8 separators may be specified.
5. If the swelling curve is to be generated then the composition of the injection or
solution gas is entered on the Composition form. On the grid labeled No. of swelling
experiments on tab Pres. levels enter the mole fraction of the gas, initial guess for the
saturation pressure of the oil/gas mixture and the saturation pressure flag. For gas
water option these data are not required.

estimated from built in correlations.
This procedure is generally performed to obtain PVT data for black-oil simulation. The
sample of reservoir liquid in the laboratory cell is brought to the bubble-point pressure, and
the temperature is set to the reservoir temperature. Pressure is reduced by increasing the cell
volume. All the gas is expelled from the cell while pressure is held constant by reducing the
cell volume. The gas is collected and its composition and volume are measured at the
experiment conditions as well as standard conditions. This enables the formation volume
factor of gas (Bg) to be calculated. The gas viscosity is also measured. A sample of the oil
phase is removed at each pressure and its viscosity is measured. The oil sample is then
flashed through the separators to obtain the formation volume factor and gas-oil ratio. The
process is repeated in steps until atmospheric pressure is reached. For the light oil model the
gas sample at each step is also put through the separators to obtain the gas shrinkage as well
as condensate production at the surface.
To obtain data corresponding to the swelling curve the procedure for the swelling experiment
is followed to obtain the saturation pressure. The reservoir oil is loaded in a cell, and the
temperature is set at the reservoir temperature. The bubble point of the oil is measured. A
small amount of injection gas is transferred into the cell. A new saturation pressure is
determined. This process is repeated until the upper bound of injection-gas concentration is
reached (e.g. 60 mol %) or the saturation pressure of the fluid is equal to the estimated
injection pressure. Each oil/gas mixture is then flashed through the separators to get the oil
formation volume factor and GOR. In addition the properties of the equilibrium gas is
measured and reported (gas formation volume factor, viscosity).
Input Data
This option is invoked by selecting Simulator PVT|Black-Oil PVT Data or by clicking on
the options toolbar button BLK PVT. The template files imex-blackoil.dat,
imex_condensate.dat and imex_voloil.dat show the data entry for all of the supported fluid
models for IMEX. Normally only a single Black-Oil PVT Data form should be included in
a data set. There are also two additional template cases, extended_blackoil.dat illustrating
generation of PVT data for an extended black oil model and format2_blackoil.dat for black
oil model with the results written out in format type 2. On tab Model select either “CMG
IMEX PVT Models”, “Extended Black-Oil PVT models” or “Black Oil PVT Model (format
II)”. If IMEX PVT model is chosen then select further one the six available fluid models, for
“Black Oil PVT Model (format II)”, choose one of the four available models. Then enter data
on Tabs Sat. Pressure, Pres. Levels, Water properties (optional), Oil properties and Gas
properties. The Solvent properties tab is also enabled for data entry if one of the pseudo-
miscible fluid models of IMEX is selected. For “Extended Black-Oil PVT models” select the
“Experiment Type” and the method of calculating oil properties, one of either “Whitson-
Torp” or “Coats”. Selection of “Whitson-Torp” implies oil phase properties are calculated by
flashing a sample of the oil phase at each pressure step of the differential liberation, constant
volume depletion or swelling test simulation. By selecting “Coats”, oil phase properties are
calculated by material balance principles where possible, that is, for pressures less than the
original oil saturation pressure. If data for pressures greater than original oil saturation
pressure is required then select the method for generating this data. There are three choices
here: “Swelling experiment”, “Extrapolation assuming relationship between parameters” and
“straight extrapolation of each individual property”.
For a description of the data on Tab Sat. Pressure, please refer to the section entitled
“Saturation Pressure”.
On Tab Pres. Levels, enter the pressure levels for the differential liberation calculation
underneath the label No. of pressure levels. These pressures should all be less than the
saturation pressure if the swelling option is being used to generate data for pressures greater
than the original oil saturation pressure. If the extrapolation option is being used enter all
pressures in the “differential liberation” table including pressures greater than the original oil
saturation pressure. Enter values starting from the highest pressure value to the lowest
pressure value. As values are entered the caption No. of pressure levels will be updated
accordingly. Rows can be added or deleted from this table by invoking the Table item on the
menu. At least one value is required.
The pressure and temperature for the separator stages can be defined in the frame labeled
Separator conditions. A maximum of eight separator stages excluding the stock tank is
allowed. The stock tank pressure is entered in the text box labeled Stock tank pressure and
the stock tank temperature in the text box labeled Stock tank temperature. The stock tank
stage is always included in the calculation whereas the inclusion of other separators is
optional. The separator pressure and temperature are entered directly on the table. Please
enter values starting from the highest pressure to the lowest pressure on the table. If there is
only one separator then the pressure and temperature for this separator should be entered on
row 1. For two separators use the first two rows.
If the swelling curve is to be generated then enter the mole fraction of the gas in column 2 of
the table labeled No. of swelling experiments. On column 3 enter the initial guess for the
saturation pressure of this mixture and column 4 enter the saturation pressure flag. Valid
entries here are either 2 or –2. A value of 2 indicates that the initial guess for saturation
pressure will be improved via stability analysis, while a value of –2 indicates that the initial
guess entered on the table will be used directly.
The tab Pressure levels corresponding to imex-blackoil.dat is shown below:

On Tab Water properties enter the properties of the water phase. These may be input
directly by the user or calculated from internal correlations by the program. To calculate
from correlations enter data for salinity, water bubble point and the reference pressure, then
click the “Apply:...” button at the bottom of the form. Alternatively, data can be entered
directly in the required fields reference pressure, formation volume factor of the water,
compressibility, viscosity at the reference pressure, pressure dependence of viscosity and
water phase density.
On Tab Oil properties, the user can enter values of certain oil properties directly instead of
accepting the values calculated internally by WinProp. To enter oil density (or alternatively
oil gravity) directly, select that option from the group of buttons under the Oil density / API
gravity frame and enter the value in the text box provided. To enter the oil viscosity pressure
dependence directly select Input oil viscosity pressure dependence and enter a value for
this property in the text box. For the undersaturated oil compressibility three options are
available. The default is to create a table of undersaturated compressibility as a function of
saturation pressure. Alternatively if only the compressibility of oil corresponding to the
original oil composition at the saturation pressure is desired then select Calculate
undersaturated oil compr. at the oil B.P pres. To enter the oil compressibility of the
original oil at saturation pressure select Input undersaturated oil compr. at the oil B.P
pres. and enter an appropriate value in the text box provided.
On Tab Gas Properties, various options for writing out the gas phase density or specific
gravity are provided. The user can either accept the WinProp generated value or enter the
appropriate value directly.

If one of the two pseudo-miscible models is selected than additional data is required on Tab
Solvent properties. This includes the solvent composition, gas-oil mixing ratio as a function
of pressure, the solvent gas mixing ratio, the minimum solvent saturation and for the pseudo-
miscible fluid model with chase gas the initial gas-oil ratio.
Extended black-oil model: Coats Material Balance equations
In the Coats method, only the reservoir vapor is taken through the separators. The oil phase
properties formation volume factor (Bo) and gas-oil ratio (Rs), are obtained from material
balance equations at each expansion step of the CVD or differential liberation experiment
from V1 to V2. These equations are:
(
ρ sto V2 b g S g + b o R sS o )2 = ρsto V1 (b gSg + b o R sSo )1
ρ stg V2 (b g R v S g + b oS o ) = ρ stg V1 (b g R v S g + b oS o )
2 1
Where ρsto and ρstg are fixed surface densities and bo = 1/Bo, bg = 1/Bg. The stock tank
densities are obtained from the output of the separators at saturation pressure. The values at
the saturation pressure are obtained by the Whitson-Torp method.
Compressibility test
Oil and gas properties calculated for IMEX or for the extended black-oil simulator are
checked to ensure that the total compressibility is greater than zero. This requires that the oil
and gas compressibilities (Co and Cg) respectively as defined by the following equations are
greater than zero:
C0 =
(
1 ⎡ − dB o dR s B g − R v Bo ⎤
+
)
⎢ ⎥
B0 ⎣ dp dp (1 − R s R v ) ⎦
Cg =
(
1 ⎡ − dB g dR v B0 − R s B g ⎤
+
)
⎢ ⎥
Bg ⎣ dp dp (1 − R s R v ) ⎦
For conventional black-oil model, Rv and dRv/dp are both zero.

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Properties and Molecular Weights for Petroleum and Coal-Tar Liquids", Fluid
Phase Equilibria, Vol. 16, 1984, pp. 137-150.
37. Walas, S.M.: Phase Equilibria in Chemical Engineering, Butterworth Publishers,
Boston, 1985.
38. Whitson, C.H.: "Characterizing Hydrocarbon Plus Fractions", Society of
Petroleum Engineers Journal, August, 1983, pp. 683-694.
39. Whitson, C.H. and Belery, P.: "Compositional Gradients in Petroleum
Reservoirs", SPE 28000, University of Tulsa Centennial Petroleum Engineering
Symposium, Tulsa, OK, Aug 29-31, 1994.
40. Whitson, C.H., Anderson T.F., and Soreide I.: "C7+ Characterization of Related
Equilibrium Fluid Using the Gamma Distribution", paper in "C7+ Characterization",
Edited by Mansoori, Chorn, Taylor and Francis, New York, 1989.
41. Whitson, C.H., and Torp, S.B.: "Evaluating Constant Volume Depletion Data",
SPE 10067, JPT, March 1983, pp. 610-620.
42. Wichert, E and Aziz, K.: "Calculate Z’s for Sour Gas Hydrocarbon Processing",
Vol. 51, pp. 119, May 1972.
43. Won, K.W.: "Thermodynamics for Solid-Liquid Equilibria: Wax Formation from
Heavy Hydrocarbon Mixtures", Fluid Phase Equilibria, Vol. 30, 1986, pp. 265-279.
44. Zick, A.A.: "A Combined Condensing/Vaporizing Mechanism in the Displacement
of Oil by Enriched Gases", SPE 15493, Proc. of 61st Ann. Conf., Oct 1996.
User's Guide WinProp References • 151

Appendix A
Case Studies
Introduction
The case studies presented in this section are designed to guide the user step-by-step through
practical phase behavior modelling problems.
Case Study Number 1 describes in detail the steps involved in heavy fraction characterization
and equation of state tuning for a gas condensate. Working through this case study will
provide practice in techniques for data set editing, the component properties updating
procedure, data specification for a number of calculation options, as well as possible methods
to use in your own regression problems.
Case Study Number 2 illustrates the use of the Oil-Gas-Water flash for predicting solubility
of gases in brine and regression on the aqueous phase solubility parameters. Generation of
the required equation of state parameters to define the fluid model for CMG’s GEM
compositional simulator is also shown.
Case Study Number 3 shows how to develop a model for predicting precipitation of
asphaltene from a black oil under pressure depletion.
Case Study Number 1: Gas Condensate Modelling
In this Case Study, the Peng-Robinson equation of state will be tuned via regression to match
the PVT behavior of a Gas Condensate fluid. Data for this example are taken from the
Petroleum Engineering Handbook (H.B. Bradley, Editor-in-Chief, Society of Petroleum
Engineers, 1987, pp. 39-6 to 39-9). The data given are typical for a fluid of this type,
including hydrocarbon analyses of separator products, and results of constant composition
expansion and constant volume depletion laboratory experiments.
Create Data Set for Splitting Calculation
Begin by double-clicking the WinProp icon in the CMG Technologies Launcher (accessed
from the Windows Start Menu). This will open WinProp with a new blank data set ready for
editing. The required forms Titles/EOS/Units, Component Selection/Properties and
Composition are placed in the new data set by default.
The first step in modelling the condensate fluid will be to split the heptanes plus fraction.
The splitting calculation is inserted into the data set by selecting Characterization|Plus
Fraction Splitting from the main menu or by clicking on the SPLT button on the options
toolbar. The data set should now look like the one below:
User's Guide WinProp Appendix A • 153

Set EOS Model and Unit System
Double-clicking on the row labelled Titles/EOS/Units opens the form for selecting the EOS
model and units system. Text to appear on the main form for the data set can be typed in the
text box labelled Comments, while text to appear in the output file can be entered into the text
boxes labelled Title 1 - 3. The text from Title 1 will also be used to label any plots that are
created. The EOS and Units selection may be left at the default values as shown below.
Specify System Components to C6

Click OK to accept the data on the form and return to the main WinProp form. Specification
of the system components is done by double-clicking on the row labelled Component
Selection/Properties. In this case all components up to hexane may be selected from the
WinProp component library. From the Component Selection/Properties form menu, select
Options|Insert library component and then use the mouse to choose the system components
as shown on the form below.
154 • Appendix A User's Guide WinProp

Again, click OK to accept the selection and return to the Component definition form. All other
information on this form can be left at the default values. Please refer to the “Components”
section for information on modifying any of the default component properties. Click OK to
return to the main form.
Specify System Composition
Composition for the selected components is specified by double-clicking on the row labelled
Composition and entering the values in mole % as shown on the following form.
A message will be issued when this form is closed, warning that the composition does not
sum to 1 or 100. Since the heptane plus fraction has not yet been included in the system, this
warning can safely be ignored.

Specify C7+ Fraction Properties
Now that all of the light and intermediate components have been defined, all that remains is to
characterize the heavy fraction as several pseudo-components. Specification of the heavy fraction
properties, splitting into single carbon number fractions, and lumping into pseudo-components is
easily done in a single step with WinProp’s splitting option. From the main form, open the Plus
Fraction Splitting form and enter the plus fraction properties on the third tab as shown below.
Specify Plus Fraction Splitting and Lumping Calculation

Now, click on the General tab to view the default parameters to be used for the splitting
and lumping calculations. The plus fraction will first be split into 25 single carbon number
fractions. Select Lee-Kesler as the critical property correlation to be used to generate the
properties of these fractions. By default, WinProp will automatically determine the number
of pseudo-components to lump into. It is also possible to select no lumping, or the user can
enter the desired number of pseudo-components. The mole fraction of the component
immediately preceding the plus fraction also has to be entered on tab 2, Distribution. In
our case the component is FC6 with mole fraction equal to 0.0173. Information on the
other tabs can be found in the “Component splitting and lumping” section. Click OK to
return to the main form.
Save the Data Set and Run the Splitting Calculation
The splitting calculation is now ready to run. Select File|Save and enter a file name. The file
extension (.DAT) will be added automatically if it is not specified. Now select File|Run to
run the data set. When control returns to WinProp, the output file can be viewed by selecting
File|View output. The distribution of single carbon number fractions and the final properties
of the lumped components are shown in the output file.

Update the System Component Specification
The next step in the tuning process is to match the available experimental data via
regression. First, the component specification must be updated to reflect the results of the
splitting calculation. This is done by selecting File|Update component properties from
the main menu, which will modify the first three forms in the data set. Open the
Titles/EOS/Units form and enter a new comment and descriptive title for this data set. On
the Component Selection/Properties form the properties of the full component
specification, including the heavy pseudo-components, can be viewed and a new comment
entered. Open the Composition form to verify that the mole fractions now sum to one. At
this point the splitting calculation can be removed from the data set by selecting the row
labelled Plus Fraction Splitting on the main form and pressing the Delete key or selecting
Edit|Delete from the main menu. To avoid overwriting the original data set, select
File|Save As … and enter a new name for the data set.
Set Up the Regression Data Set
To begin setting up the regression run, make sure the row directly under the row labelled
composition is selected. From the main menu select Regression|Start. The data set should
now look like the following:
Copy the Data for Regression

The saturation pressure, constant composition expansion and constant volume depletion
specification experimental data can now be copied from the template file Case_study-1.dat.
This file is located in the WinProp templates directory, for example cmg\WinProp\1999.10\Tpl.
Open the Case_study-1.dat data file, and select the rows from Saturation Pressure through
Constant Volume Depletion using the mouse. The WinProp window should appear as
follows:

Select Edit|Copy from the main menu to copy these calculation options to the clipboard.
Close the Case_study-1.dat file, then make sure that the row directly underneath Regression
Parameters in your data file is selected and choose Edit|Paste to paste the contents of the
clipboard into your data file. Next, click on the row underneath Constant Volume
Depletion, then select Regression|End to indicate the end of the calculation options to be
included in the regression. View the calculation specifications and experimental data by
double-clicking on the appropriate row.
Select Initial Regression Parameters
The parameters to be used in the regression can now be selected by double-clicking on the
Regression Parameters row. To begin, select the critical pressures of the C7+ pseudo-
components as regression variables. This is done by clicking on the cells in the first column
(labelled Pc) for the last 5 components in the system. The first tab on the Regression
Parameters form should now look like the following:

Click on the tab labelled Interaction Coefficients and in the same manner as for the critical
pressures, select the Hydrocarbon Interaction Coefficient Exponent and the interaction
coefficients between CO2 and Methane, and between CO2 and the C7+ pseudo-components.
Select OK. Before the Regression Parameters form closes, a message box appears asking if
you would like to change the value for the number of simultaneous regression parameters.
Click No to accept the default value of 5. This means that a subset of the 5 most sensitive
regression parameters will be used at each regression iteration. For more details please refer
to the “Regression” section of the manual.
Run the Regression Data Set
The regression data set is now ready to run. Select File|Run; since the data set has changed
since it was last saved, a message box appears asking if you would like to save the data set
before running. Click Yes to save your changes.
While the data set is running, the progress of the regression can be tracked by noting the
values of the residuals in the window displaying the run status messages. This information is
also echoed to the output file. It is important to note that the magnitude of the change from
the initial value of the residual is more important than the values of the residuals themselves.
Create Regression Summary Plots
Summary plots of the before regression and after regression results, along with the
experimental data, can be created by selecting File|Create Excel plots from the main menu.
This will create an Excel workbook with individual plots of all of the simulated results, as
well as the summary plots. Viewing the summary plots for this run quickly shows that only
minimal improvement in the fit was obtained. Note particularly that the liquid dropout values
for the constant volume depletion have large errors.
Check the Regression Summary Table
To check the numerical values for the before and after regression calculation errors, open the
output file by selecting File|View output from the main menu. At the end of this file is a
table with a summary of the regression results. Check if there has been any improvement of
the match to the saturation pressure, shown in the first row of the summary table.
Modify the Regression Specification
Modifications to the data set can now be made to improve the predictions of the volumetric
data and the saturation pressure.
Begin by opening the Component Selection/Properties form and viewing the column for the
Volume Shift parameters. Note that all components have a default volume shift of zero.
Select Volume Shift|Reset to correlation values from the menu to insert values correlated
with component molecular weight for all components.
Next, open the Saturation Pressure form, and on the tab Calculations, enter a value of 50.0
for the weight associated with the experimental saturation pressure value. This is to ensure
that the saturation pressure is more closely matched. On the Constant Volume Depletion
form, Pressure Levels tab, enter a weight of 5.0 for the liquid dropout values.
Now, open the Regression Parameters form and add the volume shift parameters for
methane and the C7+ pseudo-components as regression variables.

Run the Modified Regression Data Set
Save and run the data set again. Note the decrease in the residual values. Create the Excel
plots again. Check the match to the liquid dropout on the CVD summary plot. View the
summary table in the output file to observe the effect of increasing the weight for the
saturation pressure experimental data.
Specify Group Variables for Regression
Further improvement of the fit can be attempted using WinProp’s regression variable
grouping method. The grouping method ensures that existing trends in the original
component properties are maintained, by incrementing or decrementing all of the members of
a group by the same amount during regression. Since each group is treated as a single
regression variable, this also provides a method for varying a large number of component
properties without having to select them all as individual regression parameters.
Open the Regression Parameters form, and clear the selection of the critical pressures and
volume shifts for the components C07-C09 through C15-C17 by clicking on the cells marked
with an “X” for those components. Leave Pc and Vol shift selected for component C18+, and
then select critical temperature and acentric factor for C18+. From the menu, select
Grouping|Start group selection, then click on the cells for components C07-C09 through C15-
C17 in the critical pressure column then select Grouping|End group selection from the
menu. In the same manner, select regression variable groups for the components C07-C09
through C15-C17 for properties: critical temperature, acentric factor and volume shift. On
completion, the form should appear as follows:
The interaction coefficients can be left as they were selected for the last run.

Run the Data Set and Create Final Summary Plots
Save and run the data set with the new regression specification.
In this case, the residual is reduced significantly, indicating that a much better fit has been
obtained. Check the output file to verify that the predicted saturation pressure now matches the
experimental value quite closely. Create the Excel plots and view the regression summary plots.
The CVD summary should now show a good match of the liquid dropout as shown below.
CVD pressure levels and depletion data : CVD Calc.

Regression Summary
35.0 80.0
30.0
60.0
Liquid Volume, %
Produced Gas, %
25.0
original mol
original vol.
20.0
40.0
15.0
10.0
20.0
5.0
0.0 0.0
0 1000 2000 3000 4000 5000 6000 7000
Pressure (psia)
Final Liq. Vol. Init. Liq. Vol. Exp. Liq. Vol.

Final Prod. Gas Init. Prod. Gas Exp. Prod. Gas
Predict VLE Behavior with Tuned Model

Now that the EOS is tuned, it can be used to predict the phase behavior of the gas condensate.
Begin by updating the component properties in the data set to reflect the results of the regression
as was done after the splitting calculation. Select File|Update component properties, delete all
of the rows underneath the Composition row, then save the file under a new name.
Specify a Two-Phase Envelope Calculation
Click on the row underneath the Composition row. Select Calculations|Two-phase
Envelope from the main menu, or click on the toolbar button labeled 2P ENVP, then open
the data entry form for the envelope calculation. On the first tab, change the pressure
specification to UNKNOWN, the temperature specification to 60, and change the minimum
temperature for the X-Axis to 32; leave all of the other envelope specification controls on this
tab at the default values. The first tab should now appear like the one below.

On tab Envelope Construction Controls, the phase boundary and quality line calculation can
be specified. A value of 0.0 is already entered in the grid for Vol. frac. vapor phase. Below
this row, enter values of 0.1, 0.2 and 0.3 to generate quality lines. Also set the Initial step size
to 0.1. Save and run the data set to perform the envelope calculation.
In the output file, a table showing the Pressure, Temperature, Z-factors and K-values at all
points for the two-phase boundary and all of the specified quality lines is given. Select
File|Create Excel plots to generate the diagram as shown in the figure below.
Tuned condensate model

P-T Diagram
7000
6000
5000
Pressure (psia)
4000
3000
2000
1000
0
0 100 200 300 400 500 600 700 800
Temperature (deg F)
2-Phase boundary 90.000 volume %
80.000 volume % 70.000 volume %

Case Study Number 2: Solubility of CO2 in Brine
In this Case Study, a fluid model is generated which can be used in CMG’s compositional
simulator GEM to simulate a CO2 injection recovery process, including modelling of the
solution of CO2 into the aqueous phase. The model reservoir fluid is taken from Killough,
J.E. and Kossack, C.A.: “Fifth Comparative Solution Project: Evaluation of Miscible Flood
Simulators,” SPE paper no. 16000, presented at the Ninth SPE Symposium on Reservoir
Simulation, San Antonio, TX, 1987. For this case study, the injection fluid described in the
above paper will be replaced with pure CO2.
This case study consists of three major steps:
Estimation of CO2 solubility in brine at several pressures using WinProp’s internal model for
calculation of Henry’s constants for gaseous components in aqueous brines.
Fitting the parameters for the Henry’s law solubility model used in GEM to the predicted CO2
solubilities via regression.
Generation of a file containing the GEM fluid model keyword specifications.
Note that if experimental solubility data existed for the gas in brine of the desired
concentration, Step 1) could be bypassed. In this case study it is assumed that experimental
solubility data are not available.
Create Data Set for Prediction of CO2 Solubility in Brine
The reservoir fluid components with properties as given in the SPE Fifth Comparative Solution
Project have been defined in the data set Case_study-2.dat. This file is located in the WinProp
templates directory, for example cmg\WinProp\1999.10\Tpl. Open this data set by dragging the
file onto the WinProp icon in the CMG Technologies Launcher, or by starting WinProp by
double-clicking on the icon then selecting File|Open from the main menu. To avoid
overwriting the template data set, save the file under a new name by selecting File|Save As …
from the main menu and entering a new file name in the dialog box.
Modify the Default Aqueous Phase Solubility Parameters
Double-click on the Component Selection/Properties row of the data set to activate the data
entry form. Notice that the components CO2 and H2O are defined in addition to the
components in the reservoir fluid.
Scroll over in the grid until the columns labelled “Ref. Henry” (component Henry’s constant),
“V inf.” (molar volume at infinite dilution) and “P ref.” (Reference pressure for Henry’s
constant) are visible. These parameters are set to zero by default, which indicates that the
internal model for calculation of these values will be used. WinProp will estimate solubilities
for all components up to C8 by default.
In this study, it is desired to model only the solubility of CO2 in the aqueous phase. This is
accomplished by setting the Henry’s constants for all other components to a value of 1.0E+20
or higher. It is not necessary to adjust the parameters for the water component. Edit the
component Henry’s constants so the form appears like the one pictured below.

Specify the Brine Salinity
Click on the Aqueous phase tab of the Component Selection/Properties form. On this tab,
the aqueous phase salinity can be specified in a variety of units. The salinity is defined in
terms of NaCl concentration. Brines are modelled by assuming that the total salinity is due
only to Na+ and Cl- ions. In this case it is assumed that total salinity of the brine is 100,000
ppm, thus a value of 0.1 can be entered for the NaCl concentration with the units selected as
Weight Fraction.
By default, Henry’s constants determined using the internal model are for pure water. The
value entered for the brine salinity is used to adjust the Henry’s constants to account for the
reduced solubility of gases in solutions with electrolytes present. Click OK to return to the
main form.
Check the Stream Compositions
Open the Composition form to observe the definition of the primary and secondary
compositions, as shown below. The secondary composition is usually defined as the injection
fluid, in this case pure CO2. The primary composition is usually defined as the reservoir
fluid, thus the hydrocarbon component mole fractions corresponding to the initial reservoir
fluid composition are entered here. In this case, the composition of water in the system must
also be defined. The mole fraction of water is entered as 1.0 in the primary composition
column. After normalization, the resulting mole fraction of water in the primary stream will
be 0.5. Close the Composition form by clicking OK or Cancel.

Add Flash Calculations to the Data Set
Click on the row directly underneath the Composition. To add an Oil-Gas-Water flash to the
data set at this point, select Calculations|OGW/EOS Multiphase Flash from the main
menu. Your data set should now look like the one pictured below.
Specify Conditions for P-T Flash

Double-click on the OGW/EOS Multiphase Flash row to open the data entry form. First,
specify the primary mole fraction as 0.5. This means that the feed to the flash calculation will
consist of 50 mole % of the combined reservoir oil/water stream and 50 mole % CO2. Select
OGW (Oil-Gas-Water) from the Flash Type combo box.
Next, enter the specified reservoir temperature of 160 °F in the temperature text box. The
initial reservoir pressure is 4000 psia. To predict the solubility of CO2 in brine over the full
range of expected pressures, a series of flashes from 500 to 4500 psia will be performed.
This is accomplished by entering 500 psia in the pressure text box, a pressure step of 1000
psi, and 5 for the number of steps. The data entry form should now appear as below. Click
OK to return to the main form.

Run the Data Set
Specification of the data set to predict the solubility of CO2 in brine at 5 pressures is now
complete. Save the data set by selecting File|Save from the main menu. Perform the
calculations by selecting File|Run.
The results of the calculations can now be viewed by selecting File|ViewOutput from the main
menu. Scroll down through the output file until you reach the table with the results for the first
flash calculation at 500 psia. The results table should appear as shown on the following page.
The table consists of three sections: phase compositions, K-values and phase properties.
Note that in the third section of the results table, Phase01 is identified as the aqueous phase. The
mole% of CO2 in this phase is reported in the first section of the table as being 0.47996 %.
Verify in your results that the only components present in the aqueous phase are CO2 and water.
Write down the mole% CO2 in the aqueous phase calculated for each of the 5 flash calculations
reported in the output file. These are required for the next stage of the modelling process.
Equilibrium Properties at 500.000 psia and 160.000 deg F

Peng-Robinson Equations of State
mole percent
Component Feed Phase01 Phase02 Phase03

CO2 50.00000 0.47996 21.16229 77.25212
C1 12.50000 0.00000 3.03426 19.93130
C3 0.75000 0.00000 1.17901 0.94408
C6 1.75000 0.00000 9.11641 0.59513
C10 5.00000 0.00000 32.39168 0.09787
C15 3.75000 0.00000 24.57394 0.00264
C20 1.25000 0.00000 8.19468 0.00003
H2O 25.00000 99.52004 0.34774 1.17684

component ln (fug,atm) K-values w.r.t. phase 1
Phase01 Phase02 Phase03

CO2 3.14837E+00 1.00000E+00 4.40916E+01 1.60955E+02
C1 1.89596E+00 1.00000E+00 1.00000E+00 1.00000E+00
C3 -1.38485E+00 1.00000E+00 1.00000E+00 1.00000E+00
C6 -2.18610E+00 1.00000E+00 1.00000E+00 1.00000E+00
C10 -4.40810E+00 1.00000E+00 1.00000E+00 1.00000E+00
C15 -8.56474E+00 1.00000E+00 1.00000E+00 1.00000E+00
C20 -1.36124E+01 1.00000E+00 1.00000E+00 1.00000E+00
H2O -1.11686E+00 1.00000E+00 3.49413E-03 1.18252E-02
aqueous liquid vapor
Z-factor 0.0223 0.2764 0.8937

Molar vol, m3/kmol 0.48768 0.01849 0.22948 0.74208
MW, g/mol 48.717 18.14 138.06 38.48
Ideal H, BTU/lbmol -9215.579 4924.45 14846.18 -20994.73
Enthalpy, BTU/lbmol -12265.720 4924.45 -3351.00 -21449.12
Ideal Cp, BTU/lbmol-R 8.097 65.566 38.702
Cp, BTU/lbmol-R 8.097 79.645 40.187
Density, lb/ft3 61.2428 37.5588 3.2373
Viscosity, cp 0.9405 0.3080 0.0175
IFT, dyne/cm 0.0000 1.3805 49.6694
Phase volume % 0.9234 7.1776 91.8990
Phase mole % 24.3531 15.2536 60.3933
Set Up the Regression Run

The next phase of the modelling process is to perform a regression run using the predicted
solubilities of CO2 in brine as pseudo-experimental data. The results of the regression will be
a reference Henry’s constant and molar volume at infinite dilution for CO2 which may be
included in a GEM data set.
Modify the Initial Component Properties
Save the data set used for performing the flash calculations in the previous step under a new
name using File|Save As …. This will be used as the basis for the regression data set.
To perform regression on aqueous phase solubility parameters, valid initial values of the
parameters must be present in the component table. Open the Component Selection/Properties
form and scroll over in the table until the column with Henry’s constants is visible. Select
AqueousSolubility|Calculate component solubility parameters from the menu. This will bring
up a form to enter the temperature and pressure at which you want the initial solubility parameters
evaluated as shown below.

The pressure entered will be used as the reference pressure for calculating Henry’s constants
during regression. In this case 500 psia is used. The temperature entered should be the same
as the temperature specified for your flash calculations (160 °F). Click OK to return to the
component table when you have entered these values.
Note that molar volumes at infinite dilution and reference pressures have been filled in for all
components. Valid Henry’s constants have also been entered in the table for CO2, C1 and C3, as
these components are considered to be soluble in the aqueous phase by default. Since we are
concerned only with the solubility of CO2, the Henry’s constants for C1 and C3 should be set to
1.0E+20. The aqueous solubility parameters should now appear as shown below.

Before leaving the Component Specification/Properties form, the text box on the Aqueous
phase tab for setting the aqueous phase salinity should be cleared or set to zero. This value is
used only for predicting the effect of salinity on Henry’s constants and should not be used during
regression on aqueous phase solubility parameters. Click OK to return to the main form.
Specify the Regression Parameters
Click once on the row following the composition form to make that the active row. Select
Regression|Start from the main menu as shown below to insert a Regression Parameters
form at this point.
Double-click on the Regression Parameters row to bring up the data entry form. The only
parameters that we want to modify are the reference Henry’s constant and molar volume at
infinite dilution for CO2. Scroll over on the grid shown on the Component Properties tab to
display the last two columns in the grid. Click in the row corresponding to CO2 under the
columns labelled “Henry Const.” and “V inf.” to select the parameters to use in regression.
The form should now appear as shown below.
Click OK to return to the main form. When the dialog box appears asking if you would like
to change the number of simultaneous regression parameters, answer No to retain the default
value. When there are five or fewer regression parameters specified, the default is to set the

number of simultaneous regression parameters equal to the total number of regression
parameters specified.
Specify the Experimental Data
The experimental data must be entered in the data set by specifying a flash calculation for
each pressure that we have solubility data for. Begin by double-clicking on the OGW/EOS
Multiphase Flash row to edit the existing flash specification. Change the Pressure step to
0.0 and the Number of pressure steps to 1. Also edit the comment to reflect the new
specification if necessary. The form should now look like the one pictured below.
Click on the Exp. Solubility tab to enter the data generated earlier for solubility of CO2 in
brine. Make sure that the unit selected for entering the solubility is Mole Fraction, then
enter the value predicted for the amount of CO2 in brine from the first part of this case study.
For the flash at 500 psia, the amount of CO2 in the aqueous phase was calculated to be
0.47996 mole%, thus the entry in the table should be 0.0047996 as shown below. All of the
other entries in the table can be left blank. They will default to a value of “-1”. A negative
value indicates that a given experimental data point will not be used in the regression.

Click OK to return to the main form.
The flash specification with experimental data constructed above can now be copied and
modified for the other pressures. Make sure that the OGW/EOS Multiphase Flash row is
selected, then select Edit|Copy from the main menu (or press Control-C). Click on the first
blank row underneath the OGW/EOS Multiphase Flash, then select Edit|Paste from the
main menu (or press Control-V).
Double-click on the new OGW/EOS Multiphase Flash row to open the data entry form.
Change the pressure to 1500 psia, then click on the Exp. Solubility tab and enter the value of
CO2 solubility recorded for this pressure from the first part of this case study. This should be
a mole fraction of 0.0101982.
Create flash specifications and enter the CO2 solubility data for 2500 psia (0.0121624 mole
fraction CO2), 3500 psia (0.0131680 mole fraction CO2) and 4500 psia (0.0139434 mole
fraction CO2).
Complete and Run the Regression Data Set
After the last flash specification, make sure the first blank row at the end of the data set is
selected and then select Regression|End to enter an End Regression form into the data set.
The completed regression data set should now appear as follows:
Save and run the data set.

View the output by selecting File|View output or by pressing the F3 function key. At the
end of the output file, two summary tables are printed: “Summary of Regression Variables”
and “Summary of Regression Results.” Looking at the before and after regression values in
the regression results table in comparison to the experimental values shows that the fit has
been considerably improved. Investigation of the regression variables table, however, shows
that both of the regression variables have reached the default upper bound imposed. This
indicates that further improvement to the fit could be obtained by increasing this limit for one
or both of the parameters chosen.

A summary of the regression iterations appears roughly in the middle of the output file.
Examination of this table shows that the Henry’s constant for CO2 (indicated by the name
HEN1 in the table) reached its limit first during the regression iterations. Thus, we will try
increasing the upper bound for this parameter.
Modify the Regression Data Set
Close the output file, then double-click on the Regression Parameters row to bring up the data
entry form. Click on the Variable bounds tab, and change the upper bound for the CO2
Henry’s constant to 5500 atm. At this point the convergence tolerance can also be tightened on
the tab Regression controls. Enter a value of 0.000001 in the convergence tolerance text box.
Click OK to return to the main form, then save and run the data set.
Viewing the summary tables at the end of the output file now shows that an excellent match
of the CO2 solubility data has been obtained. Close the output file in preparation for the final
phase of the modelling process.
Create a New Data Set
Once the process of tuning the model has been completed, a new data set can be created with
all of the updated model parameters. Select File|Update component properties from the
main menu. This will overwrite the first three forms in the data set with the model
parameters obtained from the regression run. Use File|Save As … to save the file under a
new name. This new file will be used to generate the fluid model specification for GEM.
First, remove all of the calculation options below the composition form. Click on the
Regression Parameters row and drag the mouse down to the End Regression row to select
all of the calculations, then select Edit|Delete or press the Delete key to remove the
calculations as shown below.

Add GEM Fluid Model Creation to the Data Set
Click on the first blank row underneath the Composition row, then select
SimulatorPVT|CMG GEM EOS Model from the main menu as shown below.
This will insert a CMG GEM EOS Model form into the data set. Double-click on this row
to bring up the data entry form.
Under File Selection, click the check box labelled Print component properties for GEM. It is
also possible to get an echo of the component properties to the output file by clicking the check
box labelled Print detailed component properties to *.OUT. GEM does not need to have the
water component included in the component list, therefore the checkbox labeled Include H2O in
GEM component list can be left in its default unchecked state. To output Henry’s constants
and molar volumes, the check box labelled Print aqueous phase component solubility
parameters must also be checked. Note that when the solubility parameters are defined on the
Component Selection/Properties form, they are constant for a data set, and the option buttons
available under Solubility Parameters will have no effect. Selecting these options only affects
the results when the internal model is used to generate Henry’s constants and other solubility
parameters. The reservoir temperature must also be entered to complete the fluid model
description for GEM.
The completed form should now appear like the one below. Click OK to return to the main form.

Run the Data Set for the GEM Fluid Model
Save and run the data set, then view the output file. The table in the output file shows a listing
of the properties for all of the components, including the aqueous phase solubility parameters.
The GEM fluid model is saved in a file with the same root name as your data file and output
file, but with the (.gem) extension (e.g. for the Case2b.dat data file, the GEM fluid model is
stored in the file Case2b.gem). The file can be viewed by selecting File|View GEM EOS
Model from the main menu. This file contains the same information as shown in tabular form
in the output file, but written out in the keyword format required for GEM.
The GEM fluid model file can be referenced in a GEM data set using an “include” statement,
or it can be imported into a data set using CMG’s ModelBuilder program.
Case Study Number 3: Asphaltene Precipitation Modelling
This case study describes the procedure for modelling the precipitation of asphaltene from a
live reservoir oil due to pressure depletion. The thermodynamic model used to describe the
precipitation of asphaltene and the flash algorithm for solving the equations are given in
references 19 and 20. Please refer to the “Flash Calculations” chapter for further
information on Asphaltene/wax modelling.
The steps required to develop a precipitation model are:
1. Fluid characterization
2. Regression on fluid PVT
3. Specification of solid model parameters
4. Prediction of precipitation behavior

Fluid analysis and asphaltene precipitation data are taken from Burke, Hobbs and Kashou,
“Measurement and Modeling of Asphaltene Precipitation,” Journal of Petroleum Technology,
November 1990, pp. 1440-1446. The following data for “Oil 1” taken from Table 1 of Burke
et al will be used in this example.
Component Oil 1
Nitrogen 0.57
Carbon Dioxide 2.46
Methane 36.37
Ethane 3.47
Propane 4.05
i-Butane 0.59
n-Butane 1.34
i-Pentane 0.74
n-Pentane 0.83
Hexanes 1.62
Heptanes plus 47.96
Total 100.00
C7+ molecular weight 329
C7+ specific gravity 0.9594
Live oil molecular weight 171.4
Stock tank oil API gravity 19.0
Asphaltene content in stock tank oil, wt% 16.8
Reservoir temperature, °F 212
Saturation pressure, psia 2950
Fluid Characterization
To begin this case study, a data set has been prepared to characterize the fluid by defining the
compositions of components up to C6 and pseudo-components describing the C7+ fraction. The
data set is named Case_study-3-split.dat and is located in the WinProp templates directory, for
example cmg\WinProp\2000.10\Tpl. You can begin by using this file, or by constructing your
own data set as described in Case Study Number 1. From the table above, the composition data
to C6 has been used, and a Plus Fraction Splitting calculation has been specified with the C7+
molecular weight and specific gravity. The plus fraction will be lumped into 4 pseudo-
components, and the Lee-Kesler critical property correlations will be used.
Perform the splitting calculation either by running your own data set, or by running the
Case_study-3-split.dat data set.
Update the System Component Specification
After splitting, the equation of state model can now be tuned to any available PVT data via
regression. First, the component specification must be updated to reflect the results of the
splitting calculation. This is done by selecting File|Update component properties from the
file menu, which will modify the first three forms in the data set. Save the data set under a
new name to avoid overwriting the original file by selecting File|Save As ... and entering a
new name. Remove the splitting calculation from the data set by selecting the row labelled
Plus Fraction Splitting and pressing the Delete key or by selecting Edit|Delete from the

main menu. Open the Titles/EOS/Units form and enter a new comment and descriptive title.
Open the Component Selection/Properties form and click the check box to Use
temperature-dependent volume shifts. This will allow good initial predictions of the
volumetric properties of the fluid. After closing this form, the calculation options required to
perform the regression can be added to the data set.
Set up the Regression Data Set
Select the first blank row underneath the Composition row. Enter a Regression Parameters
form into the data set by selecting Regression|Start from the main menu or by clicking the
Strt Reg button the toolbar. Then enter a Saturation Pressure calculation by clicking the
Sat Pres button, and an End Regression form by clicking End Reg. Open the data entry
form for the Saturation Pressure calculation and enter a temperature of 212 °F, saturation
pressure estimate of 2500 psia, and an experimental saturation pressure measurement of 2950
psia. Close this form and open the Regression Parameters form. Go to the Interaction
coefficients tab and click the option button for Select from list, then select HCIntCoefExp –
1 from the list. This selects the hydrocarbon interaction coefficient exponent as a regression
variable. For more information about this parameter, please refer to the “Components”
section of the User’s Guide. Go to the Regression Controls tab and set the Convergence
tolerance to 0.00001 to achieve a good match to the experimental data.
Click OK to close the Regression Parameters form. Before the form closes, a dialog box
appears asking if you would like to change the number of simultaneous regression parameters.
Click No to accept the default value. The data set should now look like the following:
A copy of this data set, Case_study-3-regress.dat is available in the templates directory for
comparison to your own work. Run the data set, then view the output from the run. The
regression summary table at the end of the output file shows that an exact match to the
saturation pressure was achieved.
The model is now ready to be modified for asphaltene precipitation prediction.
First update the component properties as before, then save the file under a new name.

Specification of Asphaltene Component
Again, a new title and descriptive comment can be added to the Titles/EOS/Units form if
desired.
The asphaltene component is specified by splitting the heaviest component of the oil into
precipitating and non-precipitating components. These two components have the same critical
properties and acentric factors, however the precipitating component has higher binary
interaction coefficients with the light components up to about C5. This is achieved in
WinProp by adding a new component to the component list, then copying the properties of
the heaviest component, onto the newly added component.
Open the Component Selection/Properties form. Begin by unchecking the check box for
Use temperature-dependent volume shifts, this allows the volume shifts to be fine tuned to
density data. In the component table, click on the row directly underneath the component
C31+. Enter any hydrocarbon component from the library by selecting Options|Insert library
component, clicking on FC6, then clicking OK. Select the entire row of C31+ properties by
clicking on the row label “14” at the left side of the table. Copy the properties to the
clipboard by using Ctrl-C or selecting Edit|Copy from the menu, as shown below.
Now click on the first column in the row for the component that you just entered, i.e. click on
the component name FC6, and use Ctrl-V or Edit|Paste to paste the properties onto the new
component. The component names can now be edited, for example C31A+ and C31B+. To be
able to specify interaction coefficients with the other components individually for the C31B+
component, as opposed to calculating them with the hydrocarbon interaction coefficient
exponent, the HC flag in the column next to the component name can be set to 0. The
component list should now appear as follows:

Click on the Int. Coef. tab, and click on Show HC Int. Coef. to view the magnitude of the
binaries between C31A+ and the light components. As described in references 19 and 20, the
binaries for the precipitating component must be considerably higher than those for the non-
precipitating component to give the correct shape of the precipitation curve below the bubble
point. Values on the order of 0.2 are expected to give good results. For C31B+, enter the same
binaries as C31A+ for CO2 and N2, then enter values of 0.2 for the interactions with C1 through
nC5. All other values for C31B+ should be left as zero. Click OK to complete the component
specification.
Specification of Asphaltene Composition
The mole fraction of the asphaltene component can be determined from the relation:
xAsph MWAsph = wAsph MWOil. From the output of the regression run, the molecular weight of
the oil is calculated as 171.343, as compared to the reported value of 171.4. The asphaltene
content of the stock tank oil is given as 16.8 wt%. As the weight fraction of gas in the live oil
is usually small, the value of 16.8 wt% will be used for the live oil. From the component
table, the molecular weight of the C31B+ component is 665.624. This results in a mole fraction
of 0.04324607 for the precipitating component. Open the Composition form and enter this
value for the mole fraction of C31B+. Subtract this amount from the original mole fraction of
C31+, and enter 0.07424660 as the mole fraction for C31A+. Click OK to close the form.
Specification of Additional Regression Data
When the heaviest component is split into precipitating and non-precipitating parts, and the
binaries for the asphaltene component are adjusted, the fluid phase behavior predictions will be
affected. For this reason, regression must be performed again to ensure that the model will
predict the correct fluid and solid phase behavior. In this data set, we will add regression on the
stock tank oil API as well as the saturation pressure. Click on the End Regression row, then
click the SEP button to insert a separator calculation into the data set. Open the Separator form
and enter an estimate for the saturation pressure of 2500 psia and a temperature of 212 °F in the

first column of the separator specification. Go to the Experimental Data tab and enter 19.0 for
the stock tank oil API and click OK.
To match the experimental API, we will modify the volume shift parameters of the heavy
fraction pseudo-components. As the volume shift of the asphaltene component affects the
amount of precipitate, as well as the liquid density, it will not be adjusted during regression.
Open the Regression Parameters form and click in the Vol Shift column in the rows
corresponding to the components C07-C15, C16-C25 and C26-C30 to select these parameters as
regression variables. Click OK and again select NO on the dialog box to leave the default
number of simultaneous regression variables.
Specification of Reference Fugacity for Asphaltene Model
The equation describing the fugacity of the solid component in the solid phase is given in the
“Flash Calculations” chapter of the User’s Guide. Writing this equation for isothermal
conditions gives
ln f s = ln f s* + v s (p1 − p o ) / RTo (1.1.1)
*
where fs is referred to as the reference fugacity, at the reference conditions po and To. vs is the
molar volume of the solid. The reference fugacity is usually set equal to the fugacity of the
precipitating component calculated by the equation of state at an experimentally determined
asphaltene precipitation onset pressure for a given temperature. This ensures that the model
will predict the correct onset pressure. At other pressure conditions, the fugacity of the solid
component in the solid phase is compared to the fugacity of the solid component in the liquid
phase as predicted by the equations of state, if the fugacity of the solid component in the solid
phase is lower then asphaltene will precipitate.
With modern solid precipitation detection systems, onset pressures can usually be determined
quite accurately. In the Burke et al data, an exact onset pressure is not given, instead, a
pressure point above the saturation pressure at which a small amount of asphaltene
precipitates is determined. The data given (in Burke et al Table 5) is 0.402 wt% asphaltene
precipitated at 4014.7 psia and 212 °F. To use this data, the reference fugacity is determined
at the given pressure and temperature, but with the precipitated amount of asphaltene
removed from the system. The reported wt% of precipitated asphaltene must again be
converted to a mole fraction to enter into WinProp. Using the same formula and molecular
weights as before, the mole fraction of precipitated asphaltene is determined as 0.001034817.
Click on the Composition form, then use Ctrl-C to copy the form. Click on the row
underneath the End Regression form and use Ctrl-V to paste a copy of the composition
form. Open the new Composition form, and subtract the amount of precipitated asphaltene
from the mole fraction of component C31B+, the resulting mole fraction should be
0.042211253. When you click OK, a warning that the composition no longer sums to 1.0 will
be issued, this can be ignored as all compositions will be normalized.
Click on the row below the new composition form and then click the ASP/WAX button on
the toolbar to enter a new Asphaltene/Wax Modelling form in the data set. Open the form
and enter the reference conditions of 4014.7 psia and 212 °F on the first tab. Click on the Ref.
State tab and select CALCULATE for the Reference Fugacity Specification. This will set
the reference fugacity equal to the fugacity of the precipitating component in the liquid phase
calculated by the equation of state. Click OK. The data set should now appear as follows:

Specification of Solid Molar Volume
As discussed in reference 19, the solid molar volume should be set to a value slightly higher
than the molar volume for the precipitating component predicted by the equation of state. At
this point we can run the data set to check the regression on the fluid PVT data and to view
the solid molar volume predicted by the EOS. Run the data set and view the output file. The
regression summary table shows that both the saturation pressure and stock tank API are
matched exactly. At the end of the file, a listing of the parameters of the solid model are
given. The solid molar volume is given as 0.65883 L/mol. A good initial value to enter for the
solid molar volume is 0.67 L/mol. Return to the data set and open the Asphaltene/Wax
Modelling form and go to the Ref. State tab. Scroll over in the grid showing the properties of
the C31B+ component and enter 0.67 under Molar Vol. This molar volume will be used by all
subsequent asphaltene precipitation calculations. Click OK close the form.
Prediction of Asphaltene Precipitation
To perform predictions of asphaltene precipitation, we need to use the whole live fluid
composition, not the composition adjusted for the reference fugacity calculation. Click on the
first Composition row in the data set (row 3) and use Ctrl-C to copy it to the clipboard. Now
click on the row underneath the Asphaltene/Wax Modelling form and use Ctrl-V to paste
the Composition form. Then add a new Asphaltene/Wax Modelling form at the end of the
data set. Open the form and enter a temperature of 212 °F. We want to predict the amount of
asphaltene precipitated at various pressures. Enter a Pressure of 14.7 psia, a Pressure Step
of 200 psia and a No. of pressure steps of 31. This specification results in flashes being
performed every 200 psi from 14.7 to 6014.7 psia.

Click on the Ref. State tab and set the Reference Fugacity Specification to PREVIOUS.
This specifies that the reference fugacity for the asphaltene model will be set to that value
determined in the previous asphaltene flash, where the reference fugacity was set to
CALCULATE. The molar volume, reference pressure and reference temperature set
previously will also be used. Now go to the Plot Control tab, click on the X-Y Plots option
button, then check the Plot weight % solid phase checkbox. Click OK to close the form.
The final data set is now ready to run, and should appear like the one below.
Run the data set, and click on the button with the Excel icon on the toolbar to create the plots.
You should see that the shape of the asphaltene precipitation curve from the upper onset
pressure to the saturation pressure shows the expected trend of increasing precipitation with
decreasing pressure. Note also that the predicted amount of asphaltene at the reference
pressure of 4014.7 psia is exactly equal to the experimental value of 0.402 wt%. The shape of
the curve at lower pressures is incorrect. The final step in this case study discusses how to
adjust the solid model parameters to achieve the correct shape of the precipitation curve.
Adjustment of Solid Model Parameters
As the solid precipitation model used in WinProp is thermodynamic, as opposed to kinetic,
reversibility of precipitation is possible. i.e. precipitated solids can redissolve in the liquid
phase. This phenomena has been observed in the laboratory for pressure depletion. Usually
the maximum amount of precipitation occurs around the saturation pressure of the fluid.
Below this pressure, liberation of gas from the oil changes the solubility parameter of the
liquid phase and allows redissolution of the precipitated asphaltene. It is possible that all of
the precipitated asphaltene will go back into solution at sufficiently low pressures.
The parameters that control this behavior in the solid model are the solid molar volume and
the interaction parameter between the precipitating component and the light ends of the oil.
Increasing the solid molar volume increases the maximum amount of precipitation at the
saturation pressure. Increasing the interaction parameter with the light ends will force the

asphaltene to redissolve at lower pressures. The experimental data given in Burke et al (Table
5) indicates the maximum amount of precipitation from this fluid should be about 1%, and
that the amount of precipitation should decrease to 0.403 wt% at 1014.7 psia.
Judging from the results of the initial run, it is seen that the molar volume of the solid must be
increased slightly to increase the maximum amount of precipitation from approximately 0.8
wt% to 1 wt%. The interaction parameter between the precipitating component and the light
ends must also be increased to give the correct shape of the precipitation curve below the
saturation pressure.
As noted earlier, performing the regression within the asphaltene modelling data set allows
the model to predict the correct fluid PVT behavior when the interaction parameters for the
asphaltene component are changed.
Adjust the solid molar volume first to achieve the desired maximum amount of precipitation.
In this case, a value of 0.675 L/mol was found to give good results. After this step, adjust the
interaction parameters between the C31B+ component and the components C1 through nC5.
Using a constant value of 0.224 for all of these interactions gives a good shape to the
precipitation curve, although it doesn’t match exactly the experimental data. For comparison
with your work, the final model is given in the template data set Case_study-3-asph.dat. The
asphaltene precipitation plot from this data set is shown below.
Burke Oil 1 asphaltene modelling

Phase Properties (Solvent Mole Fraction = 0.0000)
1.20
1.00
Solid Precipitate (wt %)
0.80
0.60
0.40
0.20
0.00
0 1000 2000 3000 4000 5000 6000 7000
Pressure (psia)
212.00 deg F

Appendix B
Equations
The following are the equations used in WinProp.
Cubic Equation of State
A cubic equation of state takes the general form
RT a
p= − 2 (2.1.1a)
v − b v + vb(1 + c ) − cb 2
or
RT a
p= − (2.1.1b)
v − b (v + δ1 b )(v + δ 2 b )
where
2δ1 = (1 + c ) − (1 + c)2 + 4c
δ1 δ 2 = − c
When c=1, Equation (2.1.1a) becomes the Peng-Robinson Equation of State and when c=0, it
becomes the Soave-Redlich-Kwong Equation of State.
For pure components, the parameters a and b are expressed in terms of the critical properties
and the acentric factor:
a = a cα
a c = Ω a (RTc ) / p c
(
α = 1 + κ 1 − T / Tc )
b = Ω b RTc / p c (2.1.2)
Define
A ≡ ap /( RT ) 2
and
B ≡ bp / RT
User's Guide WinProp Appendix B • 183

the compressibility factor Z ≡pv/RT can be expressed as:
[ ] [ (
E ≡ Z 3 − Z 2 (1 − cB) + Z A − B(1 + c ) − B 2 (1 + 2c ) − AB − c B 3 + B 2 ) ]= 0 (2.1.3)
For mixtures, the parameters a and b are defined using the following mixing rule
a = ∑ x i Si
i
Si ≡ a i ∑ x j (1 − d ij ) a j
j
b = ∑ x i bi (2.1.4)
i
where dij is an empirically determined interaction coefficient.

The fugacity coefficient is derived from the equation of state (Michelsen, 1981)
~
⎛ ∂F ⎞
ln φ = ⎜⎜ ⎟⎟ − ln Z
⎝ ∂n ⎠ T , v
where
∞
~ ⎛ p N⎞
F≡∫ ⎜ − ⎟dV (2.1.5)
v ⎝ ⎠
RT V
Resulting in
ln φ i =
bi
(Z − 1) − ln(Z − B) − 1 A ⎛⎜ 2Si − b i ⎞⎟ ln⎛⎜⎜ Z + δ 2 B ⎞⎟⎟ (2.1.6)
b δ 2 − δ1 B ⎝ a b ⎠ ⎝ Z + δ1 B ⎠
Calculation of Parameters
The above equations require the knowledge of Ωa, Ωb and κ. The two parameters Ωa, Ωb are
obtained from the critical condition. At the critical point, the compressibility factor will have
three real and equal roots (Martin, 1979).
(Z − Z c )3 = 0
Comparing with the above Z equation results in
Ω b = 1 / (3Z1 + c )
Ω b = ( Z13 + c + c / Ω b )Ω 2b
Z c = Ω b Z1
where
Z1 ≡ 1 + Z 2 + 2 / Z 2
Z 2 ≡ (3 + c + Z 3 )
1/ 3
Z 3 ≡ c 2 + 6c + 1
184 • Appendix B User's Guide WinProp

Setting the value of c results in the usual equation of state:
Equation of State c δ1 δ2 Ωa Ωb Zc
Peng-Robinson (PR) 1 -0.4142 2.4142 0.45724 0.07780 0.307

Soave-Redlich-Kwong 0 0 1 0.42747 0.08664 0.333
(SRK)
Equation (2.1.7)
The κ is obtained from the following empirical correlations.

For the PR equation of state, Peng and Robinson (1976) proposes
κ = 0.37464 + 1.54226 ω − 0.26992 ω 2
and for hydrocarbons heavier than n-decane (Robinson and Peng, 1978)
κ = 0.379642 + 1.48503 ω − 0.164423 ω 2 + 0.016666 ω3
For the SRK equation of state, Soave (1972) proposes
κ = 0.480 + 1.574 ω − 0.176 ω 2
While the following equation is suggested by Grabowski and Daubert (1978)
κ = 0.48508 + 1.55171 ω − 0.15613 ω 2
Selection of Compressibility Root and Vapor/Liquid Identification
The cubic Z-factor equation may yield two real roots. In which case, the one that results in
the lowest Gibb's free energy (i.e. most stable) will be selected. Let ZA and ZB be the two real
roots resulting in free energy GA and GB respectively. Since free energy
G = ∑ x i ln f i ,
i
⎛ Z − B⎞ A ⎛ Z B + δ 2 B Z A + δ1 B ⎞
⎟⎟ − (Z B − Z A )
1
G A − G B = ln⎜⎜ B ⎟⎟ + ln⎜⎜ (2.1.8)
⎝ Z A − B ⎠ δ 2 − δ1 B ⎝ Z A + δ 2 B Z B + δ 1 B ⎠
If GA - GB > 0, ZB will be selected and vice versa. For single-phase fluids, if the above
scheme selects the largest Z root, the fluid is said to be vapor. Similarly, if the smallest
positive Z root is chosen, the fluid is said to be liquid.
In cases where the Z-factor equation yield only one real root, the naming of the phase to be
vapor or liquid is irrelevant. For identification purposes, the criteria according to Gosset et al
(1986) is used.
The fluid is designated as liquid when A/B > Ωa / Ωb and Z < (Zc/Ωb)B, else it is designated
as vapor.
For simplicity, the EOS Zc as shown in Equation (2.1.7) is used in the above criteria. For
multiphase fluids, the phases are identified according to their mass densities. The lower
density phase is arbitrarily denoted as vapor.

Volume Translation Technique
The volume translation technique of Peneloux et al (1982) is used to improve the density
prediction capability of the SRK and PR equation of states.
Consider pressure-explicit equation of state of the form:
p = p (T, V, n1, n 2, n 3, ... )
The fugacity of component i is
(v i / RT − 1 / p )dp + ln(x i p )
p
ln f i = ∫ (2.1.9)
o
where vi is the partial molar volume. The equilibrium conditions require that
ln f iL = ln f iv (2.1.10)
A volume translation modifies the molar volume of the system v predicted by the equation of
state as follows:
vt = vo − ~
v (2.1.11)
v = ∑ x i ri
~
ri = t i B ci
and
RTc
B ci = Ω b
pc
where ti is the dimensionless individual translation value for each component and the
superscripts o and t correspond respectively to the results before and after the volume
translation. Bci is the hard core molecular volume of component i. By using equation
(2.1.11), the fugacities of the component i after the volume translation become:
ln f it = ln f io − pri / RT (2.1.12)
Thus if
( ) ( )
ln f iL = ln f iv , then ln f iL ( ) t
( )
= ln f iv
t
,
i.e. the volume translation has no effect on the equilibrium conditions. Therefore, it will not
alter the saturation pressures, saturation temperatures, equilibrium compositions, etc.
However, it will modify the molar volumes, compressibility factors and densities of the fluid.
The following equations show the effect of equation (2.1.11) on the parameters of interest to
petroleum engineers.
Compressibility
(
Z t = Zo v t / vo ) (2.1.13)
Gas oil ratio, GOR
GOR t = GOR o v o / v t ( )
stc (2.1.14)

Mass density, ρ
(
ρ t = ρo vo / v t ) (2.1.15)
where the subscript stc denotes the stock tank (standard) conditions. Other equations of
interest can be derived easily using equation (2.1.11).
The use of the volume translation technique requires the knowledge of ri for each component.
These can be estimated from equation (2.1.13) at the critical conditions
(Z c )i = (Z c )EOS (v c i
− ri ) / v ci
where (Zc)EOS is the compressibility factor from the equation of state as shown in Equation (2.1.7).
Peneloux et al (1982) have tabulated values of ti for the first ten components in the alkane series.
Jhaveri et al (1984) have also developed empirical equations for ti. Generally, for phase behavior
matching, it is advantageous to treat ti as regression variables. Experience shows that it is
sufficient to introduce non-zero ti's for the C6+ components and methane only. Furthermore, for
the C6+ components, it is preferable to have one ti value for all components, e.g.
t C6 − C12 = t C13− C 20 = t C 21+ .
Enthalpy and Heat Capacity
The excess enthalpy, HE, of a fluid which follows the EOS in Equation (2.1.1) is given by:
H E ≡ H − H*
T(∂a / ∂T ) − a ⎛ v + δ 2 b ⎞
= pv − RT + ln⎜ ⎟ (2.1.16)
(δ 2 − δ1 ) ⎜⎝ v + δ1 b ⎟⎠
and the excess capacity
(
Cp E ≡ ∂H E / ∂T )
p (2.1.17)
where H is the system enthalpy and H* is the enthalpy at the ideal gas state, calculated from
H * = ∑ x i H *i
i
*
Hi is a function of temperature only and can not be derived from the EOS and has to be input
by the user in the form of a polynomial
H *i = H A + H B T + H C T 2 + H D T 3 + H E T 4 + H F T 5
With T in deg. R and Hi* in Btu/lb. HA through HF are user specified parameters. Passut and
Danner (1972) have compiled the values of HA through HF for components commonly
encountered in Petroleum Engineering.
In most practical uses, the important variables are the enthalpy differences and not the
absolute enthalpies. Thus, the reference point for H can be chosen arbitrarily. In WinProp
enthalpy is assigned zero when the component is at ideal gas state at zero kelvin.

Phase Stability Test
The tangent-plane criterion of stability analysis of a phase with compositions X results in
solving the following set of equations (Nghiem and Li, 1984):
( )
D i ≡ ln K ip + ln φ i U − ln φ i (X ) = 0
~
(2.2.1)
where
K ip = u i / x i
and
ui = ui / ∑ u k
~
k
for the primary variables U. The phase will be stable if

∑ ui <1
i
and vice versa. If the phase is unstable, the equilibrium ratio Kip is a good first guess to
initiate equilibrium calculation. Equation (2.2.1) is solved using the QNSS method described
in Viscosity Correlation section.
To solve the above stability test equation, the following initial guess can be used:
Initial Guess Description

i Pure component
u i = 1, u j, j≠i = 0 i = 1,..., N c
Nc+1 Ideal gas
ln u i = ln φ i (X ) + ln (x i )
Nc+2 Average
u i = (y il + y iv ) / 2
Nc+3 Wilson's equation
p ci + 5.373(1+ ωi )(1− Tc i / T )
ui = xi e
p
Nc+4 Inverse Wilson's equation
p + 5.373(1 + ωi ) (1 − Tci / T )
ui = xi e
p ci
Initial guess (Nc+2) is generally used to test the stability of a liquid-vapor two-phase system only.

The initial estimates of the stability test is set according to the input variable LEVEL.
Level Initial guess used for stability test

0 Nc+3, Nc+4
1 H1, L1, Nc+3, Nc+4
2 H1, L1, Nc+1, Nc+3, Nc+4
3 H1, H2, L1, L2, Nc+1, Nc+3, Nc+4
4 Ii,i=1,...,Nc, Nc+1, Nc+3, Nc+4
where H1, H2 correspond to the heaviest and next heaviest component in the system and L1,
L2 correspond to the lightest and next lightest component.
START
Solve Equation (2.2.1) for U
No Phase
Σ ui <1
unstable
Yes
Tried all initial Yes Phase

guesses stable
No
Load the next

initial guess
Flow Chart for Tangent Plane Criterion Stability Test

Two-Phase Flash Calculation
Two-phase flash calculation requires the solution of the following equilibrium and material
balance equations:
Equilibrium equation:
( ) ( )
G i ≡ ln K i − ln φ i X L + ln φ i X V = 0 i=1,...,Nc
Material balance equation:
z k (K k − 1)
G n c +1 ≡ ∑ =0 (2.3.1)
k 1 + Fv (K k − 1)
where
K i = x iV / x iL
z = global composition of the feed
Fv = vapor phase mole fraction
and
x iL = z i /[1 + Fv (K i − 1)]
When 0 < Fv < 1, the feed splits into two equilibrium systems. When F < 0, the feed is stable
at the specified pressure and temperature but addition of a phase with composition XV to the
feed Z will result in a phase with composition XL in equilibrium with XV.
The equilibrium equation is solved using the QNSS method described in Solution of Non-
Linear Equations section, the primary variables are ln Ki with initial guesses from the
Wilson's equation:
⎛ Tc ⎞
ln K i = 5.37 (1 + ωi ) ⎜⎜1 − i ⎟⎟ + ln (p ci / p ) (2.3.2)
⎝ T ⎠
In solving the material balance equation, the method of Nghiem, Aziz and Li (1983) is used
for quick single-phase detection. With
fo = ∑ zk K k
k
f1 = ∑ z k / K k (2.3.3)
k
the system is a single-phase liquid when fo < 1 and a single-phase vapor when f1 < 1.

START
Initialization
Solve material balance equation for vapor

phase mole fraction and composition
No
Single Phase
Use QNSS to solve the equilibrium

equation once and update K-values Yes
Stability Test
Unstable
No
Convergence Stable
Yes Single Phase System
Two-Phase System
STOP
Flow Chart for Two-Phase Equilibrium Calculations

Saturation Calculation
Saturation condition of a mixture XL at a particular pressure p and temperature T requires that
the tangent plane to the Gibb's free energy surface at XL is also tangent to the surface at some
other composition XV. The p and T are the saturation pressure and temperature and XV is the
equilibrium composition (Nghiem, Li, and Heidemann, 1985), i.e.
G i ≡ ln K i + ln φ iV − ln φ iL = 0 1=1,2,...,Nc (2.4.1)
⎧ ⎫
D≡∑
⎪ x iV
⎨ [
ln K i + ln φ iV − ln φ iL ]
⎪
⎬=0 (2.4.2)
⎪∑ j
V
i x ⎪
⎩ j ⎭

where G is the equilibrium equation and D is the normalized distance from the Gibb's free
surface to the tangent plane at x, evaluated at a composition y where:
(
φ iV = φ i X V , p, T )
φ iL = φ (X
i
L
, p, T )
K i = x iV / x iL (2.4.3)
For saturation pressure (temperature) calculation, the primary variables are ln Ki and p(T).
The Nc equilibrium equation (2.4.1) can be solved by the QNSS method and during each
QNSS iteration, update p(T) from the distance equation (2.4.2). This is similar to the general
scheme used to solve the two-phase flash problems.
Initialization and Convergence
In the calculations performed in WinProp, an initial set of K-values, Ki(0), is first generated
from a stability test calculation (Michelsen, 1982; Nghiem and Heidemann, 1982; Nghiem
and Li, 1984) at a specified pressure and temperature. These values of Ki(0) will satisfy
equation (2.4.1) at the given T and p, which need not be close to the phase boundary. The
following sets of yi(0) are then defined from the initial K-values, Ki(0).
y i(,01) = K i(,01) x i ; K i(,01) = K i(0 ) (2.4.4)
y i(,02) = K i(,02) x i ; K i(,02) = 1 / K i(0 )
Let D1*(0) and D2*(0) be the distances in equation (2.4.2) corresponding to y i(,01) and y i(,02)
respectively.
These distances can be regarded as functions of a single variable (temperature or pressure) as
long as the mole fractions y are held constant at values derived from equation (2.4.4).
When the saturation temperature is specified, a one-dimensional search is performed to locate
all the pressures which satisfy
D1(0 ) = 0
and
D *2(0 ) = 0 (2.4.5)
Similarly, these equations are solved for all the temperature roots at a specified saturation
pressure.

The technique used to solve equation (2.4.5) for temperature or pressure is a one-dimensional
search combined with bisection or Newton's method. The saturation calculation using one of
the Newton methods or QNSS is then initialized with the yi values given by equation (2.4.4)
and the pressure and temperature conditions that satisfy equation (2.4.5). In some cases,
equation (2.4.5) was found to have more than one pressure root (at the given temperature) or
more than one temperature root (at the given pressure). The saturation calculation can be
initialized with any one of these starting guesses. It has been observed that convergence can
be obtained to a different solution for each of the starting guesses. In some problems, several
of the converged solutions are physically meaningful, such as lower and upper dew point
pressures in retrograde systems or points where liquid-liquid separations occur.
Some of the converged points are found to lie inside the two-phase region, however, and are
"trivial" solutions in the sense that the calculated V phase is identical to the starting L phase.
It has been observed that such trivial solutions, when they are found, lie on the stability limit
of the homogeneous fluid.
Cricondenbar/Cricondentherm Equations
The cricondenbar/cricondentherm for phase X is taken as a saturation point with additional
constraints. It solves the Nc+1 saturation equations (Nghiem, Li and Heidemann, 1985):
( ) (
G i ≡ ln K i + ln φ i X V , p, T − ln φ i X L , p, T = 0 )
[ ( ) (
D ≡ ∑ y i ln K i + ln φ i X V , p, T − ln φ i X L , p, T ) ]= 0
i
with
∂D ⎛ ∂ ln φ iV ∂ ln φ iL ⎞
= ∑ y i ⎜⎜ − ⎟ = 0 for cricondenbar
⎟
∂T i ⎝ ∂T ∂T ⎠
or
∂D ⎛ ∂ ln φ iV ∂ ln φ iL ⎞
= ∑ y i ⎜⎜ − ⎟ = 0 for cricondentherm
⎟ (2.5.1)
∂p i ⎝ ∂p ∂p ⎠
Analytical derivatives for ln φ could be used. The primary variables are ln Ki, p and T.
Phase Diagram Construction
Thermodynamic criterion for phase equilibrium is that the Gibb's free energy is minimized at
equilibrium. This yields the following necessary conditions:
G i ≡ ln K i + ln φiV − ln φiL = 0 i = 1,..., N c (2.6.1)
Material balance constraint gives
Nc
G N c +1 ≡ ∑
(K i − 1)z i = 0 (2.6.2)
i =1 1 + Fv (K i − 1)
where
K i = x iV / x iL

Let the feed composition, z, be a mixture of two fluids z1 and z2.
z i = (1 − ζ ) z 1i + ζ z 2 i
For specified z1 and z2, the variables required to completely determine the system are p, T, Fv,
K1, K2,..., KNc, ζ.
A total of Nc+4 variables with Nc+1 equations (2.6.1 and 2.6.2).
All variables are designated into three groups:
i Nc+1 primary variables, α
ii 1 specified variable, β
iii 2 fixed variables
The values of the fixed variables will be kept constant throughout the calculations. For each
point in the phase envelope, the value of the specified variable is fixed and the Nc+1
equations solved to give the Nc+1 primary variables. The value of the specified variable is
then incremented and the whole process is repeated to form the complete phase diagram.
The secondary variables xiL and xiV are computed from
x iL = z i /[1 + Fv (K i − 1)] (2.6.3)
x iV = z i K i / [1 + Fv (K i − 1)]
Various phase diagrams are formed by different designation of variables:
Types of Phase Diagram
Variable p-T p-X T-X Ternary
Primary, α ln Ki ln Ki ln Ki ln Ki
ln T ln p ln T Fv
Specified, β ln p ζ ζ ζ
Fixed ζ ln T ln p ζ
Fv Fv Fv ln T
The natural log is used to bring the magnitude of all the variables to a comparable basis.
General Phase Envelope Construction Algorithm
Michelsen (1980) presented a very efficient algorithm for P-T envelope construction. His
algorithm is summarized in the following. Other phase envelopes are generated with a
similar scheme (Li and Nghiem, 1982).
Let the subscript k denote the k-th point on the phase envelope. The temperature and K-
values of the first point on the phase envelope (vector α1) are found by solving the n+1
governing equations (2.6.1 and 2.6.2) at a specified pressure (β1) after the global composition
and F are fixed. The first specified pressure is usually low (≤2000 kPa or 290 psia) so that a
good estimate of the K-values can be obtained from the following equation:

exp [ 5.4.2 (1 − Tci / T ) ]
p ci
Ki = i=1,...,n
p
Newton's method is used to solve for α1. After convergence has been achieved, i.e.
∑ (α (kk,i+1) − α (kk,i) ) < ε

n +1
2
i =1
one proceeds to the next point on the phase envelope.

The efficiency of the method depends upon:
1. the initial guess α2(0), and
2. the specified variable β2
Once β2 is specified, Michelsen obtained the initial guess α2(0) by linear extrapolation. Let J1
be the Jacobian (∂G / ∂α)1. The inverse J1-1 is known from the last Newton's iteration of the
first point on the phase envelope. Differentiation of the equation G- = 0 (equation 2.6.1) with
respect to β at α1 and β1 yields:
⎛ ∂α ⎞ ⎛ ∂G ⎞
⎜⎜ ⎟⎟ = − J 1-1 ⎜⎜ ⎟⎟
⎝ ∂β ⎠1 ⎝ ∂β ⎠1
The above equation is used to obtain the initial guess α2(0) at β2 by linear extrapolation:
⎛ ∂α ⎞
α (20 ) = α 1 + (β 2 − β1 ) ⎜⎜ ⎟⎟
⎝ ∂β ⎠1
for the k-th point on the phase envelope with k ≥ 3, Michelsen used a third order extrapolation
of the form:
α (20,k) = a k 0 + a k1β k + a k 2 β 2k + a k 3 β 3k (2.6.4)
where akj, j=0,1,...,3, are the coefficients of the polynomial computed using the information of
the last two points (i.e. k-1, k-2). The step size, or in other words, the difference between two
subsequent specifications Δβk-1 is chosen within prescribed limits such that an increase takes
place if less than 3 iterations are used to solve the equations, and a decrease takes place if
more than 4 iterations are used. Usually, the step size is multiplied by a factor greater than
one in the former case, and multiplied by a factor less than one in the latter.
Although the phase envelope construction starts with a specification of pressure, another variable
can become a specified variable at its place during the construction of the phase envelope.
Indeed, if (∂α/∂β)k-1 is large in magnitude making the extrapolation inappropriate, the variable
corresponding to βk-1 will become a primary variable for the k-th point, and the one
corresponding to αk-1,i will become the specified variable.

The phase envelope construction does not restrict to the bubble point locus (F=0) or dew point
locus (F=1) construction. The locus of any given F(0≤F≤1) can also be generated. For
convenience, the locus corresponding to 1-F is always generated along with the one
corresponding to F. Michelsen also uses an interpolation polynomial of the form (2.6.4) based
on points on each side of the critical point to estimate the latter. The criteria used are that the K-
values are equal to one at the critical point. He reported that the pc and Tc obtained are accurate
to 1 kPa and 0.01 °K respectively. The same approach is used to estimate the cricondentherm
where ∂T/∂p = 0 and the cricondenbar where ∂p/∂T = 0.
START
Specify α, β
Set up initial guess

Calculate one point
on the phase diagram
Set up Jacobian matrix
Solve the equations
Update variables
Trivial Yes
root STOP
No
Unphysical Yes Reduce
results step size
No
One point
in the phase diagram
converged
Yes
Extrapolate Stability check

variables
Output
Adjust new
step size
Complete Yes Printer
phase diagram STOP
plot
constructed
Flow Chart for Phase Diagram Construction

Three Phase Flash Calculation with Equation of State
For a liquid 1-liquid 2-gas system, the conditions for phase equilibrium are as follows:
Equilibrium equation:
ln K iv + ln φ iV − ln φ iL = 0
ln K iq + ln φ iQ − ln φ iL = 0 (2.7.1)
where
K iv = x iV / x iL
and
K iq = x iQ / x iL i=1,...,Nc
Material balance equations
(K iv − 1) z i
∑ (x )
Nc Nc
V
i − x iL = ∑ =0
i =1 i =1 Fl + Fv K iv + Fq K iq
(K iq − 1) z i
∑ (x iQ − x iL ) = ∑
Nc Nc
=0 (2.7.2)
i =1 i =1 Fl + Fv K iv + Fq K iq
with the constraint Fl + Fv + Fq = 1. Subscript L and Q denote the liquid 1 and 2 respectively.
A three phase flash calculation corresponds to solving the 2Nc+3 nonlinear equations for the
2Nc+2 primary unknowns ln(Kiv), ln(Kiq), Fl, Fv and Fq. The mole fractions are treated as
dependent variables:
x im = K im z i / (K iv Fv + K il Fl + K iq Fiq ) (2.7.3)
A stage wise procedure is used for the three phase flash calculation. A two phase calculation
is first performed. The initial guess for the third phase is then obtained from the stability test.
QNSS method is used to solve the equilibrium equations. During each iteration, equations
(2.7.2) are used to update Fl, Fq and Fv.

START
Two phase L-V flash calculation
Single phase
2 phases
Stable
Stability test
Unstable
Solve material balance equation for phase split
3 phases
Update K-values by QNSS method
Program No
converged
Yes
Sort phases according to density
L-V L
V = Vapor Phase L-Q-V

L = Liquid phase 1
Q = Liquid phase 2
- = Equilibrium
STOP
Flow Chart for Three Phase Liquid-Liquid-Gas Flash Calculation

Three Phase with Isenthalpic Flash Calculation
Isenthalpic flash calculations correspond to finding the temperature, phase splits (phase mole
fractions) and phase compositions, given the pressure, composition and enthalpy of the feed,
together with the net enthalpy added to the system (Agarwal et al, 1988).
Consider one mole of feed of composition z in a nc-component, np-phase system (Figure B.1).
After defining the thermodynamic model, there are np independent governing equations for an
isenthalpic flash calculation, one energy balance and np-1 material balance constraint equations.

H add
y 1 T 2, P
ISENTHALPIC
z, T 1, P FLASH y 2 H spec
CALCULATIONS
yn
H spec = H in + H add
Figure B.1: Isenthalpic Flash Calculations

Let the equilibrium ratios (K-values) be
y ij i = 1,..., n c
K ij = (2.8.1)
yi R i j = 1,..., n p
where yij is the mole fraction of Component i in Phase j and R is the reference phase for the K-
value definition. Note that Ri need not be the same for all components. This gives extra
flexibility to define K-values in the cases that components are not always present in all phases.
The values of these K-values are obtained from an EOS by solving equilibrium equations.
By definition KiR, = 1.
Let Fj be the mole fraction of phase j in the system, the compositions can be obtained from
material balances as follows
z i K ij
y ij = (2.8.2)
ξi
and
np
ξ i = ∑ Fk K ik (2.8.3)
k =1
In addition, the mole number of Component i in phase j, nij, is given by

z i Fj K ij
n ij = Fj y ij = (2.8.4)
ξi
From the constraints that the mole fractions must sum up to unity, (np-1) independent
equations can be derived
( )
nc
g j ≡ ∑ y ij − y in p = 0 j=1,...,np-1 (2.8.5)
i =1
Substituting Equation (2.8.2) into (2.8.5) results in
gj ≡ ∑
nc (
z i K ij − K in p )=0 j=1,...,np-1 (2.8.6)
i =1 ξi

The above are the material balance equations used in isothermal flash calculations. For
isenthalpic flash calculations, there is an additional energy balance equation, i.e.
np
g n p ≡ H − H spec = ∑ Fj ∑ (y ij h ij ) − H spec = 0
nc
(2.8.7)
j=1 i =1
where Hspec is the specified molar enthalpy of the system and hij is the partial molar enthalpy
of Component i in Phase j which is also obtained from an EOS. Equations (2.8.6) and (2.8.7)
form a system of np equations for the np unknowns T and Fj (j=1,...,np-1). As the phase mole
fractions must sum up to unity, it follows that
n p −1
Fn p = 1 − ∑ Fj (2.8.8)
j=1
The equations can readily be solved by the Newton-Raphson method.

Thermodynamic Model
The K-values are obtained from the following thermodynamic equilibrium equation
i = 1,..., n c
ln K ij + ln φ ij − ln φ iR i = 0 (2.8.9)
j ≠ Ri
Equation (2.8.9) is derived from the equality of fugacities.
φij is the fugacity coefficient of Component i in Phase j estimated from an EOS and is a
function of pressure, temperature and phase compositions.
In using an EOS, the compressibility root corresponding to the minimum Gibb's free energy is
selected unless stated otherwise. Note that Equation (2.8.9) represents a system of nc nonlinear
equations and is solved iteratively with the material balance and energy balance equations.
Flash Calculation Involving Water
For a liquid-gas-water system, the conditions for phase equilibrium are as follows:
Equilibrium equations:
ln K iv + ln φ iV − ln φ iL = 0
ln K iw + ln φ iW − ln φ iL = 0 (2.9.1)
where
K iv = x iV / x iL
and
K iv = x iW / x iL
Material balance equations:
(K iv − 1)z i
∑ (x iV − x iL ) = ∑
Nc Nc
=0
i =1 i =1 Fl + Fv K iv + Fw K iw
(K iw − 1)z i
∑ (x iW − x iL ) = ∑
Nc Nc
=0 (2.9.2)
i =1 i =1 Fl + Fv K iv + Fw K iw

with the constraint Fl + Fv + Fw = 1.
A three-phase flash calculation corresponds to solving the 2Nc+3 nonlinear equations for the
2Nc+3 primary unknowns Kiv, Kiw, Fl, Fv and Fw. The mole fractions are treated as dependent
variables:
x im = K im Z i / (K iv Fv + Fl + K iw Fw ) (2.9.3)
For the components j which are assumed not soluble in the aqueous phase, take Kjw = 0 and
remove the corresponding equilibrium equation from the equation set. The system of
equations can be solved by the quasi-Newton successive substitution method discussed in
Nghiem and Li (1984) and Mehra et al (1984).
Thermodynamic Models
The liquid and vapor phases are modelled by the cubic EOS, and the solubility in the aqueous
phase is handled by Henry's law.
Henry's law for a component sparingly soluble in the aqueous phase states
ln φ iW = ln (H i / p ) i≠w (2.9.4)
where the bold superscript w denotes the water component, and the regular subscript w
denotes the aqueous phase. Hi is the Henry's law constant of component i in the aqueous
phase. The variation of Henry's law constant with respect to pressure and temperature
follows the equation:
ln H i = ln H *i + v i∞ p / (RT ) (2.9.5)
where H* is a reference Henry's law constant.
The molar volume at infinite dilution vi∞ is computed from the correlation of Lyckman et al
(1965) reported by Heidemann and Prausnitz (1977) in the form:
⎛ p ci v i∞ ⎞ ⎛ T p ci ⎞
⎜ ⎟ = 0.0095 + 2.35⎜ ⎟⎟ (2.9.6)
⎜ RT ⎟ ⎜ CT
⎝ ci ⎠ ⎝ ci ⎠
where C is the cohesive energy density of water given by:
( )
C = h ow − h sw + p sw v sw − RT / v sw (2.9.7)
pws is the saturated vapor pressure of water at the temperature T, pws is the molar volume of
water at pws and T, and hws - hwo is the enthalpy departure of liquid water pws and T.
The fugacity of the component water in the aqueous phase can readily be obtained from the
fugacities of the solutes using the Gibb's-Duhem equation as in Prausnitz (1969):
⎡p v ⎤
f ww = x ww φ sw p ww exp ⎢ ∫ w
dp ⎥ (2.9.8)
⎢⎣ p sw RT ⎥⎦
where φws is the fugacity coefficient of pure water at pws and vpws is the molar volume of pure
water.

The vapor pressure of water
(
p sw and h ow − h sw )
can be calculated respectively from the Frost-Kalkwarf-Thodos and the Yen-Alexander
equation reported in Reid et al (1977).
The molar volume vws is estimated from a correlation due to Chou reported in Rowe and
Chou (1970). The fugacity coefficient φws is obtained from the following correlation which
was found to match reasonably well the data in Canjar and Manning (1967):
φ sw = 0.9958 + 9.68330 x 10 −5 T ' − 6.1750 x 10 −7 T '2
− 3.08333 x 10 −10 T '3 ; T ' > 90 (2.9.9)
=1 ; T ' ≤ 90
T = 1.8T − 459.67
where T is the temperature in K, and T' is the temperature in °F.
Initial guesses for the K-values are:
K iv = p ci / p exp[5.42(1 + ωi ) (1 − Tci )]
K iw = K iv p / H i
The following table summarizes the reference Henry's law constant stored in WinProp (Li
and Nghiem, 1986).
Coefficients
Component A B C Water Interaction

Coefficient
Methane 10.9554 11.3569 1.17105 0.4907
Ethane 13.9485 13.8254 1.66544 0.4911
Propane 14.6331 14.4872 1.78068 0.5469
n-Butane 13.4248 13.8865 1.71879 0.5080
n-Pentane 16.0045 16.2281 2.13123 0.5000
n-Octane 31.9431 28.6725 4.37707 0.4500
Carbon Dioxide 11.3021 10.6030 1.20696 (1)
Carbon Monoxide 10.7069 11.1313 1.08920 0.2000
Nitrogen 10.7090 11.4793 1.16549 0.2750
Hydrogen Sulfide 10.8393 9.8897 1.11984 0.1200
(1) 0.2 T ≤ 373 K
0.49852 - 0.0008 (T), T > 373 K

where
⎛ H* ⎞ ⎛ 10 3 ⎞ ⎛ 10 6 ⎞
ln⎜⎜ si ⎟⎟ = − A + B⎜⎜ ⎟ − C⎜
⎟ ⎜ T2
⎟
⎟
⎝ fw ⎠ ⎝ T ⎠ ⎝ ⎠

T : temperature, K
fws : fugacity of saturated water, atm
Hi* : reference Henry's constant, atm
START
Call hint for initialization
Two phase L-W flash calculation
L Disappears 2 Equilibrium phases
W Disappears
Unstable Stability Stable Stability Stability

Test Test Test
Stable Unstable Unstable
Disappears L-V flash calculation W-L-V flash

calculation V or L
Disappears
W L L-V W-L L-V-W
W=Aqueous phase
L = Liquid phase
V = Vapor phase
STOP
- = Equilibrium
Flow Chart for Three Phase Water-Oil-Gas Flash Calculations

Critical Point Calculations
A critical point is a stable point on the stability limit. The Heidemann and Khalil (1980) method
for calculating critical points consists of solving the following two criterion for Tc and Vc:
Q ΔN = 0 (2.10.1)
and
⎛ ∂ 3A ⎞
C=∑ ∑ ∑ ⎜ ⎟Δn i Δn j Δn k = 0 (2.10.2)
⎜ ∂n i ∂n j ∂n k ⎟
i j k ⎝ ⎠
where A is the Helmholtz' free energy and
⎛ ∂2 A ⎞ ⎛ ∂ lnf i ⎞
Q ij = ⎜⎜ ⎟ = RT⎜⎜ ⎟ (2.10.3)
⎟ ⎟
⎝ ∂n i ∂n j ⎠ T ,V ⎝ ∂n j ⎠ T ,V
An efficient successive substitution solution procedure of the above equations has been
proposed by Michelsen and Heidemann (1981) and summarized as follows:
Select an initial value of λ (≡ vc/b).

Calculate Tc such that det(Q) = 0 by Newton's method.
Evaluate ΔN such that QΔN= 0. To avoid discrete jumps in ΔN, normalize ΔN by ΔNTΔN= 1.
Evaluate the cubic form C* ≡ C (λ-1)2 and update λ
λ(k +1) = λ(k ) − C *
(k )
(λ( ) − λ( ) )/ (C ( ) − C ( ) )
k k −1 *k * k -1
The factor (λ-1)2 is added to enhance stability. Repeat this process until C* = 0.
Initial estimates suggested are λ = 3.5, Tc = 1.3∑ x i Tci . Another method to initiate the
i
calculation is to start with fixed step size of λ (say 0.1) until the cubic form (equation 2.10.1)
changes sign. Then follow the above solution procedure.
START
Initialize Tc
Set initial λ ≡ vc / b
Trace Yes
stability
limit
No Solve quadratic
form for Tc , Δ N
Calculate cubic form
Interpolate Cubic
Yes
cubic form form changes
for λ and Tc sign
Solve quadratic
form for Tc , Δ N Increase λ by
fixed steps
Calculate cubic form

Maximum No
λ reached
No Cubic
Update λ form=0
Yes
Yes
No critical
Calculate Pc from Vc , Tc point detected
STOP STOP
Flow Chart for Critical Point Calculation

Viscosity Correlation
In analogy to the Jossi, Stiel and Thodos equation, the following viscosity correlation is used
(Fong and Nghiem, 1980):

[(μ − μ )ξ + 10 ]
* −4 1 / 4
= a 0 + a 1 ρ r + a 2 ρ 2r + a 3 ρ 3r + a 4 ρ 4r (2.11.1)
The reduced density ρr is defined as
1/ α
⎡ nc ⎤
ρ r = ρv cμ = ρ⎢∑ x i v αcμi ⎥ (2.11.2)
⎣ i =1 ⎦
where vcμ is the critical molar volume used in the viscosity correlations. Generally vcμ is
identical to the critical volume of the component.
In WinProp, these are user input parameters which may be obtained from regression by matching
experimental viscosity measurements. If no information is available, they are defaulted to vc.
The mixture viscosity parameter is given by
1/ 6
⎛ ⎞
⎜⎜ ∑ x i Tci ⎟⎟
ξ= ⎝ i ⎠ (2.11.3)
1/ 2 2/3
⎛ ⎞ ⎛ ⎞
⎜⎜ ∑ x i MWi ⎟⎟ ⎜⎜ ∑ x i p ci ⎟⎟
⎝ i ⎠ ⎝ i ⎠
and the low pressure viscosities of the mixture
∑ (x i μ *i MWi1 / 2 )
μ* =
∑ (x i MWi1 / 2 )
i
(2.11.4)
i
where μi , the low pressure viscosities for pure substances are from the Stiel and Thodos
*
(1961) equation:
[
μ *i ξ i = 4.610Tr0i .618 − 2.04 exp(− 0.449Tri )
(2.11.5)
+ 1.94 exp(− 4.058Tri ) + 0.1 ]x10 −4
with
ξ i = Tc1i/ 6 MWi−1 / 2 p c−i2 / 3 (2.11.6)
and
Tr i = T / Tci (2.11.7)

The parameter vcμi resembles the critical volume for component i. In fact for most usage
v cμi = v ci . The parameters α and a0 through a4 are usually obtained by regressing the
available data. If no viscosity information is available, the following values can be used:
α = 1
a0 = 1.0230 x 10-1
a1 = 2.3364 x 10-2
a2 = 5.8533 x 10-2
a3 = -4.0758 x 10-2
a4 = 9.3324 x 10-3
These values usually produce good estimates for gas viscosities.

Solution of Non-Linear Equations
Governing equation: G ≡ (G 1 , G 2 , ... , G 4 ) = 0
T
Primary variable: ξ ≡ ( ξ1 , ξ 2 , ..., ξ Ν ) Τ

Solution: ξ (k +1) = ξ (k ) + Δξ (k ) (2.12.1)
Newton's Method
( )( ) G ( )
Δξ (k ) = − J −1
k k
J = Jacobian matrix ∂G/∂ξ (2.12.2)

QNSS Method
Quasi-Newton Successive Substitution (Nghiem and Heidemann, 1982):
Δξ (k ) = −σ (k )G (k )
Δξ (k −1) G (k -1) (k −1)

σ (k ) = σ
Δξ (k −1) ΔG (k -1)
with
σ (0 ) = QSTEP ≡ 1
and
σ limited to ≤ DGM ≡ 30
Δξ m limited to ≤ DVMAX ≡ 6 (2.12.3)
The QNSS method is restarted at every IREST iterations. Generally, IREST has the same
magnitude as the total number of components.

Plus Fraction Characterization
Characterization Method
Reservoir fluid analyses usually report composition of all light and intermediate components.
Heavy components are lumped into a 'plus' fraction, e.g. C6+ where only the molecular weight
and specific gravity are reported. It is advantageous to split the plus fraction into the single
carbon number (SCN) fractions using model distribution e.g., C6, C7, ..., C45. The properties for
each SCN are then estimated by empirical correlations. The synthetic distribution is then
regrouped into a smaller number of hypothetical components (e.g., C6-C12, C13-C20, C21+) via
mixing rules.
Distribution Model
A two-stage weighting exponential function is used as a probability function to describe the
molar distribution as a function of molecular weight
MWi +1
x ci = ∫ ξdMW
MWi
with
⎡ C − Co
ln ξ = (1 − f )⎢C o + 1 (MW − M o )⎤⎥ + f [C1 + C 2 (M − M 1 )]
⎣ M1 − M o ⎦
0; MW < M 1
f = ⎧⎨ (2.13.1)
⎩1; MW > M 1
The parameters Co, Mo are from the 'minus' fraction, the fraction immediately preceding the
plus fraction.
Co = Mole fraction of the minus fraction / 14.0
Mo = Molecular weight of the minus fraction
The parameter M1 and C1 are calculated by matching the molar distribution to the molecular
weight and mole fraction of the plus fraction, X+ and M+
∞
X+ = ∫ ξdMW =
M1
C1 − C o
(
e C1 − e Co −
C2
)
e C1
Mo
[ ]
∞ 2
⎛ M1 ⎞ Co
(M + − M o )X + = ∫ MWξd(MW ) = ⎜⎜ ⎟⎟ e 1 + (C1 − C o − 1)e C1 −Co
Mo ⎝ C1 − C o ⎠
2
⎛ 1 ⎞
+ ⎜⎜ ⎟⎟ (1 − C 2 M 1 )e Ci (2.13.2)
⎝ C2 ⎠

The parameter C2 is left as an adjustable parameter. It represents the final decline in the
molar density function. The following equation was found to represent well the conventional
oil in Canada:
C2 = - ln 10 / (14.C 3 )
C3 = A(M + - F) 2 + B(M + - F) + C(SG + - G) 2 + D(SG + - G) + E
where
A = 2.8297 x 10-3
B = 4.0001 x 10-1
C = -8.4344 x 10-3
D = -6.3014 x 102
E = 12.0
F = 200.0
G = 0.853
and SG+ is the specific gravity of the plus fraction. It can be used when no other information
is available.
Selection of Molecular Weight Range of SCN Group
The molecular weight range of each SCN group, say SCNi, is chosen to be between
M1(i) = DERM(i-η) and M2(i) = DERM(i+1-η).
The defaults are DERM = 14.026 and η(bias) = 0.75.
Properties of Single Carbon Number Fraction
With the model distribution the mole fraction and molecular weight of each single carbon
number (SCN) fraction, i, is easily calculated from the integral and the first moment:
M2
x ci = ∫ ξdMW (2.13.3)
M1
M2
1
MWci =
x ci ∫ MWξdMW + M o
M1
The specific gravity and normal boiling point for the SCN fraction are calculated from the
Hariu-Sage (1969) correlation and assuming a constant Watson's characterization factor,
Kuop, which is adjusted to match the measured specific gravity of the plus fraction SG+:
2 2
log10 (MWi )=∑ ∑ A jk Tbki K uop
j
i=6,7,8,...
j= 0 k =0
K uop = (Tb i + 459.67)1/3 / SG i i=6,7,8,...

−1
⎡ ⎤
SG + = ⎢∑ X i MWi /SG i ⎥ (2.13.4)
⎣ i ⎦

where
A00 = 0.6670202
A10 = 4.583705 x 10-3
A20 = -2.698693 x 10-6
A01 = 0.1552531
A11 = -5.755585 x 10-4
A21 = 3.875950 x 10-7
A02 = -5.378496 x 10-3
A12 = 2.500584 x 10-5
A22 = -1.566228 x 10-8
The critical properties of the SCN fractions are calculated using, for example, Twu's correlations.
Lumping into Hypothetical Components
Following Whitson (1983), the number of hypothetical components, NG, required to
characterize a plus fraction is estimated as
NG = 1 + 3.3 log10 (N-n)
where n is the first SCN fraction in a Cn+ fraction and N is the SCN fraction corresponding to
95 mole % of a Cn+ fraction.
The SCN fractions are then assigned to the hypothetical components according to their log
(K) value. The K-values are calculated using the Wilson's equations.
The Lee-Kesler (1975) mixing rules are then used to calculate the critical properties of the
hypothetical components:
ω (1) = ∑ x j ω j
j
Vc(1) =
1
∑
8 j
∑ (
x j x k Vcj1 / 3 + Vck
1/ 3
)
3
Tc(1) =
1
8Vc
∑ ∑ (
x j x k Vcj1 / 3 + Vck
1/ 3
) Tcj Tck
j k
p (c1) = Z c RTc(1) / Vc(1) = (0.2905 − 0.085ω)RTc(1) / Vc(1)

where the superscript (1) denotes lumped properties.

START
Input M+, SG+ , X+ , X-
Calculate xi , MWi of each SCN fraction
Calculate Koup , and SGi , Tb i of each SCN fraction
For each fraction calculate Pci , Tci , wi

by forcing EOS to match SGi , Tbi
Number of Yes
hypothetical components,
NG specified
No
Calculate NG
Assign SCN fractions to hypothetical component
Calculate critical properties

for each hypothetical component
STOP
Flow Chart for Plus Fraction Characterization

Interfacial Tension Calculations
The general equation for calculating the interfacial tension is (Reid et al, 1977, p. 614);
σ1/4 = p ar (ρ L − ρ V ) (2.14.1)
where σ is the interfacial tension in dyne/cm between the phases L and V. ρj is the molar
density in mol/cm3 of phase j and par is the parachor.
For hydrocarbon systems
p ari = ξCN i (2.14.2)
where
ξ = ⎧⎨40 CN ≤ 12 (2.14.3)
⎩40.3 CN > 12
CN is the carbon number of the component i given by
CNi = MWi/14 (2.14.4)
where MWi is the molecular weight of i.
For multicomponent systems
nc
σ1/4 = ∑ p ari (x i ρ L − y i ρ V ) (2.14.5)
i =1
where xi are the mole fractions in phase L and yi the mole fractions in phase V.
Regression
The major problem associated with phase-behavior matching with a cubic equation of state is
the selection of regression parameters. There are many parameters that can be selected as the
best set of parameters, and therefore a dynamic parameter-solution scheme is desired to avoid
tedious and time-consuming trial-and-error regression runs.
WinProp uses a regression technique where the most significant parameters are selected from
a large set of parameters during the regression process. This reduces the regression effort
considerably and alleviates the problem associated with the apriori selection of regression
parameters (Agarwal, Li and Nghiem, 1987).
Introduction
It is well known that cubic equations of state (EOS) will not generally predict accurately
laboratory data of oil/gas mixtures without the tuning of the EOS parameters (Coats and
Smart, 1986).
It has often been the practice to adjust the properties of the components (usually the heavy
fractions, e.g. pc, Tc, ω, etc., to fit the experimental data.

The objective function of the regression involves the solution of complex nonlinear equations
such as flash and saturation-pressure calculations. A robust minimization method is therefore
required for rapid convergence to the minimum. In WinProp a modification of the adaptive
least-squares algorithm of Dennis et al (1981) is used. The modification involves the use of
some other nonlinear optimization concepts on direction and step-size selection due to Chen
and Stadtherr (1981).
The dynamic selection of the most meaningful regression parameters from a larger set of
variables is described in Application of the Regression Method to EOS Tuning section. This
feature is extremely useful in EOS fitting because it alleviates the problem of deciding apriori
the best regression variables, which is extremely difficult.
It should be stressed that the regression procedure will not correct the deficiencies of the EOS
used, and the EOS predictive capability depends entirely on the type and the accuracy of the
data used in the regression. For predictive purposes, attempts should be made to ensure that
the "tuned" parameters are within reasonable physical limits.
The Regression Method
The implementation of the dynamic-parameter-selection strategy for tuning the EOS requires
the solution of a nonlinear optimization problem. In terms of least-squares, the optimization
problem may be stated as
nm
minimize f (x ) = R (x ) R (x ) = ∑ ri (x )
T 2
(2.15.1)
x i =1
where
x = [x 1 , x 2 ,..., x n t ]
T
is the regression-parameter vector, with nr being the number of regression parameters and nm
the number of measurements to be fitted. Usually nm > nr. The elements of R(x) are denoted
by ri (x) which are nonlinear in x. When the equation of state is adjusted to match a set of
experimental data y
e i (x ) − y i
ri =
yi
with
[ ]
E(x ) = e1 (x ), e 2 (x ),..., e n m (x ) T
and
y = [y i , y 2 ,..., y n m ]
T
where E(x) are the equation-of-state results and y the experimental data points. In this case
the nonlinear least-squares problem consists of adjusting x so that the EOS results match the
experimental measurements.

The problem (2.15.1) may be solved by various methods for nonlinear parameter estimation
(Bard, 1974), and for nonlinear optimization (Himmelblau, 1972; Schittkowski, 1981). The
general purpose optimization methods however do not take advantage of the special structure
of the nonlinear least squares optimization problem (2.15.1). Several strategies are available
to exploit this structure. Coats and Smart (1986) used a modified linear programming least
squares algorithm to solve (2.15.1). Watson and Lee (1986) use a modification of the
Levenberg-Marquardt algorithm (see More', 1978) to solve a nonlinear least-squares problem.
In WinProp a modification of the adaptive least-squares algorithm of Dennis et al (1981) is used.
The algorithm departs from the method of Dennis et al in using some other nonlinear
optimization concepts on step-direction and step-size selection due to Chen and Stadtherr (1981).
Application of the Regression
Method to EOS Tuning
It was found that the key to an efficient algorithm would be the fast and accurate (as far as
possible) estimation of the Jacobian matrix J.
It has been shown that the matrix J also determines the second derivative Hessian matrix ∇2f.
Consequently, a small change in the determination of J affects the performance of the
regression method quite dramatically.
The derivatives of the residuals R are calculated by numerical differentiation, since in most
cases it is not practical to obtain exact analytical derivatives.
The calculation of R at all times involves iterative processes, where the solution is only
available to some accuracy εi.
If the Jacobian J is to be calculated by finite differences, the perturbation in the independent
variables x must be such that it is not masked by the convergence accuracy εi or the truncation
and roundoff errors associated with the computation. It has been found that a perturbation of
1% in the independent variables is adequate to compute J by numerical differentiation.
Choice of Regression Parameters
Given a global set of regression parameters xj, j=1,...,np, the method selects an active subset
of nr parameters with which regression will be performed. The global set of regression
parameters is supplied by the user and may include any of the following parameters:
pci Critical pressure of Component i
Tci Critical temperature of Component i
vci Critical volume of Component i which affects the interaction coefficients

between hydrocarbons (see Equation 2.16.1)
ϖi Acentric factor of Component i
vit Volume translation of Component i (see Equations section)
MWi Molecular weight of Component i

dij Interaction coefficient between Components i and j
θ Exponents for computing interaction coefficients between hydrocarbons (see

Equation 2.16.1)
The interaction coefficients between hydrocarbons are estimated from the following equation
(Li, et al, 1985)
θ
⎡ 2 v1ci/ 6 v1cj/ 6 ⎤
d ij = 1 − ⎢ 1 / 3 1/ 3 ⎥
(2.16.1)
⎣⎢ v ci + v cj ⎦⎥
The volume translation technique of Peneloux et al (1982) is used to correct the molar
volume (see Equations section).
The parameters xj are scaled by using the upper bound xj,max and lower bound xj,min of the
corresponding parameter such that they always lie between zero and unity.
x j = (x j − x j,min ) / (x j,max − x j,min ) (2.16.2)
The regression scheme sorts the np parameters in the descending order of |∂f / ∂xj|.
From these np parameters, the first nr parameters are chosen for regression, i.e. the nr
parameters with the largest |∂f / ∂xj|. nr is supplied by the user.
The regression proceeds on these nr parameters and if at any time during the regression, |∂f / ∂xj|
becomes less than ri |, i=1,...,nm, the variable xj is dropped from the regression set and the next
variable on the original sorted list is added on. Indeed, since all xj are scaled between zeros and
unity, if |∂f / ∂xj| is less than all |ri|, it is likely that xj has to go beyond its bounds to further
reduce ri. Therefore, it is logical that xj should be dropped from the active parameter set.
Another condition where xj is dropped is when it tries to go out of bonds for more than two
iterations.
At convergence, if the total number of regressed variables (including those which have been
dropped) is less than five, then new variables are added to the active regression set and the
original active regression variables with the smallest |∂f / ∂xj| are removed from the active set
such that nr is preserved.
The flow chart of the parameter selection procedure is given in Figure B.2.

START
Load the initial values of the n p regression variables
Calculate ∂f / ∂x j j=1,2,...,n p and sort x j in

the descending order of magnitude of ∂f / ∂x j
Choose the first n r regression variables from the sorted set
Regress on the n r variables
Is
∂f / ∂x j < r i for all i
or
x j = x j,min
or for two iterations No
=
x j x j,max
Yes
Drop x j from the active regression set. Add the next

variable from the sorted list to the active set
No
Conv erged?
Yes
Regressed
Yes STOP
on at least five
variables?
No
Add more v ariables to the active regression set
Figure B.2: Flow Chart for Selecting the Active Regression Parameters

Properties of Components
The equations-of-state requires the critical properties as input. The critical properties for
common single real molecules have been measured and tabulated in numerous handbooks. A
fraction of the reservoir fluid, on the other hand, consists of numerous real molecules and
generally only their specific gravity, boiling point and molecular weights are measured.
Their critical properties are not determined. The components making up the reservoir fluid
are thus identified into two types: the built-in components and the user components. Built-in
components are those whose critical properties are known and have been stored in the phase
behavior package WinProp. User components are those whose properties are not stored and
must be supplied as input to WinProp.
Real Components
Component p c, v c, Tc, acentric MW,

atm. l/gmole deg. K factor g/mol
CH4 45.400 0.0990 190.60 0.00800 16.04300
C2H6 48.200 0.1480 305.40 0.09800 30.07000
C3H8 41.900 0.2030 369.80 0.15200 44.09700
iC4 36.000 0.2630 408.10 0.17600 58.12400
nC4 37.500 0.2550 425.20 0.19300 58.12400
iC5 33.400 0.3060 460.40 0.22700 72.15100
nC5 33.300 0.3040 469.60 0.25100 72.15100
nC6 29.300 0.3700 507.40 0.29600 86.17800
nC7 27.000 0.4320 540.20 0.35100 100.2050
nC8 24.500 0.4920 568.80 0.39400 114.2320
nC9 22.800 0.5480 594.60 0.44400 128.2590
nC10 20.800 0.6030 617.60 0.49000 142.2860
nC16 14.000 0.9560 717.00 0.74200 226.4480
N2 33.500 0.0895 126.20 0.04000 28.01300
CO2 72.800 0.0940 304.20 0.22500 44.0100
H2S 88.200 0.0985 373.20 0.10000 34.0800
H2O 217.60 0.0560 647.30 0.34400 18.01500
Toluene 40.600 0.3160 591.70 0.25700 92.14100
Benzene 48.300 0.2590 562.10 0.21200 78.11400
Cyclo-C6 40.200 0.3080 553.40 0.21300 84.16200
FC6 32.460 0.3440 507.50 0.26370 86.0000
FC7 30.970 0.3810 543.20 0.30240 96.0000
FC8 29.120 0.4210 570.50 0.33720 107.0000
FC9 26.940 0.4710 598.50 0.37810 121.0000
FC10 25.010 0.5210 622.10 0.41650 134.0000
FC11 23.170 0.5740 643.60 0.45530 147.0000
FC12 21.630 0.6260 663.90 0.49220 161.0000

Component pc , vc, Tc, acentric MW,
atm. l/gmole deg. K factor g/mol
FC13 20.430 0.6740 682.40 0.52480 175.0000
FC14 19.330 0.7230 700.70 0.55720 190.0000
FC15 18.250 0.7770 718.60 0.58990 206.0000
FC16 17.150 0.8350 734.50 0.62250 222.0000
FC17 16.350 0.8840 749.20 0.64960 237.0000
FC18 15.650 0.9300 760.50 0.67240 251.0000
FC19 15.060 0.9730 771.00 0.69280 263.0000
FC20 14.360 1.0270 782.90 0.71670 275.0000
FC21 13.830 1.0730 793.30 0.73610 291.0000
FC22 13.260 1.1260 804.40 0.75690 300.0000
FC23 12.830 1.1700 814.00 0.77350 312.0000
FC24 12.380 1.1510 823.20 0.93510 324.0000
FC25 11.840 1.2020 832.70 0.96690 337.0000
FC26 11.480 1.2400 841.20 0.99090 349.0000
FC27 11.130 1.2790 849.60 1.01450 360.0000
FC28 10.760 1.3230 857.70 1.03960 372.0000
FC29 10.490 1.3560 864.30 1.05850 382.0000
FC30 06.310 2.0060 832.80 1.23760 394.0000
FC35 09.910 1.5890 905.90 1.17720 445.0000
FC36 08.660 1.6320 912.10 1.19660 456.0000
FC37 08.530 1.6570 917.30 1.20850 464.0000
FC38 08.290 1.7020 923.40 1.22780 475.0000
FC39 08.130 1.7340 928.20 1.24120 484.0000
FC40 07.900 1.7800 934.30 1.26020 495.0000
FC41 07.780 1.8060 938.50 1.27070 502.0000
FC42 07.600 1.8440 942.80 1.28560 512.0000
FC43 07.460 1.8780 947.60 1.29880 521.0000
FC44 07.250 1.9280 953.70 1.31730 531.0000
FC45 07.140 1.9550 957.80 1.32750 539.0000
The properties for the first 20 are obtained from Reid et al (1977). The next 30 components,
FC6 to FC45 represent typical hydrocarbon fractions C6 to C45.
Their critical properties are calculated with the correlations of Kesler and Lee (1976), using
the averaged normal boiling points and specific gravities of C6 to C45 reported by Whitson
(Whitson, 1983; Katz and Firoozabadi, 1978). These components can be used for rough
calculations if no other information about the heavy ends are available.

User Components
For User components, usually only the physical properties molecular weight, boiling point and/or
specific gravity are known. The critical properties are calculated from empirical correlations.
Numerous such correlations are available in the literature. A survey by Whitson (1982) suggested
the use of Kesler-Lee correlations for conventional oil. For heavy hydrocarbons the correlation of
Twu (1984) generally yields reasonable results (Fu et al, 1986). These two methods are available
in WinProp to calculate the required critical properties. In view of its simplicity, the method of
Riazi-Daubert is also available. The correlations are summarized below.
Kesler and Lee (1976)
ln p c = 8.3634 − 0.0566 SG
− ( )
0.24244 + 2.2898 / SG + 0.11857 / SG 2 10 −3 Tb
+ ( )
1.46850 + 3.6480 / SG + 0.47227 / SG 2 10 − 7 Tb2
− ( )
0.42019 + 0.0000 / SG + 1.69777 / SG 2 10 −10 Tb3
Tc = 341.7 + 811 SG + (0.4244 + 0.1174 SG ) Tb
+ (0.4669 − 3.2623 SG )10 5 / Tb
For θ > 0.8
ω = −7.904 + 0.1352 K c − 0.007465 K c2 + 8.359θ
+ (1.408 − 0.01063 K ) / θ
For θ < 0.8
− ln (p c / 14.7 ) − 5.92714 + 6.09648 / θ + 1.28862 ln θ − 0.169347θ 6
ω=
15.2518 − 15.6875 / θ − 13.4721ln θ + 0.43577θ 2
where
p c in psia
Tb , Tc in o R
θ = Tb / Tc (2.17.1)
K c = (CABP) / SG
1/ 3
CABP = cubic average boiling point in o R

Twu (1984)
Critical temperature:
Tc = Tco [( 1 + 2 f T ) / ( 1 − 2 f T ) ]
2
[ (
f T = Δ SG t − 0.362456 / Tb1 / 2 + 0.0398285 − 0.948125 / Tb1 / 2 Δ SG t ) ]
[(
Δ SG T = exp 5 SG o − SG 1 − 1 )]

Critical volume:
Vc = Vco [( 1 + 2 f V ) / ( 1 − 2 f V )]
2
[ (
f V = Δ SG V 0.466590 / Tb1 / 2 + − 0.182421 + 3.01721 / Tb1 / 2 Δ SG V ) ]
[(
Δ SG V = exp 4 SG o 2 − SG 2 − 1 )]
Critical pressure:
(
p c = p oc Tc / Tco ) (V
o
c / Vco ) [( 1 + 2 f ) / ( 1 − 2 f )]
p p
2
f p = Δ SG p [( 2.53262 − 46.1955 / T 1/ 2
b − 0.00127885 Tb )
(
+ − 11.4277 + 252.140 / Tb1 / 2 + 0.00230535 Tb Δ SG p ) ]
[ (
Δ SG p = exp 0.5 SG o − SG − 1 )]
Molecular weight:
ln MW = ln MW o [( 1 + 2 f M ) / ( 1 − 2 f M )]
2
f M = Δ SG M [ x + ( − 0.0175691 + 0.193168 / T )Δ SG ] 1/ 2
b M
x = 0.0123420 − 0.328086 / Tb1 / 2
[(
Δ SG M = exp 5 SG o − SG − 1 )]
where
(
Tco = Tb 0.533272 + 0.191017 x 10 −3 Tb + 0.779681 x 10 −7 Tb2
− 0.284376 x 10 −10 Tb3 + 0.959468 x 10 28 / Tb13 )−1
(
Vco = 1 − 0.419869 − 0.505839 α − 1.56436 α 3 − 9481.70 α 14 ) −8
= (3.83354 + 1.19629 α ) 2
p oc 1/ 2
+ 34.8888 α + 36.1952 α 2 + 104.193 α 4
Tb = exp ( 5.71419 + 2.71579 θ − 0.286590 θ 2 − 39.8544 / θ
- 0.122488 / θ 2 ) - 24.7522 θ + 35.3155 θ 2

with
θ = ln MW o
α = 1 Tb / Tco (2.17.2)
All temperatures in oR, volume in ft3lb-mol and pressures in psia.

Riazi and Daubert (1980)
−2.315
p c = 3.12281 x 10 9 T b SG 2.3201
Tc = 24.2787 T 0b.58848 SG 0.3596
where
p c in psia
(2.17.3)
Tb , Tc in o R
Interaction Coefficient
The importance of interaction coefficients, dij, in the accuracy of phase behavior calculations,
especially the saturation pressures, has been demonstrated by Peng and Robinson (1976),
Conrad and Gravier (1980) and Whitson (1982) among others. Theoretically, dij is introduced
to account for the molecular interaction between dissimilar molecules. Their values are usually
obtained by fitting the predicted saturation pressure curves to experimental data.
Hydrocarbon-Hydrocarbon Interaction
Katz and Firoozabadi (1978) have published the binary interaction coefficients between
methane and other heavy hydrocarbon fractions. Their values have been fitted to the density,
ρ, of the fraction by Conrad and Gavier (1980) as:
d = 0.12903 ρ - 0.05871
Whitson and Torp (1981) have fitted the same set of data using specific gravity, SG, as
correlating parameters:
d = 0.14 (SG) - 0.0668
The Institute of Thermodynamics (Technical University of Berlin) has accumulated a
comprehensive collection of data on vapor-liquid equilibrium. It contains approximately
55,000 experimental data for more than 120 binary systems. These have been evaluated by
Oellrich, Plocker, Prausnitz and Knapp (1981) to determine the interaction coefficients (both
hydrocarbon and non-hydrocarbon systems) for the commonly used equations-of-state
including PR and SRK.
Mehra (1981) and Li (1983) both used the following relations for hydrocarbon-hydrocarbon
systems:
n
⎡ 2 V1 / 3 V1 / 3 ⎤
d ij = 1 − ⎢ 1 / 3 ⎥
ci cj
(2.18.1)
⎢ Vc + Vc1 / 3 ⎥
⎢⎣ i j
⎥⎦
with the constant n = 1. The same form is also proposed by Chueh and Prausnitz (1967) and
Chaudron, Asselineau and Renon (1973). Examining the paraffin-paraffin dij of Oellrich et al
(1981) shows that they could roughly be correlated using this equation with n = 1.2. Mehra
(1981) has also shown that this equation reproduces satisfactorily the methane interaction
coefficients of Katz and Firoozabadi (1978). Equation (2.18.1) is used in WinProp with n as a
user input parameter.

Hydrocarbon-Nonhydrocarbon Interaction
Besides Oellrich et al (1981), other researchers have also reported values of interaction
coefficients for hydrocarbon-nonhydrocarbon systems.
The reported interaction coefficient values between CO2 and hydrocarbons, dCO2-HC,
generally ranges from 0.1 to 0.13 for PR EOS (Oellrich et al, 1981; Hughes, Matthews and
Mott, 1981; Katz and Firoozabadi, 1978; Mehra, 1981). In addition, dCO2-HC correlations
have been proposed by Kato, Nagahama and Hirata (1981); Mulliken and Sandler (1980) and
Turek, Metcalfe, Yarborough and Robinson (1980). These correlations are generally
temperature dependent and complicated.
The reported interaction coefficient values between N2 and hydrocarbons, dN2-HC, generally
increases with increasing carbon number in the hydrocarbon, and range from 0.03 to 0.15
(Mehra, 1981; Oellrich et al, 1981; Katz and Firoozabadi, 1978).
The following table shows the interaction coefficients for nonhydrocarbons stored in WinProp.
N2 CO2 H2S H2O
CH4 .031 .103 .080 .4907
C2H6 .042 .130 .070 .4911
C3H8 .091 .135 .070 .5469
iC4 .095 .130 .060 .5080
nC4 .095 .130 .060 .5080
iC5 .095 .125 .060 .5000
nC5 .095 .125 .060 .5000
nC6 .100 .125 .050 .4500
nC7 .100 .120 .040 .4500
nC8 .100 .115 .040 .4500
nC9 .100 .110 .030 .4500
nC10 .100 .110 .000 .4500
nC16 .130 .090 .000 .4500
Toluene .120 .120 .000 .4800
Benzene .120 .078 .000 .4800
Cyclo-hexane .120 .106 .000 .4800
FC6-FC45 .120 .150 .000 .4800
N2 .000 -.020 .176 .2750
CO2 -.020 .000 .096 .2000
H2S .176 .096 .000 .1200
H2O .275 .200 .120 .0000

Nomenclature
a equation of state parameter
b equation of state parameter
c equation of state parameter
Cp heat capacity
dij interaction coefficient
D stability test distance
fi fugacity for component i
F degree of freedom from the phase rule
Fj mole fraction of phase j
G Gibb's free energy
GOR gas-oil ratio
hij partial molar enthalpy of component i in phase j
Hi enthalpy, or Henry's law constant for water flash for component i
Hspec specified molar enthalpy
Ki equilibrium ratio for component i
Kij equilibrium ratio for component i in phase j
L1 first liquid phase
L2 second liquid phase
MW molecular weight
n mole number
N total number of moles
Nc total number of components
Np number of phases
NHYP number of hypothetical components
p pressure
ri volume translation for component i
R universal gas constant
T temperature
T3p three phase temperature
ui number of component i in stability test
U vector of u
v partial molar volume
V vapor phase
xi phase composition of component i, mole fraction
X vector of x
zi global composition of component i, mole fraction
Z compressibility factor (pv/RT)

Subscript
c critical property
i component number
j component number, phase
k,m phase
l liquid phase 1
q liquid phase 2
Ri reference phase for component i
v vapor phase
w water phase
Superscript
E excess property
k iteration number
L liquid phase 1
o non-translated volume
Q liquid phase 2
t translated volume
V vapor phase
W water phase
* ideal state, reference state
Other Symbols
Ωa equation of state parameters
Ωb equation of state parameters
φ fugacity coefficient
δ1 equation of state parameter
δ2 equation of state parameter
ϖ acentric factor
β specified variables for phase diagram construction
ζ fraction of injection fluid for phase diagram construction
μ viscosity
ξ mixture viscosity parameter
ρr reduced density
ρ density

References for Appendix B
Agarwal, R., Li, Y.-K., and Nghiem, L., "A Regression Technique with Dynamic-Parameter
Selection for Phase Behavior Matching," paper SPE 16343, presented at the SPE California
Regional Meeting, Ventura, California, April 8-10, 1987.
Agarwal, R.K., Li, Y.-K., Nghiem, L.X., and Coombe, D.A., "Multi-Phase Multi-Component
Isenthalpic Flash Calculations with a Cubic Equation of State," presented at the 39th Annual
Technical Meeting of CIM, June 12-16, 1988, Calgary, Alberta.
Bard, Y., "Nonlinear Parameter Estimation," Academic Press Inc., 1974.
Canjar, L.N., and Manning, F.S., Thermodynamic Properties and Reduced Correlations for
Gases, Gulf Publishing Co., Houston, Texas, 1967.
Chaudron, J., Asselineau, L., and Renon, H., "Mixture Properties and Vapor-Liquid Equilibria
by Modified Redlich-Kwong Equation of State," Chem. Eng. Sci., Vol. 28, 1973, pp. 1991.
Chen, H.-S., and Stadtherr, M.A., "A Modification of Powell's Dogleg Method for Solving
Systems of Nonlinear Equations," Comp. and Chem. Eng., Vol. 5, No. 3, 1981, pp. 143-150.
Chueh, P.L. and Prausnitz, J.M., "Vapor-Liquid Equilibria at High Pressures: Calculation of
Partial Molar Volumes in Nonpolar Liquid Mixtures," AIChE J., Vol. 13, No. 6, November
1967, pp. 1099-1107.
Coats, K.H., Smart, G.T., "Application of a Regression-Based EOS PVT Program to
Laboratory Data," SPE Reservoir Eng., Vol. 1, No. 3, May 1986, pp. 277-299.
Conrad, P.G. and Gravier, J.F., "Peng-Robinson Equation of State Checks Validity of PVT
Experiments," Oil and Gas J., April 1980, pp. 77-86.
Dennis Jr., J.E., and Schnabel, R.B., "Numerical Methods for Unconstrained Optimization
and Nonlinear Equations," Prentice-Hall Series in Computation Math, Cleve Moler, Advisor,
1983.
Dennis Jr., J.E., Gay, D.M., and Welsch, R.E., "An Adaptive Nonlinear Least-Squares
Algorithm," ACM Trans. Math. Software, Vol. 7, No. 3, September 1981, pp. 348-368.
Fong, D.K.S., and Nghiem, L.X., "A Viscosity Model for Reservoir Fluids," Computer
Modelling Group Research Report R7.02, March 1980.
Fu, C.-T., Puttagunta, R., and Pors, D., "Estimation Methods in Pseudo-Critical Properties of
Heavy Hydrocarbons," ARC/AOSTRA, Industry Access Report 8586-49, January 1986.
Gay, D.M., "Computing Optimal Locally Constrained Steps," SIAM J. Sci. Stat. Comput.,
Vol. 2, No. 2, June 1981, pp. 186-197.
Gosset, Heyen, and Kalitventzeff, "An Efficient Algorithm to Solve Cubic Equations of
State," Fluid Phase Equilibria, Vol. 25, 1986, pp. 51-64.
Grabowski, M.S., and Daubert, T.W., "A Modified Soave Equation of State for Phase
Equilibrium Calculations," I.&E.C. Process Des. Dev., Vol. 17, No. 4, 1978, pp. 443-454.
Harin, G.H., and Sage, R.C., "Crude Split Figured by Computer," Hydro. Proc., April 1969,
pp. 143-148.
Heidemann, R.A., and Khalil, A.M., "The Calculation of Critical Points," AIChE J., Vol. 26,
1980, pp. 769-779.

Himmelblau, D.M., "Applied Nonlinear Programming," McGraw-Hill Inc., 1972.
Hughes, D.S., Matthews, J.D., and Mott, R.E., "Theoretical Aspects of Calculating the
Performance of CO2 as an EOR Process in North Sea Reservoirs," Proceedings, 1981
European Symposium on EOR, September 21-23, 1981, Bournemouth, England.
Jhaveri, B.S., and Youngren, G.K., "Three-Parameter Modification of the Peng-Robinson
Equation of State to Improve Volumetric Predictions," SPE paper 13118, presented at the 59th
Annual Technical Conference and Exhibition, Houston, Texas, September 16-19, 1984.
Kato, K., Nagahama, K., and Hirata, M., "Generalized Interaction Parameters for the Peng-
Robinson Equation of State: Carbon Dioxide-n-Paraffin Binary Systems," Fluid Phase
Equil., Vol. 7, 1981, pp. 219-231.
Katz, D.L., and Firoozabadi, A., "Predicting Phase Behavior of Condensate/Crude-Oil
Systems Using Methane Interaction Coefficients," J. Petrol. Technol., Vol. 30, 1978, pp.
1649-1655.
Kesler, M.G., and Lee, B.I., "Improve Predictions of Enthalpy of Fractions," Hydro. Proc.,
March 1976, pp. 153-158.
Lee, B.I., and Kesler, M.G., "A Generalized Thermodynamic Correlation Based on Three-
Parameter Corresponding States," AIChE J., Vol. 21, May 1975, pp. 510-527.
Li, Y.-K., and Nghiem, L.X., "The Development of a General Phase Envelope Construction
Algorithm for Reservoir Fluid Studies," paper SPE 11198, presented at the 57th Annual Fall
Meeting of SPE-AIME, September 26-29, 1982, New Orleans, Louisiana.
Li, Y.-K., "Heavy Fraction Characterization and Hypothetical Component Selection for Oil
and Gas Mixtures," Computer Modelling Group Research Report R12.04, May 1983.
Li, Y.-K., and Nghiem, L.X., "Phase Equilibria of Oil, Gas and Water/Brine Mixtures from a
Cubic Equation of State and Henry's Law," Can. J. Chem. Eng., 1986.
Li, Y.-K., Nghiem, L.X., and Siu, A., "Phase Behavior Computations for Reservoir Fluids:
Effects of Pseudo-Components on Phase Diagrams and Simulation Results," J. Can. Pet.
Tech., Vol. 24, No. 6, 1985, pp. 29-36.
Martin, J.J., "Cubic Equations of State - Which?," Ind. Eng. Chem. Fundam., Vol. 18, No. 2,
1979, pp. 81-97.
Mehra, R.K., "The Computation of Multi-Phase Equilibrium in Compositional Reservoir
Studies," Ph.D., Thesis, University of Calgary, 1981.
Mehra, R.K., Heidemann, R.A., and Aziz, K., "An Accelerated Successive Substitution
Algorithm, "Can. J. Chem. Eng., Vol. 61, 1984, pp. 590-596.
Michelsen, M.L., "Calculation of Phase Envelopes and Critical Points for Multicomponent
Mixtures," Fluid Phase Equilibria, Vol. 4, 1980, pp. 1-10.
Michelsen, M.L., and Heidemann, R.A., "Calculation of Critical Points from Cubic Two-
Constant Equations of State," AIChE J., Vol. 27, No. 3, 1981, pp. 521-523.
Michelsen, M.L., "The Isothermal Flash Problem, Parts I and II," Fluid Phase Equilibria, Vol.
9, 1982, pp. 1-40.

Moore, J.J., "The Levenberg-Marquardt Algorithm: Implementation and Theory," In Lecture
Notes in Mathematics, No. 630, Numerical Analysis, G. Watson, Ed., Springer-Verlag, New
York, 1978, pp. 105-116.
Mulliken, C.A., and Sandler, S.I., "The Prediction of CO2 Solubility and Swelling Factors for
Enhanced Oil Recovery," Ind. Eng. Chem. Process Des. Dev., Vol. 19, 1980, pp. 709-711.
Nghiem, L.X., and Heidemann, R.A., "General Acceleration Procedure for Multiphase Flash
Calculation With Application to Oil-Gas-Water Systems," paper presented at the 2nd
European Symposium on Enhanced Oil Recovery, Paris, France, November 8-10, 1982.
Nghiem, L.X., Aziz, K., and Li, Y.-K., "A Robust Iterative Method for Flash Calculations
Using the Soave-Redlich-Kwong or Peng-Robinson Equation of State," Soc. Petrol. Eng. J.,
Vol. 23, June 1983.
Nghiem, L.X., and Li, Y.-K., "Computation of Multiphase Equilibrium Phenomena of
Reservoir Fluid," Fluid Phase Equil., Vol. 17, 1984, pp. 77-95.
Nghiem, L.X., Li, Y.-K., and Heidemann, R.A., "Application of the Tangent Plane Criterion
to Saturation Pressure and Temperature Computations," Fluid Phase Equil., Vol. 21, 1985,
pp. 39-50.
Oellrich, L., Plocker, U., Prausnitz, J.M., and Knapp, H., "Equation-of-State Methods for
Computing Phase Equilibria and Enthalpies," Int. Chem. Eng., Vol. 21, No. 1, January 1981,
pp. 1-15.
Passut, C.A., and Danner, R.P., "Correlation of Ideal Gas Enthalpy, Heat Capacity, and
Entropy," Ind. Eng. Chem. Process Des. Develop., Vol. 11, No. 4, 1972, pp. 543-546.
Peneloux, A., Rauzy, E., and Freze, R., "A Consistent Correction for Redlich-Kwong-Soave
Volumes," Fluid Phase Equil., Vol. 8, 1982, pp. 7-23.
Peng, D.Y., and Robinson, D.B., "A New Two-Constant Equation of State," Ind. Eng. Chem.
Fundam., Vol. 15, 1976, pp. 59-64.
Reid, R.C., Prausnitz, J.M., and Sherwood, T.K., The Properties of Gases and Liquids, 3rd
Edition, McGraw-Hill, New York, 1977.
Riazi, M.R., and Daubert, T.E., "Simplify Property Predictions," Hydrocarbon Processing,
March 1980, pp. 115-116.
Robinson, D.B, and Peng, D.Y., "The Characterization of the Heptanes and Heavier Fractions
for the GPA Peng-Robinson Programs," Gas Processors Association, Research Report RR-
28, March 1978.
Rowe, A.M., and Chou, J.C.S., "Pressure-Volume-Temperature-Concentration Relation of
Aqueous NaCl Solutions," J. Chem. Eng. Data, Vol. 15, No. 1, 1970, pp. 61-66.
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Augmented Lagrangian Type Line Search Function - Parts I and II," Numer. Math, Vol. 38,
1981, pp. 83-127.
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Chem. Eng. Sci., Vol. 27, 1972, pp. 1197-1203.
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J., Vol. 7, No. 4, 1961.

Twu, C.H., "An Internally Consistent Correlation for Predicting the Critical Properties and
Molecular Weights of Petroleum and Coal-Tar Liquids," Fluid Phase Equil., Vol. 16, 1984,
pp. 137-150.
Turek, E.A., Metcalfe, R.S., Yarborough, L., and Robinson, R.L. Jr., "Phase Equilibria in
Carbon Dioxide - Multicomponent Hydrocarbon Systems: Experimental Data and an
Improved Prediction Technique," paper SPE 9231, presented at the 55th Annual Fall Meeting
of SPE-AIME, September 21-24, 1980, Dallas, Texas.
Watson, A.T., and Lee, W.J., "A New Algorithm for Automatic History Matching Production
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SPE paper 11200, presented at the 57th Annual Fall Technical Conference of SPE-AIME,
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1983, pp. 683-694.
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User's Guide

By Computer Modelling Group Ltd.

Copyright © 1987-2010 Computer Modelling Group Ltd.

The license management portion of this program is based on:

WinProp uses Intel(R) Compilers.

WinProp, CMG, and Computer Modelling Group are registered trademarks of

Computer Modelling Group Ltd.

Tel: (403) 531-1300 Fax: (403) 289-8502 E-mail: cmgl@cmgl.ca

Computer Modelling Group Ltd.

Confidentiality: All components of CMG technology including software and related

User's Guide WinProp Contents • i

Data Set Structure 31

ii • Contents User's Guide WinProp

Two-Phase Saturation and Phase Boundary Calculations 57

Three-Phase Boundary Calculation 73

User's Guide WinProp Contents • iii

Multiple Contact Miscibility Calculations 105

Compositional Grading 119

iv • Contents User's Guide WinProp

Process Flow 131

Black-Oil PVT Data Generation 135

User's Guide WinProp Contents • v

vi • Contents User's Guide WinProp

New Features in WinProp 2010.10

New Features in WinProp 2009.10

User's Guide WinProp New Features • 1

New Features in WinProp 2007.10

2 • New Features User's Guide WinProp

New Features in WinProp 2006.10

New Features in WinProp 2005.10

User's Guide WinProp New Features • 3

New Features in WinProp 2004.10

New Features in WinProp 2003.11

4 • New Features User's Guide WinProp

New Features in WinProp 2003.10

User's Guide WinProp New Features • 5

New Features in WinProp 2001.10

6 • New Features User's Guide WinProp

User's Guide WinProp New Features • 7

New Features in WinProp 2000.10

8 • New Features User's Guide WinProp

New Features in WinProp 1999.10

User's Guide WinProp New Features • 9

10 • New Features User's Guide WinProp

New Features in WinProp 98.00

12 • New Features User's Guide WinProp

User's Guide WinProp New Features • 13

New Features in WinProp 97.00

14 • New Features User's Guide WinProp

User's Guide WinProp New Features • 15

16 • New Features User's Guide WinProp

User's Guide WinProp Introduction • 17

18 • Introduction User's Guide WinProp

20 • Introduction User's Guide WinProp

Getting On-Line Help

Contents The table of contents for the help file is displayed

Creating, Opening and Saving Data Files

User's Guide WinProp Tutorial Section • 21

Running, Viewing Output and Creating Plots

22 • Tutorial Section User's Guide WinProp

Copying Between Different Data Files

Setting Up a Regression Run

Using the Update Component Properties Feature of WinProp